KR20200141420A - Polishing slurry composition - Google Patents

Abstract

The present invention relates to a polishing slurry composition which contains: abrasive particles; dispersants; stabilizers; and a polishing selectivity control agent, wherein the dispersant contains an aromatic organic acid containing at least one carboxyl group (-COOH). The present invention can provide the polishing slurry composition capable of providing an improved polishing rate for a film to be polished by maintaining dispersion stability.

Description

Polishing slurry composition {POLISHING SLURRY COMPOSITION}

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

In the chemical mechanical polishing (CMP) process, a slurry containing abrasive particles is put on a substrate, and a polishing pad mounted on a polishing device is used. At this time, the abrasive particles mechanically polish the surface under pressure from the polishing apparatus, and chemical components contained in the slurry composition chemically react the surface of the substrate to chemically remove the surface portion of the substrate. In general, there are various types of slurry compositions depending on the type and characteristics of the object to be removed.

The chemical mechanical polishing technique is an essential process for flattening an interlayer insulating film, separating and forming a shallow trench element, and forming a plug and buried metal wiring in a semiconductor device manufacturing process.

As semiconductor devices become denser, finer pattern formation techniques are used, and as the degree of integration and process standards become strict, the need for a highly planarization process of a semiconductor substrate containing various insulating films is increasing. 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 thereof is required.

The present invention is to provide a polishing slurry composition that is excellent in polishing selectivity and dispersion stability for a film to be polished and capable of stably maintaining dispersion stability.

However, the problem to be solved by the present invention is not limited to the problems mentioned above, and other problems that are not mentioned will be clearly understood by those skilled in the art from the following description.

According to an embodiment of the present invention, abrasive particles; Dispersant; Stabilizers; And a polishing selectivity modifier; Including, and the dispersing agent, it relates to a slurry composition for polishing containing an aromatic organic acid containing at least one carboxyl group (-COOH).

According to an embodiment of the present invention, the abrasive particles, metal oxide; Metal oxides coated with organic or inorganic substances; And a metal oxide in a colloidal state; and at least one selected from the group consisting of.

According to one embodiment of the present invention, the metal oxide, may be to include at least any one of silica, ceria, zirconia, alumina, titania, barium titania, germania, TKO selected from the group consisting of magnesia, and California.

According to an 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 an embodiment of the present invention, the dispersant is contained in an amount of 0.01% to 5% by weight of the slurry composition, and the dispersant is, benzoic acid, phenylacetic acid, naphthoic acid. ), Mandelic acid, Picolinic acid, Dipicolinic acid, Nicotinic acid, Dinicotinic acid, Isonicotinic acid, Quinolinic acid , Anthranilic acid, Fusaric acid, Phthalic acid, Isophthalic acid, Terephthalic acid, Toluic acid, Salicylic acid, Nitrobenzoic acid (nitrobenzoic acid) and pyridine carboxylic acid (Pyridinedicarboxylic acid) may be one containing at least any one selected from the group consisting of.

According to an embodiment of the present invention, the stabilizer is included in 0.001% to 1% by weight of the slurry composition, and the stabilizer is polyethyleneimine (PEI, Polyethyleneimine), polypropyleneimine, polypropyleneimine Polyvinylamine, polyallylamine, polyhexadimethrine, polydimethyl diallyl ammonium (salt)), poly(4-vinylpyridine) (poly(4-vinylpyridine) ), polyornithine, polylysine, polyarginine, poly-L-arginine (PARG), polyhistidine, polyvinyl imidazole ), polydiallylamine, polymethyl diallylamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine ), polyallyaminehydrochloride (PAH), poly(vinylpyridine), poly(vinylimidazole), poly-L-lysine (PLL), polyacrylamide, acrylamide ) Derived polymer, quaternary polyamine, polydimethylamine, polydiallyldimethyl ammonium chloride, poly(dimethylamine-co-epichlorohydrin), poly(methacryloyloxy Ethyltrimethylammonium chloride), poly(methacryloyloxyethyldimethylbenzylammonium chloride), polyamide- Amine (polyamide-amine), diphenylamine-epihydrin-based polymer (dimethylamine-epihydrin-based polymer), dicyandiamide, dicyandiamide, dicyandiamine, acrylamide, dimethylaminoethylacryl Rate (dimethylaminoethyl acrylate), D-glucosamine derivatives, imino-bis-propylamine, methylimino-bis-propylamine, Laurylimino bispropylamine -bis-propylamine), pentamethyldiethylenetriamine, pentamethyldipropylenediamine, aminopropyl-1,3-propylenediamine, and aminopropyl-1, It may include at least one selected from the group consisting of 4-butylenediamine (Aminopropyl-1,4-butylenediamine).

According to an embodiment of the present invention, the polishing selectivity adjusting agent may be included in an amount of 0.001 wt% to 0.5 wt% of the slurry composition, and the polishing selectivity adjusting agent may include an organic acid, an inorganic acid, or both. .

According to an 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, itaconic acid, tricarbalic acid tricarballylic acid), suberic acid, sebacic acid, stearic acid, pyruvic acid, acetoacetic acid, glyoxylic acid, azelaic acid ( azelaic acid), caprylic acid, lauric acid, myristic acid, valeric acid and at least any selected from the group consisting of palmitic acid It may contain one.

According to an embodiment of the present invention, the inorganic acid is hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, bromic acid, perchloric acid, hydrofluoric acid, iodic acid, nitrous acid, persulfuric acid, sulfurous acid, hyposulfite, boronic acid, iodic acid, phosphoric acid. , Phosphorous acid, hypophosphorous acid, superphosphoric acid, chlorous acid, hypochlorous acid, perchloric acid, bromic acid, hypobromic acid, perbromic acid, hypoiodic acid, periodic acid, hydrogen fluoride, boron trifluoride, tetrafluoroboric acid and phosphorus fluoride It may include at least any one selected from the group consisting of hydrogen acid.

According to an embodiment of the present invention, the polishing slurry composition may have a pH of 1 to 7, and the polishing slurry composition may have a zeta potential of +5mV to +70mV.

According to an embodiment of the present invention, when polishing a substrate including a nitride film or a poly film and a film to be polished using the polishing slurry composition, a selection ratio of the film to be polished to the nitride film or the poly film may be 10 or more.

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

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

According to an embodiment of the present invention, the inorganic oxide film is, fluorine doped tin oxide (FTO, SnO ₂ :F), indium tin oxide (ITO), indium zinc oxide (IZO), indium gallium zinc oxide (IGZO), and AZO. (Al-doped ZnO), AGZO(Aluminum Gallium Zinc Oxide), GZO(Ga-doped ZnO), IZTO(Indium Zinc Tin Oxide), IAZO(Indium Aluminum Zinc Oxide), IGZO(Indium Gallium Zinc Oxide), IGTO(Indium Gallium Tin Oxide), ATO (Antimony Tin Oxide), GZO (Gallium Zinc Oxide), IZON (IZO Nitride), SnO ₂ , ZnO, IrOx, and RuOx It may include at least one selected from the group consisting of.

According to an embodiment of the present invention, the polishing slurry composition may be applied to a polishing process of a semiconductor device, a display device, or both.

According to an embodiment of the present invention, colloidal ceria abrasive particles; A dispersant comprising an aromatic organic acid containing at least one carboxyl group (-COOH); Stabilizers; And a polishing selectivity modifier; It includes, and the polishing target film is ITO (indium tin oxide), relates to a polishing slurry composition.

According to an embodiment of the present invention, the polishing selectivity control agent may be included in an amount of 0.001 wt% to 0.5 wt% of the polishing slurry composition, and the polishing selectivity control agent may include a strong acidic organic acid of pKa 6 or less. have.

According to an embodiment of the present invention, the polishing slurry composition may have a pH of 2 to 5, and the polishing slurry composition may have a zeta potential of +5mV to +70mV.

According to an embodiment of the present invention, when polishing a substrate including a polishing target film and a nitride film using the polishing slurry composition, a selectivity ratio of the polishing target film to the nitride film may be 10 or more.

In the present invention, when polishing a substrate including a film to be polished (for example, an inorganic oxide film) and a film to be polished (for example, a silicon nitride film), the film to be polished is removed at a high polishing rate, and after the step is removed Due to the high polishing selectivity, the polishing rate in the polishing stop film is very slow, and thus a polishing slurry composition capable of implementing a polishing automatic stop function can be provided.

The present invention can provide a polishing slurry composition capable of maintaining dispersion stability and providing an improved polishing rate for a film to be polished.

The present invention can provide a polishing slurry composition that can be applied to a polishing process (eg, CMP) of semiconductor wiring devices, display substrates, panels, etc., which require a planarization process of an inorganic oxide film (eg, ITO). .

Hereinafter, embodiments will be described in detail with reference to the detailed description.

Various changes may be made to the embodiments described below. The embodiments described below are not intended to limit the scope of the invention to the described embodiments, and the scope to be claimed as a right through the present application should be understood to include all changes, equivalents, and substitutes thereto.

The terms used in the examples are used only to describe specific embodiments, and are not intended to limit the embodiments. Singular expressions include plural expressions unless the context clearly indicates otherwise. In the present specification, terms such as "comprise" or "have" are intended to designate the presence of features, numbers, steps, actions, components, parts, or combinations thereof described in the specification, but one or more other features. It is to be understood that it does not exclude the possibility of the presence or addition of elements or numbers, steps, actions, components, parts, or combinations thereof.

Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which the embodiment belongs. Terms as defined in a commonly used dictionary should be interpreted as having a meaning consistent with the meaning in the context of the related technology, and should not be interpreted as an ideal or excessively formal meaning unless explicitly defined in this application. Does not.

When an element or layer is referred to as being “on”, “connected to”, or “coupled to” another element or layer, it is directly the other component or It may be understood that it may be in a layer, may be connected, may be combined, or intervening elements and layers may be present.

The present invention relates to a slurry composition for polishing, and according to an embodiment of the present invention, the slurry composition for polishing comprises: abrasive particles; Dispersant; Stabilizers; And a polishing selectivity modifier; Including, and may further include a residual amount of the solvent.

According to an embodiment of the present invention, the abrasive particles may contain 0.5% to 10% by weight of the slurry composition. When the amount of the abrasive particles is less than 0.5% by weight of the slurry composition, there is a problem that the polishing rate is reduced, and when the amount is more than 10% by weight, defects such as defects and scratches due to excessive polishing may occur.

The abrasive particles provide high dispersion stability and promote oxidation of an inorganic oxide film such as a polishing target film, for example, ITO, to easily polish the inorganic oxide film to achieve high polishing characteristics while minimizing defects such as scratches. have.

The abrasive particles, metal oxide; Metal oxides coated with organic or inorganic substances; And the metal oxide in a colloidal state; and the metal oxide includes at least one selected from the group consisting of silica, ceria, zirconia, alumina, titania, barium titania, germania, mangania, and magnesia. It may include at least one selected. For example, the abrasive particles may be colloidal ceria dispersed with a positive charge.

The abrasive particles may include those manufactured by a liquid phase method. In the liquid phase method, a chemical reaction occurs in an aqueous solution of an abrasive particle precursor, a sol-gel method in which crystals are grown to obtain fine particles, a coprecipitation method in which abrasive particle ions are precipitated in an aqueous solution, and abrasive particles are formed under high temperature and high pressure. It can be manufactured by applying a hydrothermal synthesis method. The abrasive particles produced by the liquid phase method are dispersed so that the surface of the abrasive particles has a positive charge.

The abrasive particles may be monocrystalline. When single crystal abrasive particles are used, scratch reduction effects can be achieved compared to polycrystalline abrasive particles, dishing can be improved, and cleaning properties after polishing can be improved.

The shape of the abrasive particles may include at least one selected from the group consisting of a spherical shape, a square shape, a needle shape, and a plate shape, and preferably a spherical shape.

The primary particle size of the abrasive particles may be 5 nm to 150 nm, and the secondary particle size may be 30 nm to 300 nm. The measurement of the average particle diameter of the abrasive particles is an average value of the particle diameters of a plurality of particles within a field of view that can be measured by scanning electron microscope analysis, BET analysis, or dynamic light scattering. The size of the primary particles should be 150 nm or less in order to ensure particle uniformity, and when the size is less than 5 nm, the polishing rate may decrease. If the size of the secondary particles is less than 30 nm, excessive generation of small particles due to milling results in deterioration of cleanability, excessive defects occur on the surfaces of substrates and wafers used in the polishing process, and exceeds 300 nm. In this case, excessive polishing is performed, making it difficult to control the selectivity, and dishing, erosion and surface defects may occur.

In addition to single-sized particles, the abrasive particles may be mixed particles including a multi-dispersion type particle distribution. For example, two types of abrasive particles having different average particle sizes are mixed to form a bimodal particle. ) May have a particle size distribution or a particle size distribution showing three peaks by mixing three types of abrasive particles having different average particle sizes. Alternatively, four or more types of abrasive particles having different average particle sizes may be mixed to have a polydispersed particle distribution. Since the relatively large abrasive particles and the relatively small abrasive particles are mixed, it has better dispersibility and an effect of reducing scratches on the wafer surface can be expected.

The dispersant may include 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 phase stability, and when it exceeds 5% by weight, dispersion stability may be deteriorated, making it difficult to implement polishing performance .

The dispersant may be applied to induce a uniform and stable dispersion of the abrasive particles, and to control polishing performance and polishing selectivity.

The dispersant may include an organic acid containing an aromatic ring having 6 to 20 carbon atoms and at least one carboxyl group (-COOH). For example, the organic acid may be one in which a carbon atom in the aromatic ring is substituted with a nitrogen atom, and may further include 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, Phenylacetic acid, Naphthoic acid, Mandelic acid, Picolinic acid, Dipicolinic acid, Nicotinic acid acid), Dinicotinic acid, Isonicotinic acid, Quinolinic acid, anthranilic acid, Fusaric acid, Phthalic acid, Isophthalic acid , Terephthalic acid, toluic acid, salicylic acid, nitrobenzoic acid, and pyridine carboxylic acid (Pyridinedicarboxylic Acid) may include at least one selected from the group consisting of.

The stabilizer may be included in an amount of 0.001% to 1% by weight of the slurry composition, and when the content of the stabilizer is less than 0.001% by weight, dispersion stability is lowered, making it difficult to implement desired polishing performance, and 1% by weight If it is exceeded, the dispersion stability decreases due to the addition of an excessive amount of stabilizer, resulting in agglomeration, which may lead to micro-defects and scratches.

The stabilizer may serve as a pH buffer to ensure particle dispersibility and dispersion stability, and for example, various additives, for example, a polishing selectivity control agent, to control the polishing performance of the polishing slurry composition. It is possible to provide a polishing slurry composition capable of preventing a decrease in dispersion stability due to application and improving a polishing rate of a film to be polished and a stopping performance of a polishing stop film.

The stabilizer may be an amine-based compound having a repeating unit including at least one amine group and an aliphatic hydrocarbon. The amine compound may be an ionic compound, a salt, a monomer, a polymer and a copolymer including the monomer. For example, the amine-based compound is polyethyleneimine (PEI), polypropyleneimine, polyvinylamine, polyallylamine, polyhexadimethrine, polydimethyl Diaryl ammonium (polydimethyl diallyl ammonium (salt)), poly(4-vinylpyridine) (poly(4-vinylpyridine)), polyornithine, polylysine, polyarginine, poly-L -Arginine (poly-L-arginine; PARG), polyhistidine, polyvinyl imidazole, polydiallylamine, polymethyl diallylamine, diethylenetriamine (diethylenetriamine), triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyallyaminehydrochloride (PAH), poly(vinylpyridine), poly(vinylimida) Sol), poly-L-lysine (PLL), polyacrylamide, acrylamide derived polymer, quaternary polyamine, polydimethylamine, polyallyldimethyl ammonium chloride (polydiallyldimethyl ammonium chloride), poly(dimethylamine-co-epichlorohydrin), poly(methacryloyloxyethyltrimethylammonium chloride), poly(methacryloyloxyethyldimethylbenzyl ammonium chloride), polyamide-amine (polyamide-amine), diphenylamine-epihydrin-based polymer (dimethylamine- epihydrin-based polymer), dicyandiamide, dicyandiamide, acrylamide, dimethylaminoethyl acrylate, D-glucosamine derivative, iminobis Imino-bis-propylamine, methylimino-bis-propylamine, Laurylimino-bis-propylamine, pentamethyldiethylenetriamine, pentamethyldi Selected from the group consisting of propylenediamine (Pentamethyldipropylenediamine), aminopropyl-1,3-propylenediamine, and aminopropyl-1,4-butylenediamine It may include at least any one of.

The polishing selectivity adjusting agent is for adjusting the polishing selectivity by increasing the polishing rate of the polishing target film, and may be applied as an etchant for promoting polishing of the polishing target film. For example, the polishing selectivity adjusting agent may implement 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 control agent is included in 0.001% by weight to 0.5% by weight of the slurry composition, and when it is less than 0.001% by weight, it is difficult to improve the polishing performance and control the selectivity for the film to be polished, and when it exceeds 0.5% by weight It is possible to increase defects due to scratches, micro defects, corrosion of the polishing target film, etc. due to excessive polishing of the polishing target film.

The polishing selectivity adjusting agent may include an organic acid, an inorganic acid, or both. For example, the organic acid may be a strongly acidic organic acid having a pKa 6 or less. More specifically, the organic acid 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, itaconic acid, tricarballylic acid, water Suberic acid, sebacic acid, stearic acid, pyruvic acid, acetoacetic acid, glyoxylic acid, azelaic acid, carbohydrate It may include at least one selected from the group consisting of caprylic acid, lauric acid, myristic acid, valeric acid, and palmitic acid. have.

The inorganic acids are hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, bromic acid, perchloric acid, hydrofluoric acid, iodic acid, nitrous acid, persulfuric acid, sulfurous acid, hyposulfite, boronic acid, iodic acid, phosphoric acid, phosphorous acid, hypophosphorous acid, superphosphoric acid, and At least any one selected from the group consisting of chloric acid, hypochlorous acid, perchloric acid, bromic acid, hypobromic acid, perbromic acid, hypoiodic acid, periodic acid, hydrogen fluoride, boron trifluoride, tetrafluoroboric acid, and hydrophosphoric acid It can contain one.

According to an embodiment of the present invention, the polishing slurry composition may further include a pH adjusting agent. For example, nitric acid, 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, adipic acid, acetic 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, lactic acid, aspartic acid, tartaric acid, polyacrylic acid, polypropionic acid, polysalicylic acid, polybenzoic acid, polybutyric acid, and salts thereof. Acidic substances and ammonia, AMP (ammonium methyl propanol), TMAH (tetra methyl ammonium hydroxide), potassium hydroxide, sodium hydroxide, magnesium hydroxide, rubidium hydroxide, ammonium hydroxide, cesium hydroxide, sodium hydrogen carbonate, sodium carbonate , It may contain at least one selected from the group consisting of imidazole. The pH adjusting agent may be added in an amount to adjust the pH of the polishing slurry composition.

The pH of the polishing slurry composition according to the present invention is preferably adjusted to produce dispersion stability and an appropriate polishing rate according to the abrasive particles, and the pH of the polishing slurry composition is 1 to 7; Preferably, it may have an acidic pH range of 1 to 5.

The polishing slurry composition according to the present invention may be a slurry composition exhibiting a positive charge, and the zeta potential of the slurry composition may be in the range of +5mV to +70mV. Due to the positively charged abrasive particles, a high dispersion stability is maintained so that agglomeration of the abrasive particles does not occur, thereby reducing the occurrence of micro-scratches.

According to an embodiment of the present invention, the polishing slurry composition may be concentrated or diluted.

According to an embodiment of the present invention, the polishing slurry composition may be applied to a semiconductor device, a display device, or a polishing process of both, for example, a chemical mechanical polishing (CMP) process.

The polishing slurry composition may be applied to a planarization process of a semiconductor device and a display device in which a thin film including at least one selected from the group consisting of an insulating film and an inorganic oxide film is used as a polishing target film. For example, it may be applied to a planarization process of a semiconductor device to which an insulating film and an inorganic oxide film are applied, and a display device to which an inorganic oxide film is applied.

The insulating layer may include at least one selected from the group consisting of a silicon oxide layer, a silicon nitride layer, and a polysilicon layer.

The inorganic oxide layer is indium (In), tin (Sn), silicon (Si), titanium (Ti), vanadium (V), gadolium (Ga), manganese (Mn), iron (Fe), cobalt (Co) , Copper (Cu), zinc (Zn), zirconium (Zr), hafnium (Hf), aluminum (Al), niobium (Nb), nickel (Ni), chromium (Cr), molybdenum (Mo), tantalum ( Oxide containing at least one selected from the group consisting of Ta), ruthenium (Ru), tungsten (W), tin (Sn), aluminum (Al), antimony (Sb), Ir (iridium) and Ni (nickel) , Nitride or both, and may be doped with halogen or the like. For example, FTO (fluorine doped tin oxide, SnO ₂ : F), ITO (indium tin oxide), IZO (indium zinc oxide), IGZO (indium gallium zinc oxide), AZO (Al-doped ZnO), AGZO (Aluminum Gallium Zinc Oxide), GZO(Ga-doped ZnO), IZTO(Indium Zinc Tin Oxide), IAZO(Indium Aluminum Zinc Oxide), IGZO(Indium Gallium Zinc Oxide), IGTO(Indium Gallium Tin Oxide), ATO(Antimony Tin Oxide) ), GZO (Gallium Zinc Oxide), IZON (IZO Nitride), SnO ₂ , ZnO, IrOx, RuOx, and at least one selected from the group consisting of NiO.

The planarization step of the semiconductor device and the display device may include a nitride film of the above-mentioned element, for example, a nitride film such as SiN, a high-k film such as Hf-based, Ti-based, or Ta-based oxide; Semiconductor films such as silicon, amorphous silicon, SiC, SiGe, Ge, GaN, GaP, GaAs, and organic semiconductors; A phase change film such as GeSbTe; It can be further applied to polymer resin films such as polyimide-based, polybenzoxazole-based, acrylic-based, epoxy-based, and phenol-based.

The display device may be a substrate or a panel, and may be a TFT or an organic light emitting display device.

According to an embodiment of the present invention, the polishing rate of the polishing slurry composition for 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 has a lower speed than that of the film to be polished, and may be polished to 100 Å/min or less, preferably 50 Å/min or less. For example, when polishing a substrate including an inorganic oxide film such as ITO and a silicon nitride film, the ITO film may be polished at a high speed, and the silicon nitride film may be polished at a low speed to provide the function of a polishing stop film.

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

According to an embodiment of the present invention, when a pattern wafer is polished using the polishing slurry composition, a high polishing rate can be secured not only on a wafer having a small pattern density but also a wafer having a high pattern density.

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

Examples 1 to 15

According to Table 1, colloidal ceria (HC-60, Solvay) 4% by weight with an average particle size of 60 nm (BET measurement), picolinic acid as a dispersant, polyethyleneimine (PEI, as a stabilizer) according to Table 1 Polyethyleneimine) and oxalic acid as a polishing selectivity control agent and ultrapure water were mixed to prepare a polishing slurry composition according to Table 1.

Example 16 and Example 17

In the same manner as in Example 1, except for using colloidal ceria particles (HC-90, Solvay) having an average particle size of 90 nm (BET measurement) of the primary particles, polishing slurry according to Table 1 The composition was prepared.

particle Dispersant Stabilizer Polishing Selectivity Adjuster Example 1 HC60
(4wt%) 0.2 0.04 0.04 Example 2 0.2 0.02 0.04 Example 3 0.2 0.01 0.04 Example 4 0.2 0.02 0.08 Example 5 0.2 0.02 0.1 Example 6 0.2 0.02 0.12 Example 7 0.2 0.04 0.12 Example 8 0.2 0.04 0.14 Example 9 0.28 0.02 0.04 Example 10 0.36 0.02 0.04 Example 11 0.4 0.02 0.084 Example 12 0.6 0.02 0.084 Example 13 0.6 0.04 0.084 Example 14 0.8 0.04 0.084 Example 15 1.2 0.04 0.092 Example 16 HC90
(4wt%) 0.6 0.02 0.084 Example 17 1.2 0.04 0.092

(1) Evaluation of dispersion stability In order to evaluate the dispersion stability of the slurry composition of the examples, the particle size was measured on day 0 and day 1, respectively, to measure the stability over time.

Dispersion stability Initial 1day Dispersion stability Example 1 142.2 142.6 Good Example 2 145.9 143.4 Good Example 3 144.6 145.5 Good Example 4 142.9 143 Good Example 5 141.7 141.6 Good Example 6 175.4 230.7 Bad Example 7 146.3 167.4 Bad Example 8 Sedimentation Sedimentation Bad Example 9 144.3 146.5 Good Example 10 144.9 146 Good Example 11 142.5 141.7 Good Example 12 143.1 142 Good Example 13 141.0 141 Good Example 14 142.4 143.6 Good Example 15 144.3 143.8 Good Example 16 228 228.4 Good Example 17 226.8 227.4 Good

Looking at Table 2, Examples 1 to 5 and Examples 9 to 17 show good dispersion stability even when oxalic acid serving as an ITO etchant is added, and Examples 6 to 8 are due to an increase in the content of oxalic acid. It can be seen that the dispersion stability is low. (2) Evaluation of polishing properties

The substrate containing the ITO film and the SiN film was polished under the following polishing conditions using the polishing slurry composition of the example.

[Polishing conditions]

1. Polishing equipment: AP-300 from CTS

2. Wafer: 300mm ITO Membrane Wafer

3. Platen pressure: 4psi

4. Spindle speed: 100rpm

5. Platen speed: 105rpm

6. Flow rate: 300ml/min

CMP results pH ITO R.R SiN R.R ITO/SiN selection ratio Example 1 4.6 1448 50 29 Example 2 4.0 1778 61 29 Example 3 3.1 2417 186 13 Example 4 2.6 2526 115 22 Example 5 2.4 2260 127 18 Example 6 Impossible to measure due to poor dispersion Example 7 Example 8 Example 9 3.8 1969 59 33 Example 10 3.7 1703 52 33 Example 11 2.5 3922 62 63 Example 12 2.7 3734 89 42 Example 13 2.9 3520 78 45 Example 14 2.9 3508 59 59 Example 15 3.0 3110 42 74 Example 16 2.62 3882 71 55 Example 17 2.97 4672 71 66

Looking at Table 3, in the slurry compositions of Examples 1 to 5 and Examples 9 to 17, the polishing rate for the ITO film was improved, the polishing rate for the polishing stop film SiN was reduced, and thus ITO/SiN polishing It can be seen that the selection ratio is increased. The application of oxalic acid, which acts as an etchant of the ITO film, improves the polishing rate of the ITO film, and the dispersion stability of the polishing slurry by the aromatic organic acid and PEI is improved, thereby increasing the selectivity of the ITO film, thereby improving the auto-stop performance for the SiN stop film. I can. In addition, in Examples 6 to 8, it can be seen that the dispersion stability of the slurry is poor, and thus the polishing performance is difficult to be expressed. Accordingly, the polishing slurry composition of the present invention includes the polishing rate of the ITO film and the selection of ITO/SiN polishing. The excellent ratio can improve the automatic polishing stop performance for the SiN stop film.

As described above, although the embodiments have been described by the limited drawings, a person of ordinary skill in the art can apply various technical modifications and variations based on the above. For example, even if the described techniques are performed in a different order from the described method, and/or the described components are combined or combined in a form different from the described method, or are replaced or substituted by other components or equivalents. Appropriate results can be achieved.

Therefore, other implementations, other embodiments and claims and equivalents fall within the scope of the following claims.

Claims (8)

Colloidal ceria abrasive particles;
A dispersant comprising an aromatic organic acid containing at least one carboxyl group (-COOH);
Stabilizers; And
Abrasive selectivity modifiers;
Including,
The film to be polished is ITO (indium tin oxide),
Polishing slurry composition.
The method of claim 1,
The dispersant is included in 0.01% to 5% by weight of the polishing slurry composition,
The dispersant is benzoic acid, phenylacetic acid, naphthoic acid, mandelic acid, picolinic acid, dipicolinic acid, nicotinic acid acid), Dinicotinic acid, Isonicotinic acid, Quinolinic acid, anthranilic acid, Fusaric acid, Phthalic acid, Isophthalic acid , Terephthalic acid, toluic acid, salicylic acid, nitrobenzoic acid and pyridine carboxylic acid (Pyridinedicarboxylic Acid) that contains at least one selected from the group consisting of,
Polishing slurry composition.
The method of claim 1,
The stabilizer is included in 0.001% to 1% by weight of the polishing slurry composition,
The stabilizer is polyethyleneimine (PEI), polypropyleneimine, polyvinylamine, polyallylamine, polyhexadimethrine, polydimethyldiarylammonium (polydimethyl diallyl ammonium (salt)), poly(4-vinylpyridine)), polyornithine, polylysine, polyarginine, poly-L-arginine L-arginine; PARG), polyhistidine, polyvinyl imidazole, polydiallylamine, polymethyl diallylamine, diethylenetriamine, tri Ethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyallyaminehydrochloride (PAH), poly(vinylpyridine), poly(vinylimidazole), poly- L-lysine (poly-L-lysine; PLL), polyacrylamide, acrylamide derived polymer, quaternary polyamine, polydimethylamine, polydiallyldimethyl ammonium chloride , Poly(dimethylamine-co-epichlorohydrin), poly(methacryloyloxyethyltrimethylammonium chloride), poly(methacryloyloxyethyldimethylbenzylammonium chloride), polyamide-amine , Diphenylamine-epihydrin-based polymer (dimethylamine-epihydrin-b ased polymer), dicyandiamide, dicyandiamide, acrylamide, dimethylaminoethyl acrylate, D-glycosamine derivative, iminobispropylamine (Imino-bis-propylamine), methylimino-bis-propylamine, Lauryimino-bis-propylamine, pentamethyldiethylenetriamine, pentamethyldipropylenediamine (Pentamethyldipropylenediamine), aminopropyl-1,3-propylenediamine, and aminopropyl-1,4-butylenediamine (Aminopropyl-1,4-butylenediamine) at least selected from the group consisting of Which includes any one,
Polishing slurry composition.
The method of claim 1,
The polishing selectivity control agent is included in 0.001% to 0.5% by weight of the polishing slurry composition,
The polishing selectivity modifier comprises a strong acidic organic acid of pKa 6 or less,
Polishing slurry composition.
The method of claim 4,
The organic acid 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 acid), propionic acid, butyric acid, hydroxybutyric acid, aspartic acid, itaconic acid, tricarballylic acid, suberic acid acid), sebacic acid, stearic acid, pyruvic acid, acetoacetic acid, glyoxylic acid, azelaic acid, caprylic acid acid), lauric acid, myristic acid, valeric acid, and palmitic acid, which comprises at least one selected from the group consisting of,
Polishing slurry composition.
The method of claim 1,
The pH of the polishing slurry composition is 2 to 5,
The polishing slurry composition has a zeta potential of +5mV to +70mV.
Polishing slurry composition.
The method of claim 1,
When polishing a substrate including a polishing target film and a nitride film using the polishing slurry composition, the selectivity of the polishing target film to the nitride film is 10 or more
Polishing slurry composition.
The method of claim 1,
After polishing the substrate using the polishing slurry composition, the polishing rate for the polishing target film is 1000 Å/min or more,
Polishing slurry composition.