KR102122125B1 - Polishing slurry composition - Google Patents

Abstract

The present invention, iron-substituted abrasive particles; pH adjusting agent; And chelating agents; It relates to a polishing slurry composition comprising a.

Description

Polishing slurry composition {POLISHING SLURRY COMPOSITION}

The present invention relates to a slurry composition for polishing semiconductor devices and display devices.

Recently, chemical and mechanical polishing (CMP) processes of various thin films constituting devices have been required in the semiconductor and display industries.

The chemical mechanical polishing (CMP) process refers to a process in which a semiconductor wafer surface is flatly polished using a slurry containing abrasives and various compounds while rotating in contact with the polishing pad. In general, the metal polishing process is known to occur repeatedly by a process in which a metal oxide (MO _x ) is formed by an oxidizing agent and a process in which abrasive particles remove the formed metal oxide.

The polishing process of the tungsten layer, which is frequently used as a wiring for semiconductor devices, is also performed by a mechanism in which tungsten oxide (WO ₃ ) is formed by an oxidizing agent and a potential modifier and tungsten oxide is removed by abrasive particles. In addition, an insulating film may be formed under the tungsten layer, or a pattern such as a trench may be formed. In this case, high polishing selectivity between the tungsten layer and the insulating film is required in the CMP process. Accordingly, in order to improve the polishing selectivity of tungsten to the insulating film, various components are added to the slurry, or the content of the oxidizing agent and catalyst contained in the slurry is controlled. Despite these efforts, a tungsten polishing slurry has not been developed that can improve the polishing performance by implementing a high polishing selectivity or by adjusting a desired polishing selectivity.

In addition, ITO (indium tin oxide), IZO (indium zinc oxide), and ITZO (indium tin zinc oxide) are widely used as inorganic materials having high conductivity and light transmittance, which are thin layers of ITO covering the substrate surface in a display device. , It is used as a transparent electrode, antistatic film, etc. on display substrates and panels such as organic light emitting diodes (OLEDs), touch panels, and solar cells. In general, in order to deposit an ITO thin film on a substrate, DC-Magnetron Sputtering, RF-Sputtering, Ion Beam Sputtering, E-Beam Evaporation, etc. The physical vapor deposition (Physical Vapor Deposition), sol-gel (Sol-Gel), spray pyrolysis (Spray Pyrolysis), such as chemical vapor deposition (Chemical Vapor Deposition) is used, but the most widely used DC-magnetron sputtering Since the thin film has a high surface roughness of Rnms 1nm or more and Rpv 20nm or more, when it is applied to organic light emitting diodes, organic substances are damaged due to concentration of current density, causing defects such as black spots, scratching and irregularity of the ITO　 thin film, and Together with the surface residue (foreign material adsorbed on the ITO surface), it can provide a current leakage path flowing through the diode adjacent to the ITO layer, resulting in crosstalk and low resistance.

Attempts have been made to solve the above-mentioned problems through planarization of the ITO film. Representatively, there are ion beam sputtering and ion plating methods. However, such an ion assisted deposition method can deposit a thin film having a flat surface, but it is difficult to apply to mass production because the deposition rate is slow and it is difficult to make a large area, and a method of flattening the surface of the manufactured thin film by fine polishing, It has been suggested for the planarization method by a rod member having a surface having a polishing ability, the application of a liquid leveling agent using the deposition of a surface modifier, the planarization etching, the pressure 　 flattening and the ablation, but the existing polishing, surface modifier deposition, etching, etc. The planarization process has a problem of generating unwanted scratch defects, surface contamination, etc. on the surface of the ITO film after the planarization process.

The present invention is to solve the above-mentioned problems, and relates to a slurry composition for polishing, including iron-substituted abrasive particles, capable of improving the surface planarization process of thin films applied to semiconductor devices and display devices.

According to an embodiment of the present invention, iron-substituted abrasive particles; pH adjusting agent; And a chelating agent, oxidizing agent, or both.

According to an embodiment of the present invention, the iron-substituted abrasive particles may be included as 0.0001 parts by weight to 20 parts by weight with respect to the slurry composition.

According to an embodiment of the present invention, the iron-substituted abrasive particles may be included in an amount of more than 0.5 parts by weight and 5 parts by weight or less with respect to the slurry composition.

According to an embodiment of the present invention, the size of the iron-substituted abrasive particles may be 10 nm to 300 nm.

According to an embodiment of the present invention, the iron-substituted abrasive particles are atomic sites located in a length region of 30% or less from the surface of the iron-substituted abrasive particles from the surface to the center (100%). site) may be substituted with iron.

According to one embodiment of the invention, the iron-substituted abrasive particles, metal oxide; And a metal oxide coated with an organic or inorganic material. And one or more selected from the group consisting of silica, ceria, zirconia, alumina, titania, barium titania, germania, mangania, and magnesia. It may be included.

According to an embodiment of the present invention, the iron-substituted abrasive particles include iron ions having tetrahedral coordination, and the iron-substituted abrasive particles are metal (M)-O-Fe bonds, metals (M)-Fe bond (where M is selected from Si, Ce, Zr, Al, Ti, Ba, Ge, Mn and Mg.), or both.

According to an embodiment of the present invention, the iron-substituted abrasive particles may have a zeta potential of -1 mV to -100 mV at pH 1 to 12.

According to one embodiment of the present invention, the iron-substituted abrasive particles may be 10 nm to 300 nm single sized particles or 10 nm to 300 nm of mixed particles having two or more different sizes.

According to an embodiment of the present invention, the iron-substituted abrasive particles may include particles of a first size of 10 nm to 150 nm and particles of a second size of 150 nm to 300 nm.

According to an embodiment of the present invention, the chelating agent includes an organic acid, and the organic acid is citric acid, malic acid, maleic acid, malonic acid, oxalic acid, succinic acid, lactic acid, tartaric acid, adipic acid, pimelic acid, water Veric acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, acetic acid, adipic acid, butyric acid, capric acid, caproic acid, caprylic acid, glutaric acid, glycolic acid, formic acid, lauric acid, myristic acid , Palmitic acid, phthalic acid, propionic acid, pyruvic acid, stearic acid, and valeric acid.

According to an embodiment of the present invention, the chelating agent may be included as 0.00001 parts by weight to 10 parts by weight with respect to the slurry composition.

According to an embodiment of the present invention, the oxidizing agent, hydrogen peroxide, hydrogen peroxide, urea hydrogen peroxide, urea, percarbonate, periodic acid, periodate, perchloric acid, perchlorate, perbromic acid, perbromate, perborate, perborate Group consisting of permanganic acid, permanganate, persulfate, bromate, chlorate, chlorite, chromate, iodate, iodic acid, ammonium peroxide, benzoyl peroxide, calcium peroxide, barium peroxide, sodium peroxide and urea peroxide It may be to include one or more selected from.

According to an embodiment of the present invention, the oxidizing agent may be contained in 0.00001 parts by weight to 10 parts by weight with respect to the slurry composition.

According to an embodiment of the present invention, the pH adjusting agent includes an acidic substance or a basic substance, and the acidic substance is 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, It includes at least one selected from the group consisting of tartaric acid and each salt, and the basic substance is ammonium methyl propanol (AMP), tetramethyl ammonium hydroxide (tetramethyl ammonium hydroxide; TMAH), ammonium hydroxide , Potassium hydroxide, sodium hydroxide, magnesium hydroxide, rubidium hydroxide, cesium hydroxide, sodium hydrogen carbonate, sodium carbonate, imidazole and one or more selected from the group consisting of salts.

According to an embodiment of the present invention, the polishing slurry composition may be applied to polishing of a thin film including one or more selected from the group consisting of a silicon oxide film, a metal film, a metal oxide film, and an inorganic oxide film.

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, the metal film and the metal oxide film, respectively, 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 (Ta), ruthenium (Ru), tungsten (W), titanium (Ti), nickel (Ni), chromium (Cr), neodynium (Nd), rubidium (N) Rb), gold (Au) and platinum (Pt) may include one or more selected from the group consisting of.

According to an embodiment of the present invention, the inorganic oxide film, FTO (fluorine doped tin oxide, SnO ₂ : F), indium tin oxide (ITO), indium zinc oxide (IZO), indium gallium zinc oxide (IGZO), Al-doped ZnO (AZO), Aluminum Gallium Zinc Oxide (AGZO), Ga-doped ZnO (GZO), 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 NiO.

According to an embodiment of the present invention, when polishing the target film using the polishing slurry composition, the polishing rate for the target film may be 100 Å/min or more.

According to an embodiment of the present invention, the flatness of the surface after polishing the target film using the slurry composition may be 5% or less.

According to an embodiment of the present invention, the transparency of the device after polishing the target film using the slurry composition may be increased by 5% or more compared to before polishing.

The present invention, by applying the iron-substituted abrasive particles to secure a sufficient amount of polishing for each polishing target film quality, it is possible to provide a polishing slurry composition capable of free or minimize scratch defects in the polishing process.

The polishing slurry composition of the present invention is applied to a planarization process of a semiconductor device and a display device by a chemical mechanical polishing process (CMP), and specifically, an insulating film, an oxide film, a semiconductor film, an inorganic oxide film and a display device used in a semiconductor device It can be applied to the planarization process of the inorganic oxide used in.

The polishing slurry composition of the present invention can increase the efficiency for post-processing by securing flatness and/or permeability to semiconductor wiring elements, display substrates, panels, etc. that require a planarization process of an oxide film, a metal film, and an inorganic oxide film.

1 is a schematic diagram of colloidal silica abrasive particles substituted with iron (Fe) ions by hydrothermal synthesis according to an embodiment of the present invention.

Hereinafter, embodiments will be described in detail with reference to the accompanying drawings. However, various changes may be made to the embodiments, and the scope of the patent application right is not limited or limited by these embodiments. It should be understood that all modifications, equivalents, or substitutes for the embodiments are included in the scope of rights.

The terms used in the examples are used for illustrative purposes only and should not be construed as limiting. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this specification, the terms "include" or "have" are intended to indicate the presence of features, numbers, steps, actions, components, parts or combinations thereof described herein, one or more other features. It should be understood that the existence or addition possibilities of fields or numbers, steps, operations, components, parts or combinations thereof are not excluded in advance.

Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by a person skilled in the art to which the embodiment belongs. Terms, such as those defined in a commonly used dictionary, should be interpreted as having meanings consistent with meanings in the context of related technologies, and should not be interpreted as ideal or excessively formal meanings unless explicitly defined in the present application. Does not.

In addition, in the description with reference to the accompanying drawings, the same reference numerals are assigned to the same components regardless of reference numerals, and redundant descriptions thereof will be omitted. In describing the embodiments, when it is determined that detailed descriptions of related known technologies may unnecessarily obscure the subject matter of the embodiments, detailed descriptions thereof will be omitted.

The present invention relates to a slurry composition for polishing, according to an embodiment of the present invention, the slurry composition includes iron-substituted abrasive particles; pH adjusting agent; And chelating agents, oxidizing agents, or both.

According to one embodiment of the present invention, the iron-substituted abrasive particles may contain from 0.0001 parts by weight to 20 parts by weight with respect to the slurry composition, improve transparency and/or planarization after polishing, defects and stretch Back defects can be minimized. It is preferably 0.0001 part by weight to 10 parts by weight, and more preferably 0.5 to 5 parts by weight or less.

According to an embodiment of the present invention, the iron-substituted abrasive particles may be abrasive particles in which iron ions are substituted on a part of the abrasive particles. The iron-substituted abrasive particles utilize the properties of iron ions having tetrahedral coordination in the alkali region, and metal oxide element ions (for example, abrasive particles are silica) on the surface of the abrasive particles under hydrothermal synthesis conditions. Si ion, Ce for abrasive grains, Ce for abrasive grains, Zr for abrasive grains, etc.) and iron ions to modify the surface to improve dispersion stability even in the acidic region, increase the negative charge of the slurry composition, and scratch during polishing Sex defects can be free or minimized.

In the iron-substituted abrasive particles, iron ions are substituted at atomic sites located in a length region of 30% or less from the surface of the iron-substituted abrasive particles from the surface to the center (100%). , In the inside of the surface of the abrasive particles, the iron (Fe) ion may be substituted with a component of a part of the abrasive particles.

In the iron-substituted abrasive particles, abrasive particles include metal oxides; And a metal oxide coated with an organic or inorganic material; and the iron-substituted abrasive particles and/or metal oxides may be in a colloidal state. The metal oxide may include one or more selected from the group consisting of silica, ceria, zirconia, alumina, titania, barium titania, germania, mangania, and magnesia.

The iron ions may have tetrahedral coordination, and the iron-substituted abrasive particles may include metal (M)-O-Fe bond, metal (M)-Fe, or both ( Here, the metal (M) may include one or more selected from the group consisting of Si, Ce, Zr, Al, Ti, Ba, Ge, Mn, and Mg. For example, FIG. 1 is one embodiment of the present invention. It is a schematic diagram of colloidal silica abrasive particles substituted with iron (Fe) ions according to an embodiment, referring to Fig. 1, one of the silicon (Si) ions in the colloidal silica abrasive particles is replaced with iron (Fe) ions, It can be seen that Si-O-Fe and Si-Fe are included.

The size of the iron-substituted abrasive particles may be 10 nm to 300 nm. When the size of the particles is less than 10 nm, excessively small particles are generated while the flatness of the polishing target film decreases, excessive defects occur on the surface of the polishing target film, and the polishing rate decreases. Failure to achieve may result in difficulty in controlling flatness, transparency, and defects after mechanical polishing. The size may mean diameter, length, thickness, etc., depending on the shape of the particles.

The iron-substituted abrasive particles are single size particles of 10 nm to 300 nm or two or more different sizes of 10 nm to 300 nm in order to improve dispersibility in a slurry, polishing performance of a polishing target film, flattening and transparency. It may be one containing mixed particles. For example, the iron-substituted abrasive particles may include particles of a first size of 10 nm to 150 nm and particles of a second size of 150 nm to 300 nm.

The iron-substituted abrasive particles may include one or more selected from the group consisting of a spherical shape, a square shape, a needle shape, and a plate shape.

The iron-substituted abrasive particles, at pH 1 to 12,-1 mV to-100 mV zeta potential, at pH 1 to 6,-10 mV to-70 mV zeta potential; Or at pH 2.5-6, -10 mV to -70 mV. This shows an absolute value of high zeta potential even in the acidic region, and thus has high dispersion stability and can realize excellent polishing power for the polishing target film.

The iron-substituted abrasive particles may perform not only the function of the abrasive particles in the polishing slurry composition, but also the function of the oxidizing agent to oxidize the metal film.

The iron-substituted abrasive particles utilize metal ions having tetrahedral coordination in the alkali region, and metal oxide element ions on the surface of the abrasive particles under hydrothermal synthesis (for example, abrasive particles are silica) In the case of replacing Si ions, Ce if abrasive particles are ceria, Zr when abrasive particles are zirconia, and iron ions) and modifying the surface, a polishing slurry composition having high dispersion stability can be prepared. In addition, metal oxide element ions and substituted iron ions on the surface of the abrasive particles promote oxidation of the polishing target film, for example, an inorganic oxide film, thereby realizing high polishing properties that can easily polish the inorganic oxide film and scratch defects. By minimizing, it is possible to improve the flatness and transparency of the inorganic oxide film such as ITO.

According to an embodiment of the present invention, a method for preparing iron-substituted abrasive particles includes: preparing a mixture by mixing abrasive particles with an iron-containing salt, a metal ion compound, or both; And synthesizing the mixture under hydrothermal synthesis conditions.

The method of manufacturing the metal-substituted abrasive particles is to substitute metal oxide elemental ions and iron ions of the abrasive particles by using a characteristic in which the metal ions have tetrahedral coordination under alkaline conditions.

The iron-containing salt is ferric nitrate (Fe(NO ₃ ) ₃ , ferric nitrate), ferric sulfate (Fe ₂ (SO ₄ ) ₃ , ferric sulfate), ferric oxide (Fe ₂ O ₃ , ferric oxide ) And ferric chloride (FeCl ₃ , ferric chloride). In the case of ferric nitrate, it dissociates in water to provide iron ions (Fe ^{2 +} , Fe ³ ).

The metal ion compound, in the group consisting of sodium nitrate, lithium nitrate, potassium nitrate, sodium hydroxide, lithium hydroxide, potassium hydroxide, sodium sulfate, lithium sulfate, potassium sulfate, sodium chloride, lithium hydrochloride, potassium chloride, sodium carbonate, lithium carbonate and potassium carbonate It may include one or more selected.

The iron-containing salt may be 0.001 part by weight to 20 parts by weight based on 100 parts by weight of the abrasive particles. When the metal salt is less than 0.001 parts by weight, it is difficult to obtain a sufficient zeta charge, resulting in poor dispersion stability, and when the iron-containing salt exceeds 20 parts by weight, there is a possibility of contamination problems caused by unreacted iron-containing salts.

The metal ion compound may be 0.001 part by weight to 20 parts by weight based on 100 parts by weight of the abrasive particles. When the metal ion compound is less than 0.001 parts by weight, there may be a problem that the substitution of iron ions is not smoothly performed, and when the metal ion compound exceeds 20 parts by weight, contamination problems occur and dispersion stability decreases. It can be.

The step of synthesizing the mixture under hydrothermal synthesis conditions to perform the iron substitution reaction efficiently may be hydrothermal synthesis for 0.5 to 72 hours in a temperature range of 100°C to 300°C.

The pH of the mixture may be adjusted to 9 to 12 before hydrothermal synthesis, and the pH may be adjusted to 1 to 5 after hydrothermal synthesis is completed. In this case, the pH adjusting agent used may be an acid or a base, without limitation, potassium hydroxide, sodium hydroxide, ammonia, ammonia derivatives, hydrochloric acid, nitric acid, sulfuric acid, acetic acid, phosphoric acid, boric acid, amino acids, citric acid, tartaric acid, formic acid, maleic acid, One or more selected from the group consisting of oxalic acid, tartaric acid, and acetic acid may be used, and it may be used in an amount capable of adjusting the pH.

For example, referring to FIG. 1, FIG. 1 is a schematic diagram of colloidal silica abrasive particles substituted with iron (Fe) ions by hydrothermal synthesis according to an embodiment of the present invention. In FIG. 1, it can be seen that one of the silicon (Si) ions in the colloidal silica abrasive particles is replaced with iron (Fe) ions. In the alkaline condition, iron (Fe) ions are used to have tetrahedral coordination. After mixing ferric nitrate (Fe(NO ₃ ) ₃ ) as a metal salt and sodium nitrate as a metal ion compound, the metal substitution reaction efficiently reacts under hydrothermal synthesis conditions so that one of the silicon (Si) ions is an iron (Fe) ion It can be confirmed that the substitution.

According to an embodiment of the present invention, the chelating agent includes an organic acid, and the organic acid is citric acid, malic acid, maleic acid, malonic acid, oxalic acid, succinic acid, lactic acid, tartaric acid, adipic acid, pimelic acid, water Veric acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, acetic acid, adipic acid, butyric acid, capric acid, caproic acid, caprylic acid, glutaric acid, glycolic acid, formic acid, lauric acid, myristic acid , Palmitic acid, phthalic acid, propionic acid, pyruvic acid, stearic acid, and valeric acid.

The chelating agent is contained in an amount of 0.00001 parts by weight to 10 parts by weight based on the slurry composition, and when included within the above range, particle dispersibility and stability of the slurry composition may be secured.

According to an embodiment of the present invention, the pH adjusting agent is intended to prevent corrosion of a polishing target film or corrosion of a polishing machine and to implement a pH range suitable for polishing performance, including an acidic substance or a basic substance, and the acidic substance , 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, pimeline Acid, benzoic acid, succinic acid, phthalic acid, butyric acid, glutaric acid, glutamic acid, glycolic acid, lactic acid, aspartic acid, tartaric acid, and one or more selected from the group consisting of salts, and the basic substance is ammonium methyl propanol (ammoniumammonium propanol) methyl propanol; AMP), tetra methyl ammonium hydroxide (TMAH), ammonium hydroxide, potassium hydroxide, sodium hydroxide, magnesium hydroxide, rubidium hydroxide, cesium hydroxide, sodium hydrogen carbonate, sodium carbonate, imidazole and their respective It may be to include one or more selected from the group consisting of salts.

According to an embodiment of the present invention, the oxidizing agent, hydrogen peroxide, hydrogen peroxide, urea hydrogen peroxide, urea, percarbonate, periodic acid, periodate, perchloric acid, perchlorate, perbromic acid, perbromate, perborate, perborate Group consisting of permanganic acid, permanganate, persulfate, bromate, chlorate, chlorite, chromate, iodate, iodic acid, ammonium peroxide, benzoyl peroxide, calcium peroxide, barium peroxide, sodium peroxide and urea peroxide It may be to include one or more selected from.

The oxidizing agent may be included in an amount of 0.00001 parts by weight to 10 parts by weight based on the slurry composition. When included in the above range, it is possible to provide an appropriate polishing rate for the polishing target film, and to prevent corrosion, erosion, and hardening of the polishing target film due to an increase in the content of the oxidizing agent.

The pH of the polishing slurry composition according to the present invention is preferably adjusted to give dispersion stability and an appropriate polishing rate according to the abrasive particles, and the pH of the polishing slurry composition is 1 to 12, preferably 1 to 6 It may have an acidic pH range.

The polishing slurry composition may have a -1 mV to -100 mV zeta potential, preferably -10 mV to -70 mV zeta potential. When the absolute value of the zeta potential is high, the force pushing each other between particles becomes stronger, so that aggregation is less likely to occur. Therefore, the polishing slurry composition of the present invention exhibits a high zeta potential absolute value even in an acidic region, whereby high dispersion stability and high polishing power can be realized.

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

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 film, a metal film, a metal oxide film, and an inorganic oxide film as a polishing target film. For example, it may be applied to a planarization process of a semiconductor device to which an insulating film, a metal film, a metal oxide film and/or an inorganic oxide film is applied, and a display device to which an inorganic oxide film is applied.

The insulating film may be a silicon or silicon oxide film, and the metal film and the metal oxide film may each be 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 (Ta), Ruthenium (Ru), Tungsten (W), Titanium (Ti), Nickel (Ni), Chromium (Cr), Neodynium (Nd) , Rubidium (Rb), gold (Au), and platinum (Pt).

The inorganic oxide film, 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), iridium (Ir) and nickel (Ni) , Nitride or both, and halogen or the like may be doped. For example, fluorine doped tin oxide (FTO), SnO ₂ : F), indium tin oxide (ITO), indium zinc oxide (IZO), indium gallium zinc oxide (IGZO), Al-doped ZnO (AZO), Aluminum Gallium Zinc Oxide (AGZO), Ga-doped ZnO (GZO), 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 NiO.

The planarization process of the semiconductor device and the display device includes 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; Phase change films 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 slurry composition, polishing of a substrate comprising at least one selected from the group consisting of glass, silicon, SiC, SiGe, Ge, GaN, GaP, GaAs, sapphire, plastic, etc. It can be further applied to the process.

According to an embodiment of the present invention, the polishing rate for the polishing target film of the polishing slurry composition is 100 kPa/min or more; 500 kPa/min or more; It may be 1000 Å/min or 2000 Å/min or more.

According to one embodiment of the present invention, the polishing slurry composition exhibits a high polishing selectivity to a polishing target film, for example, a polishing target film to insulating film selectivity may range from 10:1 to 100:1. have.

According to an embodiment of the present invention, the flatness of the surface after polishing of the polishing target film using the polishing slurry composition may be 5% or less.

According to an embodiment of the present invention, after polishing of the polishing target film using the polishing slurry composition, the surface has a peak to valley (PV) value of 100 nm or less, or a surface roughness of 10 nm. It may be the following. The peak-to-valley value and the degree of surface roughness can be measured with an atomic force microscope.

According to an embodiment of the present invention, after polishing of the polishing target film using the polishing slurry composition, the transparency of the device may be increased by 5% or more.

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

Example 1: Preparation of Fe ion-substituted colloidal silica abrasive particles

A mixed solution of colloidal silica abrasive particles 3% by weight, iron nitrate (Fe(NO ₃ ) ₃ ) 0.05% by weight and sodium nitrate (NaNO ₃ ) 0.1% by weight was added. It was then titrated with sodium hydroxide (NaOH) until pH 10. The pH-adjusted colloidal silica-containing mixed solution was placed in a hydrothermal reactor and subjected to hydrothermal reaction at 140° C. for 24 hours to prepare Fe ion-substituted colloidal silica abrasive particles.

Example 2: A polishing slurry composition comprising Fe ion-substituted colloidal silica abrasive particles

Preparation of a polishing slurry composition of pH 2.5 by adding 4 wt% of Fe ion-substituted colloidal silica abrasive particles of Example 1, 0.5 wt% of hydrogen peroxide as an oxidizing agent, 0.1 wt% of malonic acid as a chelating agent and nitric acid as a pH adjusting agent Did.

Example 3: Polishing slurry composition comprising Fe ion-substituted colloidal silica abrasive particles

A polishing slurry composition was prepared in the same manner as in Example 2, except that the chelating agent was contained in 1.00% by weight.

Example 4: A polishing slurry composition comprising Fe ion-substituted colloidal silica abrasive particles

An abrasive slurry composition was prepared in the same manner as in Example 2, except that 6% by weight of Fe ion-substituted colloidal silica abrasive particles and 0.07% by weight of a chelating agent were included.

Example 5: Polishing slurry composition comprising Fe ion-substituted colloidal silica abrasive particles

An abrasive slurry composition was prepared in the same manner as in Example 2, except that 0.5% by weight of Fe ion-substituted colloidal silica abrasive particles and 0.5% by weight of a chelating agent were included.

Example 6: Polishing slurry composition comprising Fe ion-substituted colloidal silica abrasive particles

Preparation of a polishing slurry composition of pH 2.5 by adding 1.5% by weight of Fe ion-substituted colloidal silica abrasive particles of Example 1, 1.5% by weight of hydrogen peroxide as an oxidizing agent, 0.1% by weight of malonic acid as a chelating agent and nitric acid as a pH adjusting agent Did.

Example 7: A polishing slurry composition comprising Fe ion-substituted colloidal silica abrasive particles

A polishing slurry composition was prepared in the same manner as in Example 6, except that the hydrogen peroxide content was applied at 4.0% by weight.

Comparative Example 1:

Commercially available general colloidal silica abrasive particles were prepared.

Comparative Example 2: General colloidal silica abrasive particles polishing slurry composition

A slurry composition for polishing was prepared in the same manner as in Example 2, except that commercially available colloidal silica abrasive particles were used and 2% by weight of abrasive particles were applied without application of a chelating agent.

Comparative Example 3: General colloidal silica abrasive particles polishing slurry composition

An abrasive slurry composition was prepared in the same manner as in Example 6, except that commercially available colloidal silica abrasive particles were used.

(1) Fe ion substitution confirmation

To confirm whether Fe ion substitution of the Fe ion-substituted colloidal silica abrasive particles of Example 1 was performed well, the Fe ion-substituted colloidal silica abrasive particles of Example 1 were centrifuged to give a particle cake 110. After drying at 24° C. for 24 hours, KBr was mixed to prepare pellets and measured with an infrared spectrometer. 1 is an infrared absorption spectrum diagram of Fe ion-substituted colloidal silica abrasive particles of Example 1 of the present invention and silica abrasive particles of Comparative Example 1. The horizontal axis represents the wave number, and the vertical axis represents the transmittance. In the infrared absorption spectrum, a Si-O-Fe bonding peak can be confirmed at 668 cm ^-1 . This analysis shows that the Fe-replacement was successful.

(2) Dispersion stability evaluation (Zeta potential change)

To evaluate the dispersion stability of the abrasive particles of Example 1 and Comparative Example 1, the zeta potential of the abrasive particles according to Example 1 and Comparative Example 1 was compared with the zeta potential after 10 days. Table 1 below compares the initial zeta potential of the abrasive particles according to Example 1 and Comparative Example 1 of the present invention and the zeta potential after 10 days.

Initial zeta potential
(mV) Zeta potential after 10 days
(mV) Remark Example 1 -22.4 -17.9 stability Comparative Example 1 + 1.5 + 0.2 Cohesion

Referring to Table 1, it can be confirmed that the Fe ion-substituted silica abrasive particles of the present invention have higher dispersion stability than the abrasive particles of Comparative Example 1 due to the high absolute zeta potential even after 10 days.

(3) Evaluation of polishing properties

(i) Using the polishing slurry compositions of Examples and Comparative Examples, the ITO film-containing substrate was polished under the following polishing conditions.

[Polishing conditions]

1. Polishing equipment: CETR CP-4 from Bruker

2. Wafer: 6 cm X 6 cm ITO film transparent substrate

3. Platen pressure: 3 psi

4. Spindle speed: 69 rpm

5. Platen speed: 70 rpm

6. Flow rate: 100 ml/min

To evaluate the polishing properties, polishing rates and flatness were compared after polishing the ITO film substrate using the polishing slurry compositions according to Examples 2 to 5 and Comparative Example 2. Table 2 below shows the polishing rate and flatness after polishing the ITO film substrate using the polishing slurry composition according to Example 2 and Comparative Example 2 of the present invention.

Abrasive particle type Abrasive particle content
(wt %) Chelating agent content
(wt %) Polishing speed
(Å/min) flatness
(%) transparency
Change (after polishing/before polishing) Example 2 Fe-substituted colloidal silica 4.0 0.10 503 3% +15% Example 3 Fe-substituted colloidal silica 4.0 1.00 610 2% +18% Example 4 Fe-substituted colloidal silica 6.0 0.07 671 2% +20% Example 5 Fe-substituted colloidal silica 0.5 0.50 406 5% +13% Comparative Example 2 Common colloidal silica 2.0 0.00 52 17% +2%

Referring to Table 2, in the case of using a polishing slurry composition to which Fe ion-substituted colloidal silica according to Examples 2 to 5 of the present invention is used, both the polishing rate and flatness for an ITO film are excellent, and scratch It can be seen that the transparency of the substrate was improved by minimizing the sexual defect.

(ii) Using the polishing slurry compositions of Examples and Comparative Examples, the tungsten film-containing substrate was polished under the following polishing conditions.

[Polishing condition]

1.Polishing equipment: KCTech Co. ST-01

2.Platen speed: 100 rpm

3.Carrier speed: 103 rpm

4.Wafer pressure: 3.0 psi

5. Slurry flow rate: 250ml/min

6. Pad: IC 1000

Abrasive particle type Abrasive particle content
(wt %) Fruit tree content (wt%) W RR
(Å/min) Ox RR
(Å/min) Example 6 Fe-substituted colloidal silica 1.5 1.5 1,154 169 Example 7 Fe-substituted colloidal silica 1.5 4.0 3,180 67 Comparative Example 3 Common colloidal silica 1.5 1.5 431 243

Referring to Table 3, when using a polishing slurry composition to which Fe ion-substituted colloidal silica according to Examples 6 to 7 of the present invention is used, providing a high polishing rate and polishing selectivity for a tungsten film Can be confirmed.

As described above, although the embodiments have been described with limited drawings, those skilled 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 than the described method, and/or the described components are combined or combined in a different form from the described method, or replaced or replaced by another component or equivalent 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 (21)

Iron-substituted abrasive particles;
pH adjusting agent; And
A polishing slurry composition comprising a chelating agent,
The chelating agent includes an organic acid,
The organic acid, malic acid, malonic acid, succinic acid, lactic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, adipic acid, butyric acid, capric acid, caproic acid, caprylic acid, Glutaric acid, glycolic acid, lauric acid, myristic acid, palmitic acid, phthalic acid, propionic acid, pyruvic acid, stearic acid and valeric acid;
The chelating agent is contained in more than 0.1 parts by weight and 10 parts by weight or less based on 100 parts by weight of the slurry composition,
Fluorine doped tin oxide (FTO), SnO ₂ : F), indium tin oxide (ITO), indium zinc oxide (IZO), indium gallium zinc oxide (IGZO), Al-doped ZnO (AZO), Aluminum Gallium Zinc Oxide (AGZO) , GZO(Ga-doped ZnO), IZTO(Indium Zinc Tin Oxide), IAZO(Indium Aluminum Zinc Oxide), IGTO(Indium Gallium Tin Oxide), ATO(Antimony Tin Oxide), GZO(Gallium Zinc Oxide), IZON(IZO Nitride), SnO ₂ , ZnO, IrOx, RuOx and is applied to the polishing of the inorganic oxide film containing at least one member selected from the group consisting of NiO,
The transparency of the element after polishing of the inorganic oxide film is increased by 5% or more compared to before polishing,
Polishing slurry composition.
According to claim 1,
The iron-substituted abrasive particles are contained in 0.0001 parts by weight to 20 parts by weight based on 100 parts by weight of the slurry composition, abrasive slurry composition.
According to claim 1,
The iron-substituted abrasive particles, the slurry composition for polishing is contained in more than 0.5 parts by weight and 5 parts by weight or less based on 100 parts by weight of the slurry composition.
According to claim 1,
The size of the iron-substituted abrasive particles is 10 nm to 300 nm, abrasive slurry composition.
According to claim 1,
The iron-substituted abrasive particles,
Of the length of the iron-substituted abrasive particles from the surface to the center (100%), iron is substituted at the atomic site (atomic site) located in a length region of 30% or less from the surface, the polishing slurry composition for polishing.
According to claim 1,
The iron-substituted abrasive particles include a metal oxide; And a metal oxide coated with an organic or inorganic material. Contains at least one of
The metal oxide is in a colloidal state,
The metal oxide comprises at least one selected from the group consisting of silica, ceria, zirconia, alumina, titania, barium titania, germania, mangania, and magnesia.
According to claim 1,
The iron-substituted abrasive particles include iron ions having tetrahedral coordination,
The iron-substituted abrasive particles, metal (M)-O-Fe bond, metal (M)-Fe bond (where M is selected from Si, Ce, Zr, Al, Ti, Ba, Ge, Mn and Mg .), or both, a polishing slurry composition.
According to claim 1,
The iron-substituted abrasive particles, at pH 1 to 12,-1 mV to-100 mV will have a zeta potential, the slurry composition for polishing.
According to claim 1,
The iron-substituted abrasive particles, 10 nm to 300 nm is a single sized particles or 10 nm to 300 nm comprising a mixture of particles having two or more different sizes, abrasive slurry composition.
According to claim 1,
The iron-substituted abrasive particles, 10 nm to 150 nm of the first size and 150 nm to 300 nm size of the second size of the particles comprising abrasive slurry composition.
delete delete According to claim 1,
The pH adjusting agent includes an acidic substance or a basic substance,
The acidic substance, 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 and one or more selected from the group consisting of salts,
The basic substance is ammonium methyl propanol (AMP), tetramethyl ammonium hydroxide (TMA), ammonium hydroxide, potassium hydroxide, sodium hydroxide, magnesium hydroxide, rubidium hydroxide, cesium hydroxide, carbonic acid A polishing slurry composition comprising at least one selected from the group consisting of sodium hydrogen carbonate, sodium carbonate, imidazole and each salt.
delete According to claim 1,
The polishing slurry composition is applied to a polishing process of a semiconductor device, a display device, or both, a polishing slurry composition.
delete delete delete delete delete According to claim 1,
Further comprising an oxidizing agent,
The oxidizing agent, hydrogen peroxide, hydrogen peroxide, urea hydrogen peroxide, urea, percarbonate, periodic acid, periodate, perchloric acid, perchlorate, perbromic acid, perbromic acid, perboric acid, perborate, permanganic acid, permanganate, persulfate, Contains at least one selected from the group consisting of bromate, chlorate, chlorite, chromate, iodate, iodic acid, ammonium peroxide, benzoyl peroxide, calcium peroxide, barium peroxide, sodium peroxide and urea peroxide,
The oxidizing agent is contained in 0.00001 parts by weight to 10 parts by weight based on 100 parts by weight of the slurry composition, polishing slurry composition.

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