KR102268208B1 - Polishing slurry composition - Google Patents

Abstract

The present invention, abrasive particles; dispersant; stabilizers; and a polishing selectivity control agent; wherein the dispersing agent includes an aromatic organic acid containing at least one carboxyl group (-COOH).

Description

Slurry composition for polishing {POLISHING SLURRY COMPOSITION}

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

A chemical mechanical polishing (CMP) process is performed by injecting a slurry containing abrasive particles onto a substrate and using a polishing pad mounted on a polishing apparatus. At this time, the abrasive particles are subjected to pressure from the polishing apparatus to mechanically polish the surface, and the chemical component contained in the slurry composition chemically reacts 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.

Chemical mechanical polishing technology is an essential process in the manufacturing process of a semiconductor device, such as planarization of an interlayer insulating film, formation of shallow trench device isolation, and formation of plugs and buried metal wiring.

As semiconductor devices become high-density, finer pattern forming techniques are used, and as the degree of integration increases and the standards of the process become stricter, the need for a high-level planarization process for semiconductor substrates 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.

An object of the present invention is to provide a polishing slurry composition having excellent polishing selectivity and dispersion stability for a film to be polished, and capable of stably maintaining dispersion stability.

However, the problems to be solved by the present invention are not limited to the problems mentioned above, and other problems 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 an abrasive selectivity control agent; Including, the dispersing agent relates to a slurry composition for polishing, which comprises an aromatic organic acid containing at least one carboxyl group (-COOH).

According to an embodiment of the present invention, the abrasive particles, a metal oxide; metal oxides coated with organic or inorganic materials; and metal oxides in a colloidal state; may include 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 dispersing agent is included in 0.01 wt% to 5 wt% of the slurry composition, and the dispersing agent 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 comprising at least 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, poly Vinylamine, 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 ), polyallyamine hydrochloride (PAH), poly(vinylpyridine), poly(vinylimidazole), poly-L-lysine (PLL), polyacrylamide, acrylamide ) Derived polymers, quaternary polyamines, 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, dicyandiaminede, acrylamide (acrylamide), dimethylaminoethylacryl Rate (dimethylaminoethyl acrylate), D-glycosamine (D-glucosamine) derivative, imino-bis-propylamine, methylimino-bis-propylamine, laurylimino -bis-propylamine), pentamethyldiethylenetriamine (Pentamethyldiethylenetriamine), pentamethyldipropylenediamine (Pentamethyldipropylenediamine), aminopropyl-1,3-propylenediamine (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 (oxalic acid), succinic acid (succinic acid), tartaric acid (tartaric acid), citric acid (citric acid), lactic acid (lactic acid), glutaric acid (glutaric acid), glycolic acid (glycollic acid), Formic acid, fumaric acid, propionic acid, butyric acid, hydroxybutyric acid, aspartic acid, itaconic acid, tricabalic acid ( tricarballylic acid, suberic acid, sebacic acid, stearic acid, pyruvic acid, acetoacetic acid, glyoxylic acid, azelaic acid ( azelaic acid), caprylic acid (caprylic acid), lauric acid (lauric acid), myristic acid (myristic acid), valeric acid (valeric acid) and at least one selected from the group consisting of palmitic acid (palmitic acid) It may include one.

According to an embodiment of the present invention, the inorganic acids are hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, hydrobromic 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, hydrobromic acid, hypobromic acid, perbromic acid, hypoiodic acid, periodic acid, hydrogen fluoride, boron trifluoride, tetrafluoroboric acid and phosphorus fluoride It may include at least 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 +5 mV to +70 mV.

According to an embodiment of the present invention, when polishing the polishing target film and the substrate including the nitride or poly film using the polishing slurry composition, the selection ratio of the polishing target film to the nitride or 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 layer may include fluorine doped tin oxide (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), Antimony Tin Oxide (ATO), Gallium Zinc Oxide (GZO), IZO Nitride (IZON), SnO ₂ , ZnO, IrOx, and RuOx 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 for 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 an abrasive selectivity adjuster; It relates to a polishing slurry composition, including, the polishing target film is ITO (indium tin oxide).

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 polishing slurry composition, and the polishing selectivity adjusting agent may include a strongly acidic organic acid having a pKa of 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 +5 mV to +70 mV.

According to an embodiment of the present invention, when the polishing slurry composition is used to polish the polishing target layer and the substrate including the nitride layer, the selection ratio of the polishing target layer to the nitride layer may be 10 or more.

In the present invention, when polishing a substrate including a polishing target film (eg, an inorganic oxide film) and a polishing stop film (eg, a silicon nitride film), the polishing object film is removed at a high polishing rate, and after the step is removed, It is possible to provide a polishing slurry composition capable of realizing an automatic polishing stop function because the polishing rate is very slow in the polishing stop film due to the high polishing selectivity.

The present invention can provide a polishing slurry composition capable of providing an improved polishing rate for a polishing target film by maintaining dispersion stability.

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. requiring 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 it should be understood that the scope to be claimed as a right through the present application includes all modifications, equivalents or substitutes thereto.

Terms used in the examples are only used to describe specific examples, and are not intended to limit the examples. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present specification, terms such as “comprise” or “have” are intended to designate that a feature, number, step, operation, component, part, or combination thereof described in the specification exists, but one or more other features It is to be understood that this does not exclude the possibility of the presence or addition of numbers, steps, operations, 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 such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related art, and should not be interpreted in an ideal or excessively formal meaning unless explicitly defined in the present 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 related to the other element or layer. It may be understood that there may be layers, connected or coupled or intervening elements and layers may be present.

The present invention relates to a polishing slurry composition. According to an embodiment of the present invention, the polishing slurry composition comprises: abrasive particles; dispersant; stabilizers; and an abrasive selectivity control agent; and may further include a residual amount of solvent.

According to an embodiment of the present invention, the abrasive particles may include 0.5 wt% to 10 wt% of the slurry composition. If the abrasive particles are less than 0.5% by weight of the slurry composition, there is a problem in that the polishing rate is reduced, and if it is more than 10% by weight, defects such as defects and scratches may occur due to excessive polishing.

The abrasive particles provide high dispersion stability and facilitate the polishing of the inorganic oxide film by accelerating the oxidation of the polishing target film, for example, ITO, etc. to minimize defects such as scratches and achieve high polishing properties. have.

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

The abrasive particles may include those prepared by a liquid phase method. The liquid phase method is a sol-gel method in which abrasive particle precursors are chemically reacted in an aqueous solution and crystals are grown to obtain fine particles, a co-precipitation method in which abrasive particle ions are precipitated in an aqueous solution, and abrasive particles are formed under high temperature and pressure. It can be prepared by applying a hydrothermal synthesis method, etc. The abrasive particles prepared 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 monocrystalline abrasive particles are used, a scratch reduction effect can be achieved compared to polycrystalline abrasive particles, dishing can be improved, and cleanability 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 abrasive particles may have a primary particle size of 5 nm to 150 nm, and a secondary particle size of 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 to ensure particle uniformity, and if it is less than 5 nm, the polishing rate may be reduced. When the size of the secondary particles is less than 30 nm, if excessively small particles are generated due to milling, the cleaning property is deteriorated, and excessive defects occur on the surface of the substrate, wafer, etc. used in the polishing process, exceeding 300 nm In this case, excessive polishing is made, making it difficult to control the selectivity, and dishing, erosion, and surface defects are likely to occur.

As the abrasive particles, in addition to single-size particles, mixed particles including a multi-dispersion type particle distribution may be used. For example, abrasive particles having two different average particle sizes are mixed to form a bimodal (bimodal) particle. ) shape, or may have a particle size distribution showing three peaks by mixing abrasive particles having three different average particle sizes. Alternatively, four or more kinds of abrasive particles having different average particle sizes may be mixed to have a polydisperse particle distribution. By mixing relatively large abrasive particles and relatively small abrasive particles, it has better dispersibility, and the effect of reducing scratches on the wafer surface can be expected.

The dispersant may include 0.01 wt% to 5 wt% 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 is lowered and it may be difficult to implement polishing performance.

The dispersing agent may be applied to induce uniform and stable dispersion of the abrasive particles, thereby controlling polishing performance, polishing selectivity, and the like.

The dispersant may include an organic acid including 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 (Terephthalic acid), toluic acid (Toluic acid), salicylic acid (Salicylic acid), nitrobenzoic acid (nitrobenzoic acid) and pyridinecarboxylic acid (Pyridinedicarboxylic acid) It may include at least one selected from the group consisting of.

The stabilizer may be included in an amount of 0.001 wt% to 1 wt% of the slurry composition, and when the content of the stabilizer is less than 0.001 wt%, dispersion stability is lowered, making it difficult to implement a desired polishing performance, and 1 wt% When it exceeds, dispersion stability is reduced due to the input of an excessive amount of stabilizer, and aggregation occurs, which may cause micro defects and scratches.

The stabilizer may act as a pH buffer to secure particle dispersibility and dispersion stability, and for example, various additives, for example, a polishing selectivity control agent for controlling 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 the polishing rate of the polishing target film and the stopping performance of the 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-based compound may be an ionic compound, a salt, a monomer, or a polymer or copolymer including the monomer. For example, the amine-based compound is polyethyleneimine (PEI, Polyethyleneimine), polypropyleneimine (polypropyleneimine), polyvinylamine (polyvinylamine), polyallylamine (polyallylamine), polyhexadimethrine (polyhexadimethrine), polydimethyl Diarylammonium (polydimethyl diallyl ammonium (salt)), poly (4-vinylpyridine) (poly (4-vinylpyridine)), polyornithine (polyornithine), polylysine (polylysine), polyarginine (polyarginine), poly-L -Arginine (poly-L-arginine; PARG), polyhistidine, polyvinyl imidazole, polydiallylamine, polymethyldiallylamine, diethylenetriamine (diethylenetriamine), triethylenetetramine (triethylenetetramine), tetraethylenepentamine (tetraethylenepentamine), pentaethylenehexamine (pentaethylenehexamine), polyallyamine hydrochloride (PAH), poly (vinylpyridine), poly (vinylimida) sol), poly-L-lysine (PLL), polyacrylamide, acrylamide derived polymer, quaternary polyamine, polydimethylamine, polyallyldimethyl ammonium chloride (polydialyldimethyl ammonium chloride), poly(dimethylamine-co-epichlorohydrin), poly(methacryloyloxyethyltrimethylammonium chloride), poly(methacryloyloxyethyldimethylbenzylammonium chloride), polyamide-amine (polyamide-amine), diphenylamine-epihydrin-based polymer (dimethylamine- epihydrin-based polymer), dicyandiamide, dicyandiamine, acrylamide, dimethylaminoethyl acrylate, D-glycosamine derivative, iminobis Propylamine (Imino-bis-propylamine), Methylimino-bis-propylamine (Methylimino-bis-propylamine), Laurylimino-bis-propylamine (Laurylimino-bis-propylamine), Pentamethyldiethylenetriamine (Pentamethyldiethylenetriamine), Pentamethyldi Propylenediamine (Pentamethyldipropylenediamine), aminopropyl-1,3-propylenediamine (Aminopropyl-1,3-propylenediamine), and aminopropyl-1,4-butylenediamine (Aminopropyl-1,4-butylenediamine) selected from the group consisting of It may include at least any one of

The polishing selectivity control 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 accelerating polishing of the polishing target film. For example, the polishing selectivity control 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% 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 of the polishing target film, 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, and the like due to excessive polishing of the polishing target film.

The polishing selectivity control 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 of 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, ca It may include at least one selected from the group consisting of prilic acid (caprylic acid), lauric acid (lauric acid), myristic acid (myristic acid), valeric acid (valeric acid) and palmitic acid (palmitic acid) have.

The inorganic acids are hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, hydrobromic 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, At least any one selected from the group consisting of chloric acid, hypochlorous acid, perchloric acid, hydrobromic acid, hypobromic acid, perbromic acid, hypoiodic acid, periodic acid, hydrogen fluoride, boron trifluoride, tetrafluoroboric acid and hydrofluoric acid may 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, hydrobromic 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 , selected from the group consisting of pimelinic 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 At least one acidic substance 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 , may include 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 obtain dispersion stability and an appropriate polishing rate depending on 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 +5 mV to +70 mV. Due to the positively charged abrasive particles, it is possible to maintain high dispersion stability, 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 used after concentration or dilution.

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 the two, 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 using a thin film including at least one selected from the group consisting of an insulating layer and an inorganic oxide layer as a polishing target layer. For example, it may be applied to a planarization process of a semiconductor device to which an insulating layer and an inorganic oxide layer are applied, and a display device to which an inorganic oxide layer 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), gadorium (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), Ga-doped ZnO (GZO), Indium Zinc Tin Oxide (IZTO), Indium Aluminum Zinc Oxide (IAZO), Indium Gallium Zinc Oxide (IGZO), Indium Gallium Tin Oxide (IGTO), Antimony Tin Oxide (ATO) ), Gallium Zinc Oxide (GZO), IZO Nitride (IZON), SnO ₂ , ZnO, IrOx, RuOx, and NiO may include at least one selected from the group consisting of.

The planarization process 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 dielectric constant film such as an 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; Polyimide-based, polybenzoxazole-based, acryl-based, epoxy-based, phenol-based polymer resin films, etc. can be further applied.

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 polishing target film may be 1000 Å/min or more, preferably 2000 Å/min or more. The polishing rate of the polishing stop film may be lower than that of the polishing target film, and may be polished at 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 a function of a polishing stop film.

According to an embodiment of the present invention, when polishing using the polishing slurry composition, the polishing target film may be selectively removed, and the selectivity of the polishing target film 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 selectivity ratio of the inorganic oxide film to the silicon nitride film may be 30:1 (inorganic oxide film: nitride film) or more, and the polishing according to the present invention The inorganic oxide film can be polished at high speed when polishing using the slurry composition, 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 low pattern density but also on a wafer having a large pattern density.

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

Examples 1 to 15

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

Examples 16 and 17

Polishing slurry according to Table 1 in the same manner as in Example 1, except that colloidal ceria particles (HC-90, Solvay Co.) having an average particle size of 90 nm (measured by BET) were used for the abrasive particles in Example 1 A composition was prepared.

particle dispersant stabilizer abrasive selectivity control agent 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) Dispersion stability evaluation In order to evaluate the dispersion stability of the slurry composition of Examples, the particle size was measured on day 0 and day 1, respectively, to measure stability over time.

dispersion stability Initial 1 day 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 due to the increase in the content of oxalic acid It can be seen that dispersion stability is low. (2) Evaluation of polishing properties

Using the polishing slurry composition of Example, the ITO film and the SiN film-containing substrate were polished under the following polishing conditions.

[Grinding Conditions]

1. Grinding equipment: CTS AP-300

2. Wafer: 300mm ITO Film 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 selectivity 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 Unable 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, the slurry compositions of Examples 1 to 5 and Examples 9 to 17, the polishing rate for the ITO film is improved, the polishing rate for the polishing stop film SiN is reduced, ITO / SiN polishing It can be seen that the selection cost is increased. The application of oxalic acid, which serves as an etchant for the ITO film, improves the polishing rate of the ITO film, and the dispersion stability of the polishing slurry by aromatic organic acid and PEI is improved, thereby increasing the selectivity of the ITO film, thereby improving the automatic stop performance for the SiN stop film. can In addition, in Examples 6 to 8, it can be seen that the dispersion stability of the slurry is poor, so that it is difficult to express the polishing performance. Accordingly, the polishing slurry composition of the present invention has a polishing rate of ITO film and 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 with reference to the limited drawings, those skilled in the art may apply various technical modifications and variations based on the above. For example, even if the described techniques are performed in an order different from the described method, and/or the described components are combined or combined in a different form from the described method, or replaced or substituted by other components or equivalents Appropriate results can be achieved.

Therefore, other implementations, other embodiments, and equivalents to the claims are also 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 modifier;
including,
The polishing target film is ITO (indium tin oxide),
The polishing selectivity adjusting agent is included in an amount of 0.001% by weight or more and less than 0.1% by weight of the polishing slurry composition,
The polishing selectivity control agent, pKa 6 or less will include a strong acid organic acid,
Abrasive Slurry Composition.
According to claim 1,
The dispersant is included in 0.01 wt% to 5 wt% 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 comprising at least one selected from the group consisting of (Pyridinedicarboxylic Acid),
Abrasive Slurry Composition.
According to claim 1,
The stabilizer is included in an amount of 0.001 wt% to 1 wt% of the polishing slurry composition,
The stabilizer is, polyethyleneimine (PEI, Polyethyleneimine), polypropyleneimine (polypropyleneimine), polyvinylamine (polyvinylamine), polyallylamine (polyallylamine), polyhexadimethrine (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 (PLL), polyacrylamide, acrylamide derived polymer, quaternary polyamine, polydimethylamine, polyallyldimethyl ammonium chloride , poly(dimethylamine-co-epichlorohydrin), poly(methacryloyloxyethyltrimethylammonium chloride), poly(methacryloyloxyethyldimethylbenzylammonium chloride), polyamide-amine , diphenylamine-epihydrin-based polymer (dimethylamine-epihydrin-b ased polymer), dicyandiamide, Dicyandiaminde, acrylamide, dimethylaminoethyl acrylate, D-glycosamine derivative, iminobispropylamine (Imino-bis-propylamine), Methylimino-bis-propylamine, Laurylimino-bis-propylamine, Pentamethyldiethylenetriamine, Pentamethyldipropylenediamine (Pentamethyldipropylenediamine), aminopropyl-1,3-propylenediamine (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,
Abrasive Slurry Composition.
delete According to claim 1,
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 comprising at least one selected from the group consisting of,
Abrasive Slurry Composition.
According to claim 1,
pH of the polishing slurry composition is 2 to 5,
The polishing slurry composition has a zeta potential of +5mV to +70mV
Abrasive Slurry Composition.
According to 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,
Abrasive Slurry Composition.
According to claim 1,
After polishing the substrate using the polishing slurry composition, the polishing rate for the film to be polished is 1000 Å/min or more,
Abrasive Slurry Composition.