KR20100109155A - Process for preparation of thin film capacitor - Google Patents

Abstract

PURPOSE: A process for preparation of a thin film capacitor is provided to allow a user to manufacture a high quality thin film capacitor by improving the interface characteristics between an electrode layer and a dielectric layer. CONSTITUTION: A PET film(1) is provided to manufacture a thin film capacitor. A metal ink composition is coated on the PET film by using a gravure coating device. A bottom electrode layer(2) of 0.1um is formed on the PET surface through a thermal process. A polyimide solution of 1% which is diluted by N-Methyl-2-Pyrrolidone is coated on the PET film to form a dielectric layer(3) of 0.15um thickness.

Description

Process for preparation of thin film capacitor

The present invention relates to a method for manufacturing a thin film capacitor, and more particularly, in a thin film capacitor including a lower electrode layer, a dielectric layer, and an upper electrode layer, the lower electrode layer and the upper electrode layer are formed of an organic metal complex. It relates to a method for manufacturing a thin film capacitor, characterized in that formed by printing or coating a metal ink as an essential component.

In recent years, with the rapid spread of information media such as computers, semiconductor devices are also rapidly developing. In terms of its function, the semiconductor device is required to operate at a high speed and to have a large storage capacity. In response to these demands, manufacturing techniques have been developed for semiconductor devices to improve the degree of integration, reliability, and response speed. Therefore, in the case of a memory device, it is increasingly difficult to obtain the capacitance required for device operation. Accordingly, in manufacturing a capacitor required to operate a gigabit-class memory device, the thickness of the dielectric film is reduced and the capacitance of the capacitor is increased. In order to increase the effective cross-sectional area, efforts have been made to employ various types of lower electrodes and to use dielectric films having high dielectric constants. In the case of employing a dielectric layer having a high dielectric constant, it is known to form a capacitor in a metal-insulater-metal structure. The polysilicon electrode used in the polysilicon-insulator-polysilicon structure requires a low dielectric layer to suppress the reaction with the dielectric layer, which is a limitation in improving the overall capacitance. Indicates. In the metal-insulator-metal capacitor, which forms an electrode with a metal layer having a large work function, a barrier layer is formed at an interface between the metal electrode layer and the dielectric layer, and since the leakage current is controlled by the barrier layer, stable electrical The characteristics can be secured, and as a result, the capacitance can be increased by thinning the dielectric layer. However, the surface uniformity of the lower electrode layer acts as a very important factor for forming a thin film of the dielectric layer, but has a limitation that is difficult to apply to the electrode forming method by the printing method, not the current electrode forming method.

In US Patent Publication No. 6,962,844, it is mentioned that the formation of upper and lower electrodes of a memory holding is formed by an inkjet printing method. In Japanese Patent Laid-Open No. 2007-273990, an inkjet is used to deposit a metal ink in which colloidal dispersion of nanometals is used. It describes a method of forming a, but does not present a specific technical solution.

In order to solve the above problems, the present invention is a thin metal capacitor consisting of a lower electrode layer, a dielectric layer (dielectric layer), and an upper electrode layer, the metal ink having the lower electrode layer and the upper electrode layer as an essential component of the organic metal complex (Organic Metal Complex) Can be formed by printing or coating to improve the surface uniformity of the lower electrode layer and the interface characteristics with the dielectric layer, and the manufacturing process can be applied to a roll-to-roll solution printing process to manufacture a dielectric capacitor capable of mass-producing a capacitor at low cost. To provide a way.

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, in this thin film capacitor which consists of a lower electrode layer, a dielectric layer, and an upper electrode layer, the metal ink which makes a lower electrode layer and an upper electrode layer an essential component of an organic metal complex (Organic Metal Complex) is essential. It is characterized by forming by printing or coating. It also relates to a method of forming a capacitor of a thin film comprising a physical or chemical surface treatment process of an electrode layer.

Hereinafter, the present invention will be described in more detail.

As shown in FIG. 1, the thin film capacitor manufactured by the present invention coats the lower electrode layer 2 and the dielectric, which are formed by printing or coating a metal ink including a metal complex compound on a substrate 1 that is generally used. And an upper electrode layer 4 formed by printing a thin metal dielectric layer 3, a metal complex compound, or a metal ink containing a conductor or a metal precursor.

The type of organometallic complex compound used for forming the electrode layer is not particularly limited, and the metal ink is present in the form of organometallic in the metal ink. Can be achieved.

In particular, the use of a metal ink containing an organometallic complex compound having a special structure filed by the applicant of the patent application No. 2005-34371 has the uniform thickness and excellent conductivity of the metal thin film, and also has a low firing temperature. It is preferred because there is no residue after the conductive material.

The preparation of the metal ink including the metal complex compound is carried out by reacting the metal ink with one or two or more mixtures selected from a metal compound and an ammonium carbamate compound, an ammonium carbonate compound or an ammonium bicarbonate compound. Ammonium carbamate-based compound, ammonium carbonate-based compound or ammonium bicarbonate-based compound] to prepare a composite, and to prepare a metal ink comprising the same, the same production method was used in the present invention.

The metal ink including the metal complex compound may include a metal complex compound obtained by reacting at least one metal or metal compound represented by Formula 1 with at least one ammonium compound represented by Formula 2, Formula 3, or Formula 4. It features.

[Formula 1]

MnX

(M is a metal or a metal alloy, n is an integer of 1 to 10, X is absent, hydrogen, ammonium, oxygen, sulfur, halogen, cyano, cyanate, carbonate, nitrate, nitrite, sulfate, And at least one substituent selected from phosphate, thiocyanate, chlorate, perchlorate, tetrafluoroborate, acetylacetonate, merceto, amide, alkoxide, carboxylate and derivatives thereof.)

[Formula 2]

(3)

[Formula 4]

(The R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are independently of each other hydrogen; a substituted or unsubstituted C ₁ ~ C ₃₀ aliphatic alkyl group, alicyclic alkyl group, aryl group or aralkyl group; polymer A compound group; a heterocyclic compound group; and derivatives thereof, wherein R ₁ and R ₂ or R ₄ and R ₅ may be linked to each other to form a ring.)

Specifically, for example, in the case where n is 1 and X is absent, the compound of Formula 1 may be Au, Cu, Zn, Ni, Co, Pd, Pt, Ti, V, Mn, Fe, Cr, Zr, Nb, Metals such as Mo, W, Ru, Cd, Ta, Re, Os, Ir, Al, Ga, Ge, In, Sn, Sb, Pb, Bi, Sm, Eu, Ac, Th, or alloys thereof; Other metal compounds are, for example, copper oxide, zinc oxide, vanadium oxide, nickel sulfide, palladium chloride, copper carbonate, iron chloride, gold chloride, nickel chloride, cobalt chloride, bismuth nitrate, acetylacetonated vanadium, cobalt acetate, Tin lactate, manganese oxalate, gold acetate, palladium oxalate, copper 2-ethyl hexanoate, iron stearate, nickel formate, ammonium molybdate, zinc citrate, bismuth acetate, copper cyanide, cobalt carbonate, platinum chloride, chlorochloric acid, tetrabu Toxytitanium, Dimethoxyzirconium Dichloride, Aluminum Isopropoxide, Tin Tetraplo To include borate, tantalum methoxide, dodecyl meokep rabbit gold, indium acetylacetonate and its derivatives such as, but not particularly limited thereto.

And in Chemical Formula 2, Chemical Formula 3 or Chemical Formula 4, R ₁ to R ₆ may be, for example, hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, hexyl, ethylhexyl, heptyl, Octyl, isooctyl, nonyl, decyl, dodecyl, hexadecyl, octadecyl, docodecyl, cyclopropyl, cyclopentyl, cyclohexyl, allyl, hydroxy, methoxy, hydroxyethyl, methoxyethyl, 2-hydroxy Propyl, methoxypropyl, cyanoethyl, ethoxy, butoxy, hexyloxy, methoxyethoxyethyl, methoxyethoxyethoxyethyl, hexamethyleneimine, morpholine, piperidine, piperazine, ethylenediamine , Propylenediamine, hexamethylenediamine, triethylenediamine, pyrrole, imidazole, pyridine, carboxymethyl, trimethoxysilylpropyl, triethoxysilylpropyl, phenyl, methoxyphenyl, cyanophenyl, phenoxy, tolyl, benzyl And derivatives thereof, and polyallyl Or it may include a polymer compound and a derivative thereof such as the polyethyleneimine is not particularly limited thereto.

Specific examples of the compound include, for example, ammonium carbamate compounds of formula (2) are ammonium carbamate, ethylammonium ethyl carbamate, isopropylammonium isopropylcarbamate, n-butylammonium n-butylcarbamate, isobutylammonium isobutyl Carbamate, t-butylammonium t-butylcarbamate, 2-ethylhexyl ammonium 2-ethylhexyl carbamate, octadecylammonium octadecyl carbamate, 2-methoxyethylammonium 2-methoxyethylcarbamate, 2-sia Noethylammonium 2-cyanoethylcarbamate, dibutylammonium dibutylcarbamate, dioctadecylammonium dioctadecylcarbamate, methyldecylammonium methyldecylcarbamate, hexamethyleneimineammonium hexamethyleneiminecarbamate, morpholinium Morpholine carbamate, pyridinium ethylhexyl carbamate, triethylenedium isopropyl carbamate, benzyl ammonium benzyl carbamate, tri Ethoxysilyl propyl ammonium triethoxy silyl propyl carbamate, etc., The ammonium carbonate-based compound of Formula 3 is ammonium carbonate, ethyl ammonium ethyl carbonate, isopropyl ammonium isopropyl carbonate, n-butyl ammonium n-butyl carbonate , Isobutylammonium isobutyl carbonate, t-butylammonium t-butylcarbonate, 2-ethylhexyl ammonium 2-ethylhexyl carbonate, 2-methoxyethylammonium 2-methoxyethyl carbonate, 2-cyanoethylammonium 2-cya Noethyl carbonate, octadecyl ammonium octadecyl carbonate, dibutylammonium dibutyl carbonate, dioctadecyl ammonium dioctadecyl carbonate, methyl decyl ammonium methyl decyl carbonate, hexamethylene imine ammonium hexamethylene imine carbonate, morpholine ammonium morphocarbonate, Benzyl Ammonium Benzyl Carbonate, Triethoxysilylpropyl Ammonium Triethoxysilylpropyl carbonate, triethylene dimethyl amine isopropyl carbonate, etc. The ammonium bicarbonate-based compound of Formula 4 is ammonium bicarbonate, isopropyl ammonium bicarbonate, t-butylammonium bicarbonate, 2-ethylhexyl ammonium Bicarbonate, 2-methoxyethylammonium bicarbonate, 2-cyanoethylammonium bicarbonate, dioctadecylammonium bicarbonate, pyridinium bicarbonate, triethylenedidium bicarbonate and the like.

A metal complex compound is prepared by reacting a metal or a metal compound with an ammonium carbamate, ammonium carbonate-based or ammonium bicarbonate-based compound prepared as described above. The metal ink of the electrode layer used in the present invention may be a solvent, stabilizer, dispersant, binder resin, mold releasing agent, reducing agent, or surfactant as necessary in addition to the metal complex compound and the metal or nonmetal compound or at least one of these mixtures. additives such as surfactants, wetting agents, thixotropic agents or leveling agents may be included.

The metal conductor does not need to be particularly limited. That is, any known one may be used as long as it is suitable for the purpose of the invention. That is, as the type of conductor, for example, Ag, Au, Cu, Zn, Ni, Co, Pd, Pt, Ti, V, Mn, Fe, Cr, Zr, Nb, Mo, W, Ru, Cd, Ta, Selected from the group of transition metals such as Re, Os, Ir, or a group of metals such as Al, Ga, Ge, In, Sn, Sb, Pb, Bi, or lanthanides such as Sm, Eu, At least one metal selected from the group of actinides-based metals, or alloys or alloy oxides thereof is included.

In addition, the metal precursor is not particularly limited. That is, it can be used when the purpose of the present invention is met, and in particular, it is more preferable to exhibit conductivity through heat treatment, oxidation or reduction treatment, infrared ray, ultraviolet ray, electron beam, laser treatment, and the like. Specifically, for example, gold acetate, palladium oxalate, silver 2-ethylhexanoate, copper 2-ethylhexanoate, iron stearate, nickel formate, zinc sheet Carboxylic acid metals such as zinc citrate, silver nitrate, copper cyanide, cobalt carbonate, platinum chloride, gold chloride, tetrabutoxy titanium, dimethoxyzirconium dichloride, aluminum isopropoxide, tin tetrafluoroborate, Metal compounds such as vanadium oxide, indium-tin oxide, tantalum methoxide, bismuth acetateo, dodecyl mercetoxide, indium acetylacetonate, and the like.

In addition, the shape of the metal conductor and the metal precursor may be spherical, linear, plate-shaped, or a mixture thereof, and may be in the form of particles containing nanoparticles, powder, flake, colloid ( It can be used in various states such as colloid, hybrid, sol, solution, or a mixture of one or more of them.

The size or the amount of the metal conductor or metal precursor need not be particularly limited as long as it meets the metal ink characteristics of the present invention. That is, the size is preferably 10 microns or less, more preferably 1 nanometer (nm) or more and 1 micron or less, considering the uniformity of the coating film after firing, the amount of use does not exceed a certain limit so that the firing temperature is too high or printing process If you do not have a problem. Usually, the amount used is preferably in the range of 1 to 95 percent, more preferably 1 to 50 percent by weight, based on the total ink composition.

The solvent contained in the metal ink may be selected from water, alcohols, glycols, acetates, ethers, ketones, aliphatic hydrocarbons, aromatic hydrocarbons or halogenated hydrocarbon-based solvents, specifically, water, methanol, ethanol, isopropanol, 1- Methoxypropanol, butanol, ethylhexyl alcohol, terpineol, ethylene glycol, glycerin, ethyl acetate, butyl acetate, methoxypropyl acetate, carbitol acetate, ethyl carbitol acetate, methyl cellosolve, butyl cellosolve, di Ethyl ether, tetrahydrofuran, dioxane, methyl ethyl ketone, acetone, dimethylformamide, 1-methyl-2-pyrrolidone, dimethyl sulfoxide, hexane, heptane, dodecane, paraffin oil, mineral spirit, benzene, toluene At least one selected from xylene, chloroform, methylene chloride, carbon tetrachloride and acetonitrile can do.

The coating or printing method of the metal ink for forming the electrode layer is spin coating, roll coating, spray coating, dip coating, flow according to the physical properties of the metal ink and the form of the substrate, respectively. Coating, Comma Coating, Key Coating, Die Coating, Doctor Blade, Dispensing, Inkjet, Offset, Screen, Pad, Gravure, Flexography, Stencil , Imprinting, electrostatic coating, electrodeposition (electro-deposition) coating, etc., if the present invention is not particularly limited thereto.

On the other hand, when coating or printing using the above method, the thickness of the electrode layer does not need to be particularly limited, but usually 1 nanometer to 10 microns, more preferably 1 nanometer to 2 microns. The printing thickness can be adjusted by controlling the concentration of metal ink, the printing speed or the transfer amount.

The post-treatment step may be heat treated under a normal inert atmosphere, but may be processed in air, nitrogen, carbon monoxide, or even a mixed gas of hydrogen and air or another inert gas, if necessary. The heat treatment is usually performed at 80 to 400 ° C, preferably at 90 to 300 ° C, more preferably at 100 to 250 ° C. In addition, heat treatment of two or more steps at low and high temperatures within the above range is also good for the uniformity of the thin film. For example, it is good to process for 1 to 30 minutes at 80-150 degreeC, and to process for 1 to 30 minutes at 150-300 degreeC.

In order to improve the surface uniformity of the electrode layer formed above and the interface characteristics with the dielectric layer, the electrode layer may be treated on the electrode layer by physical and chemical methods.

Physical methods for improving surface uniformity include direct pressurization on thin films, such as pressurization using gases such as air or nitrogen, pressurization and crimping using conveyor belts, rolls or presses, vacuum chambers, and gas injection. Or any method that can pressurize indirectly can be used.

At the time of performing the physical process, after the coating or printing of the metal ink, the firing process is not overwhelming, but more preferably, most of the volatile liquid is removed and the shape of the metal thin film is smeared or buried by the pressure process. Not good point. The temperature of the process is generally within the range of 50 to 600 ℃, preferably 80 to 500 ℃, most preferably 100 to 500 ℃ in a range in which the substrate and the metal thin film is not damaged in consideration of the characteristics of the substrate. In addition, treating the two or more physical processes at low and high temperatures within the above range is also good for the uniformity of the thin film. For example, it is good to process at 80-150 degreeC for 5 second, and to process at 150-300 degreeC for 15 second. In addition, the physical process may use a pressurization process or a depressurization process, and may be used simultaneously if necessary. Pressure of the pressurized process or vacuum process is one in a range in consideration of the properties of the substrate that does not damage the substrate and the metal layer, the pressing step is preferably at a pressure ranging from reduced pressure process of 1Kg / cm ² to about 5000Kg / cm ² to 10 ² The range of torr-10 ^-6 torr is preferable.

In addition, chemical treatment methods for improving the interfacial properties between the electrode layer and the dielectric layer include SiO ₂ sol, fatty acids such as oleic acid, silicone compounds such as methylsilyl isocyanate, cellulose derivatives such as polysaccharide, phosphoric acid or phosphonic acid. Phosphate derivatives or the like (thiol group) in which 6-24 alkyl groups having 6 to 24 carbon atoms are introduced, such as 1-hexyl, dodecyl, lauryl, hexadecyl, and octadecyl And the like and a mixture of one or two or more thereof may be used to surface-treat the electrode layer by various methods.

The dielectric used for the dielectric layer of the thin film capacitor according to the present invention does not need to be particularly limited as long as it meets the characteristics of the present invention. That is, the characteristics of the dielectric may be large or low in the dielectric constant, have a ferroelectric characteristic, have a piezoelectric characteristic, or the size of the refractive index (refractive index) need to be limited to such characteristics none. Such dielectrics include, for example, polyethylene, polypropylene, polystyrene, polyethylene terephthalate (PET), polycarbonate (PC), polyvinylidene fluoride (PVDF), various fluoropolymers, polyimides, polyolefins, polyphenylene sulfides ( PPS), polypyrrole (PPy), polythiophene, polyurethane, various acrylic resins, epoxy, silicone resins, Teflon, acrylonitrile resins, ethyl cellulose, polyvinylphenol (PVP), various polymer resins such as BaCo ₃ , CaCO ₃ , TiO ₂ , ZnO ₂ A ceramic material, BaTiO _3, such as an _{[(Ba x Ca 1-x} ) M (Ti y Zr 1-y) O 3] was added, such as TiO _2, BaTiO _3, CaTiO ₃ in the composition of the powder as a main component, etc., and Lead acetate, ceramic material containing Mg, Mn and added one or two or more rare earth elements selected from Ho, Y, Er, Tm, Yb, Lu, Sm, Eu, Gd, Tb and Dy Lead Zirconate titanate with Mg, Zr, Ti, Zn, Nb, La, Sr, etc. added to Pb organic material selected from the group consisting of Pb (CH3CHO2) 2 3H2O] and lead nitrate [Pb (NO3) 2]. (PZT), Lead Magnesium Niobate (PMN), Lead zinc Niobate (PZN) and other materials, SrBi2Ta ₂ O ₃ (SBT), SrTiO ₃ (STO), Bi (La, Ti) O ₃ (BLT), Bi (Sr, Ti) O ₃ (BST) and others TiO ₂ , SiO ₂ , ZrO ₂ , HfO ₂ , Ta ₂ O ₃ , CaTiO ₃ , TaNbO, KNbO ₃ , NaTaO ₃ , SrZrO ₃ , BiFeO ₃ At least one dielectric may be selected from ceramic compounds such as the above, or a composite mixture thereof may be used.

In addition, the shape of the dielectric may be powder, fiber, rod, flake, film, sheet, colloid, hybrid, sol. It can be used in various states, such as solution, composite state, or mixed form in which one or more kinds thereof are selected.

According to the present invention, the interfacial characteristics between the electrode layer and the dielectric layer are greatly improved, and thus, a high quality thin film capacitor can be manufactured, and the manufacturing process can be applied to a roll-to-roll solution printing process, thereby enabling mass production of the capacitor at low cost.

In addition, through the present invention, it is possible to easily mass-produce thin film devices for various applications such as capacitors, memories, sensors, piezoelectric elements, varistors, energy harvesting elements, and the like at low cost.

The present invention will be described in more detail with reference to the following examples. However, the following examples are merely examples to help understanding of the present invention, and the claims of the present invention are not limited thereto.

Preparation of Metal Ink Composition 1

34.89 grams (129.8 mmol) of viscous liquid containing 7: 3 2-ethylhexyl ammonium 2-ethylhexyl carbamate and butylammonium butyl carbamate in a molar ratio in a 250 milliliter Schlenk flask with a stirrer 12.03 grams (51.92 mmol) of silver oxide (manufactured by Aldrich Co., Ltd.) was added thereto, and the mixture was reacted with stirring at room temperature for 2 hours. As the reaction proceeded, the complex initially formed in a black suspension. The color faded, and finally 46.92 grams of a yellow, transparent liquid silver complex was obtained. The thermal analysis (TGA) revealed that the silver content was 23.65 weight. Percent. The silver complex solution was diluted with IPA to prepare metal ink solution 1 having a silver content of 10% by weight and a viscosity of 14 cps.

Preparation of Metal Ink Composition 2

Into a 250 milliliter Schlenk flask with a stirrer was added 58.93 grams of metal ink 1 and 41.07 grams of silver nanoparticles (manufactured by Ferro) and stirred for 30 minutes at room temperature. The stirred liquid was secondly stirred through a three-rod roll mill to prepare Metal Ink 2 having a content of 55 wt% silver and a viscosity of 6000 Cps (Brook field DVII pro, 15 spindle, 50 rpm).

Example 1

For preparing a thin film capacitor, a 300 mm wide, 200 m long PET film was prepared, and then the metal ink composition 1 was prepared using a gravure coater at 10 M / min. After coating at a speed, heat treatment was performed at 150 ℃ to form a lower electrode layer with a thickness of 0.1um on the surface of PET. A 1% polyimide solution diluted in N-Methyl-2-Pyrrolidone at a rate was coated to form a 0.15um thick dielectric layer. The metal ink composition 1 on the gravure coating machine to form a 0.1um thick upper electrode to prepare a thin film capacitor. The Ra value of the lower electrode was 13 nm and the surface resistance was 350 mPa / sq.

[Example 2]

For preparing a thin film capacitor, a 300 mm wide, 200 m long PET film was prepared, and then the metal ink composition 1 was prepared using a gravure coater at 10 M / min. After coating at speed, heat treatment at 150 ℃ and pressurizing process at 140 ℃ for 45 seconds using 20Kg / cm ² thermocompressor to form a lower electrode layer with a thickness of 0.1um on the surface of PET. / min. A 1% polyimide solution diluted in N-Methyl-2-Pyrrolidone at a rate was coated to form a 0.15um thick dielectric layer. Metal ink composition 1 was formed thereon using a spin coating coater to form an upper electrode having a thickness of 0.1um to prepare a thin film capacitor. The Ra value of the lower electrode was 6 nm and the surface resistance was 280 mPa / square.

Example 3

After preparing a silicon wafer for manufacturing a thin film capacitor, the metal ink composition 1 was coated at a speed of 10 rpm using a spin coater, followed by heat treatment at 150 ° C. to form a lower electrode layer having a thickness of 0.09 μm on a PET surface, and then a 1-hexyl merketane solution. After dipping in, dried and coated with a 1% polyimide solution diluted in N-Methyl-2-Pyrrolidone at 15rpm using a spin coater to form a dielectric layer of 0.13um thickness. A metal thin film capacitor was prepared by forming an upper electrode having a thickness of 0.09 μm using a spin coater on the metal ink composition 1. The Ra value of the lower electrode was 12 nm and the surface resistance was 360 mPa / square.

Example 4

For preparing a thin film capacitor, a 300 mm wide, 200 m long PET film was prepared, and then the metal ink composition 1 was prepared using a gravure coater at 10 M / min. After coating at a speed, heat treatment was performed at 150 ℃ to form a lower electrode layer with a thickness of 0.1um on the surface of PET. Propylene glycol monomethyl ether acetate diluted 2% polyvinylidene fluoride solution was coated at a rate to form a dielectric layer of 0.17um thickness. The metal ink composition 1 on the gravure coating machine to form a 0.1um thick upper electrode to prepare a thin film capacitor. The Ra value of the lower electrode was 13 nm and the surface resistance was 350 mPa / sq.

Example 5

For preparing a thin film capacitor, a 300 mm wide, 200 m long PET film was prepared, and then the metal ink composition 1 was prepared using a gravure coater at 10 M / min. After coating at a speed, heat treatment was performed at 150 ℃ to form a lower electrode layer with a thickness of 0.1um on the surface of PET. A 5% TiO ₂ Sol solution was coated at a rate to form a 0.2um thick dielectric layer. A metal thin film capacitor was prepared by forming the upper electrode having a thickness of 0.1 μm using a gravure coater on the metal ink composition 1. The Ra value of the lower electrode was 13 nm and the surface resistance was 350 mPa / □.

Example 6

For preparing a thin film capacitor, a 300 mm wide, 200 m long PI film was prepared, and then the metal ink composition 1 was subjected to 10 M / min using a gravure coater. After coating at a rate and heat-treated at 150 ℃ to form a lower electrode layer of 0.1um thickness on the PET surface and immersed in a polysaccharide solution, using a microgravure coater on it 10M / min. 5% PZT (Lead Zirconate titanate) solution was coated to form a 0.3um thick dielectric layer. The metal ink composition 1 on the gravure coating machine to form a 0.1um thick upper electrode to prepare a thin film capacitor. The Ra value of the lower electrode was 13 nm and the surface resistance was 350 mPa / sq.

Example 7

For preparing a thin film capacitor, a 300 mm wide, 200 m long PET film was prepared, and then the metal ink composition 1 was prepared using a gravure coater at 10 M / min. After coating at a speed, heat treatment was performed at 150 ℃ to form a lower electrode layer with a thickness of 0.1um on the surface of PET. A 1% polyimide solution diluted in N-Methyl-2-Pyrrolidone at a rate was coated to form a 0.15um thick dielectric layer. A metal thin film capacitor was formed on the metal ink composition 2 by using a silkscreen coating machine to form an upper electrode having a thickness of 0.7 μm. The Ra value of the lower electrode was 13 nm and the surface resistance was 350 mPa / sq.

Example 8

After preparing a silicon wafer for manufacturing a thin film capacitor, the metal ink composition 1 was coated at a speed of 10 rpm using a spin coater, and then heat treated at 150 ° C. and pressurized at 140 ° C. for 45 seconds using a 20 Kg / cm ² thermocompressor. The lower electrode layer having a thickness of 0.1 μm was formed and a 1% polyimide solution diluted in N-Methyl-2-Pyrrolidone was coated at 15 rpm using a spin coater to form a dielectric layer having a thickness of 0.15 μm. A metal ink composition 1 was formed thereon using a spin coater to form an upper electrode having a thickness of 0.1 μm to prepare a capacitor of a thin film. The Ra value of the lower electrode was 5 nm and the surface resistance was 270 mPa / square.

1 is a structure of a thin film capacitor according to the present invention

 <Explanation of symbols for the main parts of the drawings>

1: Substrate 2: Lower electrode

2: dielectric layer 4: upper electrode layer

Claims (12)

In the method of manufacturing a thin film capacitor consisting of a lower electrode layer, a dielectric layer, and an upper electrode layer, the lower electrode layer and the upper electrode layer are formed by printing or coating a metal ink including a metal complex compound as an essential component, and then baking the same. Method of manufacturing a thin film capacitor, characterized in that The thin film capacitor of claim 1, wherein the organometallic complex compound is obtained by reacting at least one metal or metal compound represented by Formula 1 with at least one ammonium compound represented by Formula 2, Formula 3, or Formula 4. Manufacturing Method [Formula 1] MnX (M is a metal or a metal alloy, n is an integer of 1 to 10, X is absent, hydrogen, ammonium, oxygen, sulfur, halogen, cyano, cyanate, carbonate, nitrate, nitrite, sulfate, And at least one substituent selected from phosphate, thiocyanate, chlorate, perchlorate, tetrafluoroborate, acetylacetonate, merceto, amide, alkoxide, carboxylate and derivatives thereof.) [Formula 2]

(3)

[Formula 4]

(The R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are independently of each other hydrogen; a substituted or unsubstituted C ₁ ~ C ₃₀ aliphatic alkyl group, alicyclic alkyl group, aryl group or aralkyl group; polymer A compound group; a heterocyclic compound group; and derivatives thereof, wherein R ₁ and R ₂ or R ₄ and R ₅ may be linked to each other to form a ring.) The method of claim 2, wherein the metal or metal compound is Au, Cu, Zn, Ni, Co, Pd, Pt, Ti, V, Mn, Fe, Cr, Zr, Nb, Mo, W, Ru, Cd, Ta, Re, Os, Ir, Al, Ga, Ge, In, Sn, Sb, Pb, Bi, Sm, Eu, Ac, Th, Copper Oxide, Zinc Oxide, Vanadium Oxide, Nickel Sulfide, Palladium Chloride, Copper Carbonate, Iron Chloride Gold chloride, nickel chloride, cobalt chloride, bismuth nitrate, vanadium acetylacetonate, vanadium acetate, cobalt acetate, tin lactate, manganese oxalate, gold acetate, palladium oxalate, 2-ethyl hexanoate, iron stearate, nickel formate, ammonium molybdate , Zinc citrate, bismuth acetate, copper cyanide, cobalt carbonate, platinum chloride, gold chloride, tetrabutoxy titanium, dimethoxyzirconium dichloride, aluminum isopropoxide, tin tetrafluoro borate, tantalum methoxide, dodecyl mercury Either one selected from the group of gold earth and indium acetylacetonate Characterized in that it comprises the components of the method of manufacturing a thin film capacitor according to According to claim 2, wherein R ₁ to R ₆ of the ammonium compound is hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, hexyl, ethylhexyl, heptyl, octyl, isooctyl, nonyl, decyl, Dodecyl, hexadecyl, octadecyl, docodecyl, cyclopropyl, cyclopentyl, cyclohexyl, allyl, hydroxy, methoxy, hydroxyethyl, methoxyethyl, 2-hydroxy propyl, methoxypropyl, cyanoethyl , Ethoxy, butoxy, hexyloxy, methoxyethoxyethyl, methoxyethoxyethoxyethyl, hexamethyleneimine, morpholine, piperidine, piperazine, ethylenediamine, propylenediamine, hexamethylenediamine, tri Ethylenediamine, pyrrole, imidazole, pyridine, carboxymethyl, trimethoxysilylpropyl, triethoxysilylpropyl, phenyl, methoxyphenyl, cyanophenyl, phenoxy, tolyl, benzyl and its derivatives, and polyallylamine Polymerization like Polyethylenimine Method for producing a thin film capacitor, characterized in that it comprises any one or more components selected from the group and derivatives thereof The thin film capacitor of claim 1, wherein the metal ink further comprises a metal conductor, a solvent, a stabilizer, a dispersant, a binder resin, a release agent, a reducing agent, a surfactant, a humectant, a thixotropic agent, or a leveling agent, alone or in combination. Manufacturing Method The method of claim 1, wherein the lower electrode layer or the upper electrode layer has a thickness of 1 nanometer to 10 microns. The method of manufacturing a thin film capacitor according to claim 1, wherein the firing step is performed in parallel with a heating step and a pressure step. 8. The method of manufacturing a thin film capacitor according to claim 7, wherein the pressure step is selected from a pressurization method using a gas, a pressurization press method using a conveyor belt, a roll or a press, and a method using a vacuum chamber. 8. The method of claim 7, wherein the pressure process is performed at the time when the metal nanoparticle is formed by the reduction of the organometallic complex compound upon the firing of the metal ink, or when the metal nanoparticle is formed. The method of claim 1, further comprising surface treatment of the electrode layer to improve an interface property between the electrode layer and the dielectric layer. The surface treatment of claim 10, wherein the surface treatment is selected from fatty acids, silicone compounds, cellulose derivatives, phosphoric acid derivatives, or methane having 6 to 24 carbon atoms in which alkyl groups are introduced. Process for producing a thin film capacitor, characterized in that the treatment. 10. The method of claim 9, wherein the fatty acid is SiO ₂ sol, oleic acid, the silicone compound is methylsilyl isocyanate, the cellulose derivative is a polysaccharide, the phosphoric acid derivative is phosphoric acid or phosphonic acid, the alkyl group having 6 to 24 carbon atoms The introduced methane is selected from 1-hexyl methane, dodecyl methane, lauryl methane, hexadecyl methane, and octadecyl methane.

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