KR101457304B1 - Method of preparing high dielectric insulating material and insulating device using the same - Google Patents

Abstract

The present invention provides a method of manufacturing a high-dielectric insulating material which includes the steps of: introducing high-dielectric nanoparticles and high fluorinated carboxylic acid ligand into high fluorinated solvent to react with each other (first step); collecting the high-dielectric nanoparticles transposed to high fluorinated carboxylic acid ligand by acetone (second step); and removing remaining acetone (third step). Thus, a high-dielectric insulating material is provided to enable a solution process in high fluorinated solvent. The high-dielectric insulating material, which is in a state of solution dissolved in the high fluorinated solvent, may be used as an insulating device for a transistor or a solar cell through various printing schemes. In addition, the high fluorinated solvent does not damage chemically, physically and electrically an organic semiconductor layer formed at a lower portion of an dielectric layer, so that layers having a high quality can be laminated.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method of manufacturing a high dielectric constant insulating material and an insulating device using the high dielectric constant insulating material,

The present invention relates to a high-k insulating material, and more particularly, to a method of manufacturing a high-k insulating material capable of performing a solution process in a solvent having excellent chemical stability.

In general, as semiconductor devices or multilayer wiring boards are miniaturized, highly integrated, and densified, high dielectric constant insulating materials are required. A silicon oxide film, a silicon nitride film, a polyimide resin, or the like is used widely as a semiconductor element buffer coat film or a multilayer wiring board interlayer insulating film. The relative dielectric constant is about 4 to 5, 7 to 9, and 3.5 to 4, respectively.

Particularly, since the fluororesin has excellent properties such as high heat resistance and high endurance, the development of insulating materials using fluororesins has been actively conducted. However, since the semiconductor element or the multilayer wiring board is a composite with a wiring metal or another inorganic insulating film and is exposed to a high temperature of 200 to 450 DEG C in the manufacturing process and the mounting process, the fluororesin has a low glass transition temperature, Or a small modulus of elasticity and a high coefficient of linear expansion cause the reliability of the device or the wiring board to be lowered, making it difficult to use an insulating material.

Japanese Patent Application Laid-Open No. 6-340710 discloses a fluorine-containing polymer containing a triazine ring. However, an electronic article or an insulating material having a thin film of this polymer is not disclosed.

According to Korean Patent Laid-Open Publication No. 10-2006-0025788, the mold oxide film and the regenerated oxide film pattern are removed using the fluororesin or the fluorine-based solvent, and the rinsing and drying process is performed to prevent the lower electrodes from falling down And discloses a method of manufacturing a capacitor that can process processes cleaner and faster.

However, in order to satisfy demands for large-sized and flexible electronic devices, a high-dielectric insulating material prepared by a solution process using a fluorine-based solvent having excellent chemical stability has not been disclosed, and it is dissolved in a fluorine- It is still necessary to develop a possible high dielectric constant insulating material which can be produced by a printing technique.

An object of the present invention is to provide a method of manufacturing a high dielectric constant insulating material capable of performing a solution process in a high fluorine solvent and to provide an insulating element using a high dielectric constant insulating material.

The present invention relates to a process for preparing a high fluorine-containing solvent by adding high-k nanoparticles and a high fluorine-containing carboxylic acid ligand to a high fluorine solvent (first step); Recovering the high-k nano-particles substituted with a high fluorine-containing carboxylic acid ligand with acetone (second step); And removing the remaining acetone (third step). The present invention also provides a method of manufacturing a high dielectric constant insulating material.

And 10 to 20 parts by weight of high-dielectric constant nano-particles and 30 to 60 parts by weight of a high-fluorine-containing carboxylic acid ligand are added to 100 parts by weight of the high fluorine solvent.

The high fluorine-based solvent may be selected from the group consisting of hydrofluoroethers, perfluorocarbons, hydrofluorocarbons, and fluorinated aromatic solvents.

The high-permittivity nanoparticles may be any one selected from hafnium oxide, zirconium oxide, and barium titanate.

The high fluorine-containing carboxylic acid ligand has an ether group and has a fluorine content of 60 to 64%.

The high fluorine-containing carboxylic acid ligand may be at least one of perfluoro-3,6,9-trioxatridecanoic acid, perfluoro phosphonic acid, , (7,7,8,8,9,9,10,10,11,11,12,12,13,13,14,14,14-heptadecafluorotetradecanooic acid solution seeds (7,7, 12, 13, 13, 14, 14, 14-heptadecafluorotetradecanoic acid), 2- (5,5,6,6,7,7,8, 8,8,9,9,10,10,11,11,12,12,13,13,14,14,14- , 8,9,9,10,10,11,11,12,12,12-heptadecafluorododecyl) malonic acid solution (2- (5, 5, 6, 6, 7, , 9,9,10,10,11,11,12,12,12-heptadecafluorododecyl) malonic acid), 7,7,8,8,9,9,10,10,11,11,12,12,13 , 14,14,14-hexadecafluoro-2- (5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-hepta (7,7,8,8,9,9,10,10,11,11,12,12,13,14,14,14-hexadecafluoro-2- (5) -tetradecanoic < / RTI & , 5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heptadecafluorododecyl) tetradecanoic acid), 2- (5,5,6,6, 7,7,8,8,9,9,10,10,11,11,12,12,12-heptadecafluorododecyl) -2- (5,5,6,6, 7,7,8,8,9,9,10,10,11,12,12,12-hexadecafluorododecyl) malonic acid (2- (5,5,6,6,7,7- 8,8,9,9,10,10,11,11,12,12,12-heptadecafluorododecyl) -2- (5,5,6,6,7,7,8,8,9,9,10, 10, 11, 12, 12, 12-hexadecafluorododecyl) malonic acid, perfluorodecanoic acid and perfluorooctadecanoic acid.

Also disclosed is an insulating device obtained by dissolving a high dielectric constant insulating material in a high fluorine solvent and performing thin film molding.

The insulating device may also be at least one selected from the group consisting of transistors, solar cells, coatings, non-volatile memories, backplanes for flexible displays, secondary battery electrolytes, flexible integrated circuits, flexible electronic paper displays, It can be characterized that it is applied.

According to the method of manufacturing a high dielectric constant insulating material according to the present invention, a high dielectric constant insulating material which can be subjected to a solution process in a high fluorine solvent is provided. The high dielectric constant insulating material dissolved in a high fluorine solvent can be used as an insulating element such as a transistor or a solar cell through various printing techniques. In addition, since a high fluorine-based solvent is not chemically, physically, or electrically damaged in the organic semiconductor layer formed under the dielectric layer, high-quality layers can be stacked.

FIG. 1 is a configuration diagram of a thin film transistor according to an embodiment of the present invention,
2A shows a process of synthesizing TOPO-capped hafnium isopropoxide isopropanol and trioctylphosphine oxide (TOPO) in hafnium chloride to synthesize hafnium isopropoxide isopropanol and hafnium chloride, Also,
2B is a schematic view showing a process of synthesizing zirconium oxide nanoparticles in which TOPO is capped by adding zirconium isopropoxide isopropanol and zirconium chloride,
3 is a TEM image of a high dielectric constant insulating material in which hafnium oxide nanoparticles are dispersed in a high fluorine solvent,
4 is a TEM image of a high dielectric constant insulating material in which zirconium oxide nanoparticles are dispersed in a high fluorine solvent,
5 is a schematic diagram showing a process in which a ligand surrounding a hafnium oxide nanoparticle in a high fluorine solvent is substituted with a high fluorine-containing carboxylic acid ligand,
FIG. 6 is a graph showing the results of a pre-combination structural formula of a high fluorine-based solvent according to an embodiment of the present invention,
FIG. 7 is a photograph of a high fluorine solvent-dispersed high dielectric constant insulating material made of hafnium oxide nanoparticles according to an embodiment of the present invention,
FIG. 8 is a photograph of a high fluorine solvent-dispersed high dielectric constant insulating material made of zirconium oxide nanoparticles according to an embodiment of the present invention,
9 and 10 are graphs showing the dielectric constant of the insulating device according to the present invention, respectively.

The present invention relates to a process for preparing a high fluorine-containing solvent by reacting high-k nanoparticles and a high fluorine-containing carboxylic acid ligand in a high fluorine solvent (first step); Recovering the high-k nano-particles substituted with a high fluorine-containing carboxylic acid ligand with acetone (second step); And removing the remaining acetone (third step). The present invention also provides a method of manufacturing a high dielectric constant insulating material.

The high-k insulating material can be subjected to a solution process in a high-fluorine-based solvent excellent in chemical stability, thereby providing an insulating device applied to a transistor through various printing techniques.

 10 to 20 parts by weight of high-dielectric constant nano-particles and 30 to 60 parts by weight of a high-fluorine-based carboxylic acid ligand may be added to 100 parts by weight of the high fluorine solvent.

The high fluorine-based solvent may be selected from the group consisting of hydrofluoroethers, perfluorocarbon, hydrofluorocarbons, and fluorinated aromatic solvents.

The HFE is a composite organic solvent which is liquid at room temperature due to its low viscosity and high molecular weight, and therefore, when the solubility of the high-dielectric insulating material is increased to use the high-dielectric insulating material in a solution process, the high- It may be dissolved in a solvent to form a liquid phase.

The high-k component nanoparticles may be any one selected from hafnium oxide, zirconium oxide, and barium titanate.

The hafnium oxide may be prepared by adding trioctylphosphine oxide (TOPO) to hafnium isopropoxide isopropanol and hafnium chloride to form trioctylphosphine oxide-capped oxide Hafnium nanoparticles can be synthesized.

The zirconium oxide may be prepared by adding zirconium isopropoxide isopropanol and zirconium chloride to synthesize zirconium oxide nanoparticles in which TOPO is capped with zirconium isopropoxide isopropanol and zirconium chloride.

The high fluorine-containing carboxylic acid ligand may have an ether group and a fluorine content of 60 to 64%.

The high fluorine-containing carboxylic acid ligand may be at least one selected from the group consisting of perfluoro-3,6,9-trioxatridecanoic acid solution, perfluorophosphonic acid, 7,7,8,8,9,9,10,10, 11,11,12,12,13,13,14,14,14-heptadecafluorotetradecanoic acid solution juice, 2- (5,5,6,6,7,7,8,8,9,9 , 10,10,11,11,12,12,12-heptadecafluorododecyl) malonic acid liquid, 7,7,8,8,9,9,10,10,11,11,12,12, 13,14,14,14-hexadecafluoro-2- (5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12- Heptadecafluorododecyl) tetradecanoic acid liquoride, 2- (5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12- Heptadecafluorododecyl) -2- (5,5,6,6,7,7,8,8,9,9,10,10,11,12,12,12-hexadecafluorododecyl) Malonic acid, perfluoroorecanoic acid, and perfluoro-octadecanoic acid.

The ratio of the high-permittivity nanoparticle to the high-fluorine-containing ligand in the step of adding and reacting the high-permittivity nanoparticle and the high-fluorine-containing carboxylic acid ligand (step 1) is 1: 2 to 3, can do.

In the step of adding and reacting the high-permittivity nanoparticle and the high-fluorine-containing carboxylic acid ligand (first step), the high-permittivity nanoparticle and the high fluorine-containing carboxylic acid ligand may be introduced into a reactor and stirred under nitrogen, The temperature may be raised to 130 ° C, and the reaction may be carried out for 3 to 4 hours.

The step of recovering the high-k rate nanoparticles substituted with the high fluorine-containing carboxylic acid ligand as the acetone may further include a step of recovering the high-k < th >

The high-k insulating material is dissolved in a high-fluorine-based solvent and thin-film-molded to manufacture an insulating device. FIG. 1 shows a configuration of a thin film transistor according to an embodiment of the present invention. Since the high-dielectric insulating device fabricated in a liquid phase can be subjected to a solution process, it is possible to cope with the enlargement and softening of electronic devices, and a solvent such as HFE does not cause chemical, physical, or electrical damage to the organic semiconductor layer formed under the dielectric layer It is possible to carry out the lamination process with high quality multilayer.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.

< Example  1> High permittivity  Nanoparticle manufacturing

1. Manufacture of hafnium oxide nanoparticles

Hafnium isopropoxide isopropanol (2 mmol, 0.95 g), hafnium chloride (2 mmol, 0.65 g) and trioctylphosphine oxide (TOPO, 26 mmol, 10.0 g) &Lt; / RTI &gt; and stirred under nitrogen.

The reaction vessel was rapidly heated to 360 &lt; 0 &gt; C and stirred rapidly for 2 hours. After the reaction was completed, the temperature was lowered to 60 ° C., and hafnia nanoparticles were recovered with an excess of acetone, and unreacted TOPO was washed through a centrifuge.

Since the hafnium oxide particles were not dispersed in hexane, TOPO was added to carry out the reaction to prepare TOPO capped hafnium oxide nanoparticles. The TOPO capped hafnium oxide nanoparticles were dispersible in hexane.

The nanoparticles dispersed in a small amount of hexane were recovered and then recycled to acetone.

The residual solvent was removed to recover the hafnium oxide (HfO ₂ ) nanoparticles, and the yield of the hafnium oxide nanoparticles was 75 to 80%.

2. Manufacture of zirconium oxide (hafnium oxide) nanoparticles

Zirconium isopropoxide isopropanol (2 mmol, 0.78 g), zirconium chloride (2.5 mmol, 0.583 g) and trioctylphosphine oxide (26 mmol, 10.0 g) were charged into a reaction vessel And stirred under nitrogen.

The reaction vessel was rapidly heated to 340 ° C and stirred rapidly for 2 hours. After the reaction was completed, the temperature was lowered to 60 ° C.

Zirconia nanoparticles were recovered with excess acetone. Unreacted TOPO was washed through a centrifuge.

Since the zirconium oxide nanoparticles were not dispersed in hexane, the reaction proceeded by adding TOPO to prepare TOPO-capped zirconium oxide nanoparticles. The TOPO-capped zirconium oxide nanoparticles were dispersible in hexane.

The nanoparticles dispersed in a small amount of hexane were recovered and then recycled to acetone. The residual solvent was removed to recover zirconium oxide (ZrO ₂ ) nanoparticles.

The yield of zirconium oxide nanoparticles was 75 to 80%.

< Example  2> High fluorine Carboxylic acid Ligand  selection

One. Preparation of Ligand

1) Purpleoro-3,6,9-trioxatridecanoic acid

In order to replace the ligand of the high-k nano-particle with the high-fluoric carboxylic acid ligand, perfluoro-3,6,9-trioxatridecanoic acid (perfluoro-3,6- 9-trioxatridecanoic acid) was purchased from Fluorochem and used.

In order to compare the dispersion stability of the ligands, the following ligands were additionally prepared.

2) 2- (5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heptadecafluorododecyl) malon juice seeds ( Ligand 6)

Ligand 6 was synthesized as shown in Scheme 1 below. That is, a 100 cm ³ round bottom flask was charged with diethyl 2- (5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heptadeca (0.391 g, 0.6166 mmol) dissolved in 10 cm &lt; ³ &gt; of distilled ethanol (absolute EtOH) was added to a solution of 0.138 g (2.46 mmol) KOH. The reaction was carried out at 80 DEG C under nitrogen for about 6 hours. After the reaction was completed, the temperature was lowered to room temperature. 36% HCl solution was slowly added dropwise to adjust the pH to 2, 30 cm ³ of distilled water was added, extracted with ethyl acetate, and the remaining water was removed through Na ₂ SO ₄ to synthesize ligand 6.

[Reaction Scheme 1]

3) 7,7,8,8,9,9,10,10,11,11,12,12,13,13,14,14,14-heptadecafluorotetradecanoic acid solution seed (ligand 7)

 As shown in Reaction Scheme 1, ligand 6 was dissolved in dimethylformamide (DMF) in a 100 cm 3 round bottom flask and distilled at a temperature of 150 ° C to synthesize a brown wax product, ligand 7.

4) 2- (5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heptadecafluorododecyl) maloylate- (2- (5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heptadecafluorodecyl) maloylate (ligand 9 )

Ligand 9 was synthesized as shown in Reaction Scheme 2 below. Namely, a 100 cm 3 round bottom flask was charged with diethyl 2,2-bis (5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12- Heptadecafluorodecyl) malonate (1.393 g), and 13 cm 3 of 50% potassium hydroxide (KOH) dissolved in 13 cm 3 of distilled ethanol (absolute EtOH). The reaction was carried out at 80 DEG C under nitrogen for 24 hours. After the reaction was completed, the temperature was lowered to room temperature. 36% HCl solution was slowly added dropwise to pH 2, 100 ml of distilled water was added, and 100 ml of ethyl acetate was added to obtain a ligand. Then, remaining water was removed through sodium sulfate (Na ₂ SO ₄ ).

[Reaction Scheme 2]

5) 7,7,8,8,9,9,10,10,11,11,12,12,13,14,14,14-hexadecafluoro-2- (5,5,6,6, 7,7,8,8,9,9,10,10,11,11,12,12,12-heptadecafluorododecyl) tetradecanoate solution (ligand 10)

As shown in Reaction Scheme 2, ligand 9 was dissolved in dimethylformamide (DMF) in a 100 cm 3 round bottom flask and distilled at 150 ° C to synthesize a brown wax product, ligand 10.

< Example  3> High permittivity  Of nanoparticles High fluorine Carboxylic acid As a ligand  substitution

1. Hafnium oxide surface modification

1 g of hafnium oxide (HfO ₂ ) nanoparticles was added to 3 g of perfluoro-3,6,9-trioxatridecanoic acid which is a high fluorine-based carboxylic acid ligand , And 2 ml of a high fluorine-based solvent HFE-7500 (Hydrofluoro ether, 3M) were added and reacted under a nitrogen atmosphere. At this time, the reaction temperature was maintained at 130 ° C. and the reaction was carried out for 4 hours.

After completion of the reaction, the reaction solution was cooled to room temperature, and a high-k rate nanomaterial (HfO ₂ ) substituted with a high fluorine-containing carboxylic acid ligand with an excess of acetone was recovered using a centrifugal separator.

The remaining solvent, acetone, was removed using a centrifuge and hafnium oxide (HfO ₂ ) nanoparticles substituted with a high fluorine-based carboxylic acid ligand were recovered. At this time, the yield of the hafnium oxide nanoparticles was 90 to 95%.

2. Zirconium oxide surface modification

1 g of zirconium oxide (ZrO ₂ ) nanoparticles was added to 3 g of perfluoro-3,6,9-trioxatridecanoic acid, and 2 ml of a high fluorine solvent HFE-7500 (Hydrofluoro ether, 3M) . At this time, the reaction temperature was maintained at 130 ° C. and the reaction was carried out for 4 hours.

After the completion of the reaction, the solution was cooled to room temperature, and then the high-k nano particles (ZrO ₂ ), which was substituted with an excess of acetone and replaced with a high-fluorine system, was recovered.

The remaining solvent, acetone, was removed from the centrifugal separator to obtain zirconium oxide (ZrO ₂ ) substituted with high fluorine. At this time, the yield of the zirconium oxide nanoparticles was 90 to 95%.

< Example  3> Thin-film molded  Manufacture of insulating devices

0.1 g of the prepared high-dielectric insulating material was dispersed in 1 ml of a high fluorine-based solvent HFE-7500. Dispersed high - k insulating material was formed as a liquid phase, and an insulating device for measuring the dielectric constant was manufactured to check whether it could be used as an insulating layer of a thin film transistor.

Spin coating was performed by a solution process. Spin coating was performed at 1500 rpm for 20 seconds at an acceleration time of 1500 rpm for 20 seconds.

< Experimental Example  1> High permittivity  Structure of nanoparticles

FIG. 2A is a schematic view showing a process for synthesizing TOPO-capped hafnium oxide nanoparticles by adding TOPO to hafnium isopropoxide isopropanol and hafnium chloride as starting materials, and FIG. FIG. 3 is a schematic view showing a process of synthesizing TOPO-capped zirconium oxide nanoparticles by adding TOPO to zirconium isopropoxide isopropanol and zirconium chloride. FIG.

When the hafnium oxide nanoparticles and the zirconium oxide nanoparticles prepared in the above Examples were examined, it was confirmed that the high fluorine ligand surrounds the hafnium oxide and zirconium oxide core.

< Experimental Example  2> High fluorine Ligand  Review dispersion stability

The dispersion stability of the high fluorine type solvent was measured when the type of high fluorine type ligand was varied.

The size of the nanoparticles was measured using a particle size analyzer (ELS-Z) and the distribution of nanoparticles having a size of 10 to 15 nm was confirmed.

 As a result, it was found that both the ligand 6 and the ligand 6 having one high fluorine chain and one carboxyl group, the ligand 9 having two high fluorine chains and the two high carboxyl groups, the two highly fluorinated chains and the ligand 10 having one carboxyl group were all dissolved over time Followed by a white precipitate.

The ligand 6, the ligand 7, the ligand 9 and the ligand 10 appeared to have poor dispersion stability, whereas the precipitation of the perfluoro-3,6,9-trioxatridecanoic acid solution did not occur for 3 months or longer, .

As the fluorine-based ligand, it was confirmed that the perfluoro-3,6,9-trioxatridecanoate solution seed was superior in the powder stability.

< Experimental Example  3> High fluorine Carboxylic acid As a ligand  Substituted High permittivity  Characteristics of insulating materials

The high-k insulating material prepared using a transmission electron microscope (TEM, Philips-CM200) was analyzed to confirm the overall layer structure and component distribution of the multilayer thin film of the high-permittivity nanoparticles.

FIG. 3 is a TEM image of a high dielectric constant insulating material in which hafnium oxide nanoparticles are dispersed in a high fluorine solvent, and FIG. 4 is a TEM image of a high dielectric constant insulating material in which zirconium oxide nanoparticles are dispersed in a high fluorine solvent. It was confirmed that the nanoparticles were uniformly dispersed in a high fluorine solvent.

5 is a schematic diagram showing a process in which a ligand surrounding a hafnium oxide nanoparticle in a high fluorine solvent is substituted with a high fluorine-containing carboxylic acid ligand. When the hafnium oxide nanoparticles are substituted with a high fluorine-containing carboxylic acid ligand, the ligand surrounding the nanoparticles has an ether group and the fluorine content is increased to 60 to 64%.

FIG. 6 is a pre-combination structural formula of a high fluorine-based solvent according to an embodiment of the present invention.

FIG. 7 is a photograph of a high fluorine-based solvent dispersed in a high-dielectric insulating material made of hafnium oxide nanoparticles according to an embodiment of the present invention. FIG. This is a photograph in which a fluorine-based solvent is dispersed in a dielectric insulating material.

Thus, the high-k nanoparticles increased in fluorine content by being substituted with a high fluorine-containing carboxylic acid ligand showed increased solubility in a high fluorine-based solvent (HFE).

< Experimental Example  4> Measurement of dielectric constant of insulating device

In order to measure the dielectric constant of the insulating device fabricated in the previous example, a probe connected to an LCR meter (Agilent 4284A) was connected to both plate electrodes at a predetermined level (1 V) The measured capacitance values were recorded. The thin film thickness of the insulating device was measured using an Alpha-step (KLA-Tenco), and the area of the top electrode of the device made of a laminated structure was measured using an opto-microscope.

The dielectric constant was measured using the above three values.

FIG. 9 is a graph showing the dielectric constant of an insulating device using a high dielectric constant insulating material in which hafnium oxide nanoparticles are dispersed. FIG. 10 is a graph showing the dielectric constant of an insulating device using a high dielectric constant insulating material in which zirconium oxide nanoparticles are dispersed Fig.

The dielectric constant of each insulating element was measured as 4 to 4.5, and it was confirmed that the dielectric constant exhibited a high dielectric constant.

Taken together, the high-permittivity nanoparticles were prepared, and the high-fluorine-based carboxylic acid ligands were added to the reaction solution to react the ligands surrounding the nanoparticles with fluorine-containing high-fluorine carboxylic acid ligands.

When the high-permittivity nano-particles are selected as a high-k insulating material and dispersed in a high-fluorine-based solvent, the high-concentration fluorine contained in the ligand increases the solubility and obtains a high-k insulating material dispersed in a high fluorine-based solvent.

The high dielectric insulating material can be used as an ink used in a solution process or a printing technique, and a high fluorine-based solvent does not cause chemical, physical, or electrical damage to the semiconductor layer formed under the dielectric layer. Respectively.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that such detail is solved by the person skilled in the art without departing from the scope of the invention. will be. It is therefore intended that the scope of the invention be defined by the claims appended hereto and their equivalents.

100: Aluminum 200: Permittivity layer
300: Di-F-TESADT 310: Drain
320: source 400: glass

Claims (8)

Adding a high-fluorine-containing carboxylic acid ligand to the high-fluorine-containing solvent and reacting (step 1);
Recovering the high-k nano-particles substituted with a high fluorine-containing carboxylic acid ligand with acetone (second step); And
Step of removing residual acetone (third step)
Wherein the high dielectric constant insulating material has a high dielectric constant. The method according to claim 1,
Wherein 10 to 20 parts by weight of high-dielectric constant nano-particles and 30 to 60 parts by weight of a high-fluorine-containing carboxylic acid ligand are added to 100 parts by weight of the high fluorine-based solvent. The method of claim 1, wherein the high fluorine-based solvent is selected from the group consisting of hydrofluoroethers, perfluorocarbon, hydrofluorocarbons, and fluorinated aromatic solvents. A method of manufacturing a high dielectric constant insulating material.
The method according to claim 1,
Wherein the high dielectric constant nano particles are any one selected from hafnium oxide, zirconium oxide and barium titanate. The method according to claim 1,
Wherein the high fluorine-containing carboxylic acid ligand has an ether group and a fluorine content of 60 to 64%. The method of claim 5,
The high fluorine-containing carboxylic acid ligand may be,
Perfluoro-3,6,9-trioxatridecanoic acid, perfluoro phosphonic acid, (7, 7, 8, 8, 9,9,10,10,11,11,12,12,13,13,14,14,14-heptadecafluorotetradecanooic acid solution seeds (7, 7, 8, 8, 9, 9, 10, 10,11,11,12,12,13,13,14,14,14-heptadecafluorotetradecanoic acid), 2- (5,5,6,6,7,7,8,8,9,9,10,10 , 11,11,12,12,12-heptadecafluorododecyl) malonic acid solution (2- (5,5,6,6,7,7,8,8,9,9,10,10,11 , 11,12,12,12-heptadecafluorododecyl) malonic acid), 7,7,8,8,9,9,10,10,11,11,12,12,13,14,14,14-hexadecafluoro (5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heptadecafluorododecyl) tetradecanoic &lt; / RTI &gt; solution (7,7,8,8,9,9,10,10,11,11,12,12,13,14,14,14-hexadecafluoro-2- (5,5,6,6,7,7 , 8,8,9,9,10,10,11,11,12,12,12-heptadecafluorododecyl) tetradecanoic acid), 2- (5,5,6,6,7,7,8,8,9, 9,10,10,11,11,12,12,12-heptadecafluorododecyl) -2- (5,5,6,6,7,7,8,8,9,9,10,10 , 11,12,12,12-hexadecafluorodecane Decyl) malonic acid (2- (5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heptadecafluorododecyl) -2- (5 , 5,6,6,7,7,8,8,9,9,10,10,11,12,12,12-hexadecafluorododecyl) malonic acid, perfluorodecanoic acid, and perfluorodecanoic acid, A perfluoroctadecanoic acid, and a perfluorooctadecanoic acid. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt; An insulating element obtained by dissolving the high-dielectric insulating material according to any one of claims 1 to 6 in a high-fluorine-based solvent and forming the thin film. 8. The method of claim 7, wherein the insulating element is selected from the group consisting of transistors, solar cells, coatings, non-volatile memories, backplanes of flexible displays, secondary battery electrolytes, flexible integrated circuits, flexible electronic paper displays, Is applied to the insulating layer.

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