KR20110135612A - Processing of fto film on physically stabilized ultra-flexible thin substrate - Google Patents

Abstract

PURPOSE: A processing of FTO film on physically stabilized ultra-flexible thin substrate is provided to stabilize nucleation at coating process and conduct uniform grain growth by restraining vibration, drying, dusting, broking and elongation generated in super soft/ultra-light substrate. CONSTITUTION: A processing of FTO film on physically stabilized ultra-flexible thin substrate comprises a step of stabilizing by one method selected from physical fixing, electromagnetic fixing, chemical fixing and fluid mechanical fixing. The physical fixing is operated by pushing, weighting, physical connecting, etc. The electromagnetic fixing is operated by magnetic force, electromagnetic force, etc. The chemical fixing is operated by adhesive, binder, paste, etc. The fluid mechanical fixing is operated by reducing pressure, vacuum, etc. In the next step, the conducting film for a super soft substrate is formed. The super soft substrate is one among ceramics, glass, polymer, cotton flannel composite material. The super soft glass substrate is one among ultra-thin-sheet glass, and glass ribbon. The super soft polymer substrate is one among polyimide[PI], Teflon resin[PTFE], poly norborene resin[PNB], composite resin containing clay.

Description

Process of FTO film on physically stabilized ultra-flexible thin substrate

The present invention provides a first process and a high quality transparent conductive film (FTO (F-doped Tin Oxide), AZO, ZnO) for physically stabilizing a very thin, ultra-lightweight, ultra-flexible substrate having a thickness of ˜100-200 m or less. The present invention relates to a process technology for fusing a second process to form a transparent conductive film, particularly an FTO film, on a super flexible substrate.

Ultra-flexible substrates, especially glass substrates, which are major materials in the IT field, are classified into general glass, thin glass (500-1500m), and ultra-thin glass (5- ~ 100-200m). It can be bent at more than 90-360 and twisted, making it easy to produce glass rolls. In particular, glass ribbons with thicknesses of several tens of meters or less show super-flexible properties that are even slightly wrinkled.

On the other hand, general glass and thin glass (500-1500m), which are currently commercially available, may be slightly bent while maintaining high hardness, but may not exhibit super flexible properties such as ultra thin glass.

Recently, transparent and super flexible heat-resistant plastic substrates have been developed to solve the disadvantages (brokenness / expensiveness) of conventional ceramic or glass super flexible sheets. Representative examples include polyimide (PI), Teflon resin (PTFE), polynorbornin (PNB) -based, and nanoclay composite membrane resins having very high glass or melting points.

Ultra-flexible substrates (ceramic, glass, polymer, fused materials, etc.) with thicknesses of 100-200m or less can be bent to 90-360 and twisted in addition to the advantages of reducing the light weight and material cost. (Ultra lightweight devices, high brightness devices, flexible devices, etc.) are expected as substrate materials.

Transparent conductive film is a transparent and electrically conductive material, which is the most essential material for IT and solar cells. Typical examples include sputtering (including roll-to-roll: R2R process), atmospheric CVD, spray pyrosol, CVD, PVD, and vapor deposition of thermal deposition. In the present invention, as an example, the present invention is intended to be completed by applying the principles of the present invention to the formation of the FTO film having the most difficult process conditions. A common FTO manufacturing principle is the technique of vaporizing or sending droplets of FTO precursors (Sn and F-containing compounds, solvents, additives, etc.) onto a heated substrate for coating.

However, the super-flexibility, twisting, and ultra-light weight properties of the super flexible thin glass cause the following problems in the transparent conductive film coating process, making it impossible to apply the existing transparent conductive film forming process technologies.

As a representative problem,

(1) Curing phenomenon when heated

(2) Flying, shaking, or deviating under tropical and flow conditions

(3) Substrate vibration phenomenon in in-line process and mechanical vibration

(4) Movement and departure phenomenon of the substrate due to inertia during the continuous process of stopping / progressing

(5) There is a phenomenon in which the substrate breaks or stretches in the tensile tension applied to maintain tension during R2R coating.

In other words, substrates with a thickness of ~ 100-200 m or less are very light and super flexible, so they can be easily removed from their original position by flying or moving even under minute flow conditions. The vibration of the substrate itself is easily generated by the vibration.

The problem of detachment of superflexible board is the most serious, and it is impossible to produce the product itself, and even the vibration of the board itself has a great influence on the precursor generated from the gas phase and the nucleation on the board, which greatly affects the uniformity and quality of the thin film. These problems easily occur in vacuum deposition equipment such as sputter and CVD, but FTO coating method using atmospheric pressure CVD and spray pyrosol, which generate mass flow, in fact, substrates of ~ 100-200m thick It is almost impossible to use in the usual way.

However, in conventional conventional substrate materials, these problems are not a problem of the process due to its own load.

In addition, when performing R2R coating using a roll of super flexible foil, tension retention, which is usually applied to a considerable tensile strength, is a phenomenon of cracking of a substrate in the case of a super flexible ceramic (including glass) roll, and a substrate in the case of a super flexible plastic roll. Because of this increasing phenomenon (which adversely affects the coating film when the tensile stress is released after the coating finish), even in the case of the super flexible R2R coating process, an additional process different from the existing process must be developed to obtain a good transparent conductive film, especially FTO.

In the present invention, by suppressing the vibration, lifting, curling, flying, leaving, cracking (R2R), elongation (R2R) phenomenon occurring in the super flexible / ultra-lightweight substrate having a thickness of about ~ 100-200m or less nucleation during the coating process ( Stabilization of nucleation and homogeneous grain growth were attempted to obtain a high quality transparent conductive film or FTO film.

Therefore, the present invention attempts to physically stabilize the super-flexible substrate using the following four immobilization principles.

(1) physical fixation of super-flexible substrates (pressing, gravity, load, physical connection (screws, etc.)),

(2) chemical immobilization (adhesive, ceramic bond, paste, carbon paste, silver paste, etc.)

(3) hydrodynamic immobilization (suction, etc.)

(4) Electromagnetic immobilization (electrostatic attraction, magnetic force, etc.).

These four immobilization principles are physically stabilized in processes such as sputtering on a flexible substrate, atmospheric pressure CVD, spray pyrosol, and R2R to obtain a high quality transparent conductive film (including FTO).

In particular, the FTO film has the most excellent heat resistance (stable up to 500 degrees) and chemical resistance properties of the transparent conductive film, so the FTO coated material on the super flexible substrate is the next generation ultra light or super flexible IT substrate module (display) , Touch panel, etc.), as well as a super flexible transparent heating heater, a super flexible sensor module, and a super flexible solar cell (DSSC, thin film solar cell electrode).

As a specific solution (see Fig. 1),

(1) It is a method of forming a physical crimping part on the edge upper end of the super flexible substrate having a thickness of 100 m or less and stabilizing the super flexible substrate from the harsh external environment and then coating (FIG. 1 (b)). As the principle of physical fixation, gravity, screw fixing (physical tightening), magnetic force (magnet, electromagnet: magnetic force between the physical crimp and the bottom of the substrate), electromagnetic force (electrostatic, etc.) may be utilized. Figure 1 (a) is an example showing a case where the stabilization process of the substrate is not performed.

(2) It is a method of stabilizing the super-flexible thin plate from the harsh external environment through chemical bonding to the edge of the super-flexible substrate less than 100 m thick (Fig. 1 (c)). Various adhesives may be utilized as the chemical fixation principle, and it is preferable to use the metal paste through heat treatment using a metal bond, a paste, a silver paste, and a carbon paste. In the present invention, silver paste is used as an example. To immobilize the substrate to obtain an FTO coating.

(3) A method of performing a coating process after stabilizing ultra-thin glass from harsh external environment by providing a suction system on a substrate conveyor, susceptor, or heater located at the lower side of a super-flexible substrate to hydrodynamically decompress (or pressurize) the substrate. (FIG. 1 (d)). As a hydrodynamic fixing principle, a substrate may be fixed by suction by providing a plurality of holes and hole arrays, a plurality of gaps or line arrays, and a mesh type at the lower end of the substrate. In addition, it is possible to stably transport the substrate or to control physical movement by using a pressurization device such as gas jetting in the upper layer portion (or part or the entire edge) of the super flexible substrate.

Super flexible substrates with a thickness of ~ 100-200 m or less proposed in the present invention are ceramics, glass, and high heat resistant films (Tg is more than 300 degrees polyimide (PI), Teflon resin (PTFE), polynorbornin (PNB)). Resins, clay-containing composite resins, and the like), and fused and composite materials.

In addition, general glass (soda lime glass), aluminum borosilicate glass, glass for LCD, low iron glass (Low-Fe glass, 150 ppm or less of iron), tempered glass, low thermal expansion glass, and the like may be used as the super flexible glass substrate. And commonly called ultra thin glass, glass ribbons, and glass rolls. In particular, soda-lime glass included in the normal glass, alkali ions are diffused to the upper portion of the transparent conductive film during the heat treatment, in order to prevent this can be a SiO ₂ or TiO ₂ barrier film.

In addition, in order to improve the adhesion on the resin film of the FTO thin film FTO on the transparent resin film formed with an organic-inorganic coating layer such as epoxy-based silane, methyl tetratriethoxysilane (MTMS), phenyl tetratriethoxysilane (PTMS) A thin film forming technique, and coating with tetraethoxysilane (TEOS), MTMS, PTMS, etc. as a protective film on the FTO coating layer may be additionally included.

The coating process carried out through the super-flexible substrate stabilization process of the present invention is the following process (1) CVD, (2) PVD (sputter, thermal evaporation, etc.), (3) atmospheric pressure CVD, (4) spray pyrosol 4 Eggplant meteorological processes are representative,

In the present invention, the coating method of the FTO transparent conductive film by spray pyrolysis is 500 ^o as an aqueous solution using Corning Co., Ltd. as the second tin chloride (SnCl ₄ ) 100, water 5, 10 hydrochloric acid 3 It may include a manufacturing method for the NESA film prepared by spraying on a substrate heated in C, Pilkington Co. in 1988 SnCl ₄ or C ₄ H ₉ SnCl ₃ (MBTC), (CH ₃ ) ₂ SnCl ₂ (DMT) A method of preparing by reacting with water and oxygen may be included, or HF or CF ₃ COOH or CHF may be used to improve conductivity.

In addition, in the present invention, a low cost and stable spray coating solution may be prepared by using SnCl ₄₂ O, SnCl ₂ , SnCl ₂₂ O, etc. as a coating solution with water as a solvent, and NH ₄ F may be added as a doping material to dope fluorine. (Molar ratio of F / Sn in the amount of fluorine doping is in the range of 0.5-2.0).

As the second transparent conductive film coating process performed after the first step of the super flexible substrate stabilization of the present invention, there are FTO, ITO, AZO, ZnO, SnO ₂ , IZO, GZO, TiO ₂ , but the principle of the present invention is such a transparent conduction. It is not limited to the film | membrane.

The present invention implements a transparent conductive film (including FTO), which is very important for the IT, semiconductor, energy, and electronics industries, on a superflexible substrate, to produce a next generation superflexible display, a superflexible touch panel, a superflexible electronic paper, and a superflexible thin film silicon solar cell. It can be used in batteries (Thin-Si), super flexible dye-sensitized solar cells (DSSC), super flexible sensors, and super flexible heating heaters.

1 is a conceptual diagram of a method for physically stabilizing ultra-thin glass having a thickness of 100 m or less proposed in the present invention in a harsh environment
Fig. 2. Schematic diagram of the present invention in which the nozzle portion and the exhaust portion are formed at the side part
3. Schematic diagram of the in-line device of the present invention consisting of a nozzle portion and an exhaust portion each in the upper layer portion;
4. Schematic diagram of the roll-to-roll (R2R) device of the present invention composed of one nozzle portion and one exhaust portion in an upper layer portion thereof.
Fig. 5. Another nozzle structure of the present invention having two nozzles on both sides with one nozzle part in the upper part as a center. Such a nozzle is applicable to Figs. 2 and 4, and the number of nozzles and the exhaust part is dependent on the length and output of phosphorus. Many can be configured.
6. Cross-sectional FE-SEM photographs in which an FTO coating film was formed on an ultra-thin glass substrate having a thickness of 20 m by using the principles of FIGS. 1 (b) and 2 (see FIG. 7).
Figure 7.FTO surface FE-SEM picture of Figure 6
8. Cross-sectional FE-SEM photograph of the FTO coating film formed on the ultra-thin glass substrate having a thickness of 20 m using the principle of FIGS. 1 (d) and 3 (top layer FTO grains are blurred)
9. A cross-sectional FE-SEM photograph in which an FTO coating film was formed on an ultra-thin glass roll substrate having a thickness of 20 m using the principles of FIGS. 1 (b) and 4 clearly shows an FTO film having a thickness of 100-200 nm.
10. As a result of quantitative analysis of the FTO of FIG. 9 by the EDS method, it can be seen that F is contained in about 1.5% of Sn.
11. Cross-sectional and surface photographs of FTO membrane coated on polyimide film (see Table 1.2)

Example  1: process equipment and process technology

The production of a super flexible glass lamina FTO film having a thickness of 20 m is based on the known Spray Pyrosol principle, the principle of FIG. 1, the equipment devised in the present invention (FIGS. 2 to 5), and the result thereof. ~ Is shown in detail in FIG. 10.

In the spray pyrosol coating method of the present invention, the precursor of tin oxide is SnCl ₄ 5H ₂ O, (C ₄ H ₉ ) ₂ Sn (CH ₃ COO) ₂ , (CH ₃ ) ₂ SnCl ₂ , (C ₄ H _{9 3} ) tin-containing organometallic compounds such as SnH and SnCl ₄ may be used. Various fluorine sources such as NH ₄ F, CF ₃ Br, CF ₂ Cl ₂ , CH ₃ CClF ₂ , CF ₃ COOH, CH ₃ CHF ₂ , HF can be used as the fluorine source that acts as a fluorine source doped with tin oxide. It does not specifically limit. The Sn / F ratio is mixed so as to be a predetermined ratio to produce an FTO precursor. The solvent may be water and alcohol, or a mixing system thereof, but in terms of stability, water and ethanol system may not be used, and water and ethanol may be mixed. Typically 5 wt% ethanol (H ₂ O ratio) may be used as the solvent.

The FTO precursor solution is sprayed onto the substrate along with the carrier gas through a nozzle (spray nozzle, ultrasonic spray nozzle, ultrasonic mist spray), and the sprayed micro droplets are deposited on the substrate. At this time, the deposition chamber is provided with an appropriate exhaust system to extract the reaction gas and the unreacted material. The method of forming the precursor microdroplets through the nozzle may use a general spray nozzle and a slit nozzle, but such a method tends to form relatively large droplets. In order to form finer droplets, it is desirable to first form an ultrafine mist precursor by means of ultrasonic spraying and transport it to the deposition chamber as appropriate through a carrier gas system and a vent system. At this time, the substrate can be rotated in case of batch type, and in case of continuous in-line and roll-to-roll (R2R) coating system, gas curtains (air knives, etc.) are formed at the lower ends of both sides of the deposition chamber and sealed and transported. It can be possible.

Example  2: SiO2  And TiO2 Barrier  Film formation process

In general glass materials used as ultra-thin sheets, impurities such as Na ⁺ and K ⁺ diffuse onto the substrate when heated to 400-600 degrees, thereby damaging the surface of the glass substrate. This results in a decrease in film adhesion and film quality even when the FTO film is coated. Therefore, a barrier layer coating must be applied between the glass substrate and the FTO film to block impurities from entering. Generally, many ceramic films such as SiO ₂ and TiO ₂ are used, but in the present invention, SiO ₂ is typically represented. Barrier film was formed by using dip coating and spray coating at about 5-50 nm. In the case of a small substrate, a dip coating method was used, and in the case of a large substrate and a curved surface, a SiO ₂ barrier film was formed using a spray coating method.

In the dip coating method, a silica sol [ethanol (95%): Tetraethyl silicate: Nitric acid = 90: 11: 0.5 (volume ratio)] was prepared, dip coated at a speed of 150 mm / min, and then heat-treated at 300-400 degrees for 5 minutes. SiO ₂ barrier film was formed. Spray coating was performed on large area substrates or curved glass substrates. Silane reagents (SiH ₄ , SiH ₂ Cl ₂ , Si (OC ₂ H ₅ ) ₂ , etc.) can be easily formed on the glass substrate heated to 400-600 degrees in air or in an oxygen atmosphere by using the CVD principle (spray). there was. When using high quality glass, ie, when using a glass substrate with few impurities, such as Na and K (for example, borosilicate glass), it is not necessary to form a barrier film.

Example  3: FTO Precursor  Manufacturing method

FTO precursor solution was prepared by dissolving SnCl ₄ 5H ₂ 0 in tertiary distilled water to 0.68 M, and dissolving NH ₄ F as an F dopant in ethanol to 1.2 M, then mixing and stirring the two solutions and filtering. . In addition, the coating solution was prepared by mixing and stirring SnCl ₄ 5H ₂ O to 0.68 M in a solvent in which 5% ethanol was mixed with pure DI water, and the source of F was NH ₄ F with a ratio of F / Sn of 1.76. Synthesis was carried out as possible. In addition, the precursor solution may additionally add alcohols, ethylene glycol (Ethylene glycol) in addition to the solution composition in order to prepare a variety of forms of FTO film.

In order to control the amount of F doping, the amount of NH ₄ F may be changed from 0.1 to 3 M, or 0-2 M of hydrofluoric acid (HF) may be added. Therefore, the precursor solution for preparing the FTO membrane is not limited to the composition shown above.

Example  4: Precursor  Micro Droplets  ( Mist  Way)

In order to atomize the FTO precursor in the gas phase to obtain the precursor flow of FIGS. 2 to 5, the precursor source portion is separately connected with three apparatuses, a spray coating method, an ultrasonic spray coating method, and an ultrasonic spray spray method.

In brief, the spray coating method is a method of spraying the liquid precursor into the micro droplets as the force to attract the liquid when the external gas is expanded through the fine nozzle unit. Ultrasonic spraying is a method in which a liquid precursor is vibrated by an ultrasonic vibrator and atomized by a carrier gas, just like a general ultrasonic humidifier. Finally, ultrasonic spray spraying is a method in which the ultrasonic vibrator portion is changed like a spray nozzle to spray the atomized precursor according to the spray principle.

Example  5: various coating process

2 shows a schematic diagram of the simplest batch type FTO coating system with side precursor introduction and side vent structure. The substrate 2 introduced into the pretreatment chamber 1 may be surface treated or heated. That is, a heater (not shown in the drawing: a plate heater or a hot wall heater) and a plasma surface treatment agent (not shown) may be separately provided. This pretreated substrate is transported to the deposition chamber 3. At this time, through the shutter or the air curtain (4) provided between the chamber between the chamber is closed and closed. The deposition chamber may have a separate heating system (not shown: plate heater or hot wall heater). In addition, although omitted in the drawings, it is possible to increase the uniformity during coating by rotating the heater or by rotating the substrate.

Embodiments using the equipment of FIG. 3 in the present invention all utilize a rotating heater system. One side portion of the deposition chamber 3 is provided with a nozzle portion 8 and a precursor flow 9 supplied from an external precursor source portion 7 is introduced into the deposition chamber 3 through the nozzle portion 8. Will enter. At this time, the movement of the precursor flow can be easily adjusted by the exhaust unit 10 provided on the opposite side portion. The exhaust unit 10 may also contain the reaction product gas, the unreacted gas, and the carrier gas (evaporated from the deposition chamber). 9) It is also responsible for the exhaust of the lamp.

The FTO coated substrate 12 produced in the deposition chamber 3 is transferred to the aftertreatment chamber 11 through the shutter 4. The aftertreatment chamber 4 may be separately equipped with devices of a heater (not shown: plate heater or hot wall heater), a cooling device, a quenching device (such as tempered glass or FTO substrate surface morphology change).

3 is a system for transporting flat substrates in an inline conveyor system (1) and continuously coating the coating unit (3) with a nozzle unit (4) capable of injecting precursor mist from the top and a vessel making a flow in one direction. There is a base (5). In addition, the substrate preheating unit 6 and the substrate cooling unit 7 may be fastened and used, and a shutter or an air knife 8 may be used between the chambers to block the gas flow.

4 has a structure similar to that of FIG. 3, but is effective when a roll type super flexible substrate roll is used. The roll type substrate material of the present invention may be a glass ribbon roll (ultra thin glass), a polymer, or the like. However, in the case of ultra-thin ceramic rolls, it is desirable to use the lower suction principle of FIG.

FIG. 5 is a structure in which a precursor maximizes a contact fraction with a substrate by simultaneously installing exhaust parts at both sides of a nozzle for one upper nozzle, and may be used in parallel with the system of FIGS. 3 and 4. The number of such nozzles and the exhaust portion may be provided in a large number depending on the inline length, the roll length, the production amount.

Example  5: Super Flexible  Ceramic substrate and Cottage  Coating on glass substrate

6 is a cross-sectional view of the FTO film formed when the solvent is coated by heating the ultra-thin glass having a thickness of 20 m at 450 degrees using the principle of FIG. 1 (c) and the equipment of FIG. Can be. Almost no deformation of the glass substrate was observed, and as shown in FIG. 7, FTO grains were well grown. As a principle of FIG. 1 (c) used, a commercially available silver paste was attached to a lower end of an ultra thin glass edge having a thickness of 20 m, and was used by heat treatment. Silver paste heat treatment is performed automatically during substrate preheating. Such chemical fixation methods are possible with various adhesives but preferably graphite, metals, ceramic pastes and adhesives. The transmittance was 92% (at 550 nm wavelength) and the sheet resistance was about 200 ohms. Therefore, if the thickness of the film is further reduced, the transmittance is further increased and can be immediately used as a top touch panel device.

FIG. 8 is a cross-sectional FE-SEM photograph in which an FTO coating film is formed on an ultra-thin glass substrate having a thickness of 20 m using the principles of FIGS. 1 (d) and 3 (upper FTO grains are blurred). A water / ethanol 5% mixed solution was used and carried out at a temperature of 450 degrees. The hydrodynamic fixing method is an ultra-thin glass susceptor with a thickness of 20 m. The substrate is adhered to the susceptor by making a 5 mm diameter hole at the bottom of the four corners and the center of the SiC coated graphite plate and continuously depressing the air at the bottom. This made it happen.

FIG. 9 is a cross-sectional FE-SEM photograph in which a glass roll-like FTO coating film having a thickness of 20 m is formed using the principles of FIGS. 1 (b), 4, and 5, and an FTO film having a thickness of 100-200 nm is clearly identified. As a result of quantitative analysis of the FTO of FIG. 9 using EDS, it can be seen that F is contained in about 1.5% of Sn (FIG. 10). In the present invention, the physical pressing on the upper edge of the stable substrate of the inline-type ultra-thin glass substrate can be solved most simply. This physical pressing is useful to use gravity by weight, magnetic force by magnet, electromagnetic force by electrostatic, etc. Can be. However, in the R2R coating of FIG. 4, it is most preferable to have a lower suction system while maintaining low tension, but it is also possible to use a guide having a certain height.

Example  5: Super Flexible Polymer  Substrate Coating

Table 1 shows the electrical characteristics according to the thickness change of the FTO thin film on the super-flexible PI substrate (see FE-SEM picture of FTO1, FTO2, FTO3 in Figure 11). The principle of Fig. 1 (c) and the equipment of Fig. 2 were used. As a principle of FIG. 1 (c), a commercial silver paste was attached to the lower edge of the super flexible plastic and heat-treated at 400 degrees. As can be seen from the table, the thickness of 550nm-1000nm film showed a specific resistance in the range of 5.31-8.80 * 10 ^-4 Ohmcm and the sheet resistance was about 3.4-15 ohm. The concentration of the spray coating solution was used as a solvent, SnCl ₄ 5H ₂ O was the most suitable concentration of 0.5-1.5M. If the concentration of the solvent is too high, the stability of the solution is apt to produce a precipitate, if the concentration is too low, there is a disadvantage that the coating time is lowered and the process time is reduced. As shown in Table 2, the optical characteristics showed a lower transmittance at a thickness of 550 nm, with a range of 12-24%, and a transmittance of 42-53% at a wavelength of 700 nm. At this wavelength of 550 nm, that is, the shorter wavelength, the transmittance is lowered because the PI film is yellow. Therefore, when the transparent heat resistant film such as PNB or PTFE is used, the decrease in transmittance at low wavelength is expected to be small, and in order to increase the transmittance, it can be seen that the coating should be thinner than 500 nm thickness. Sectional and surface FE-SEM photographs of the FTO 1, 2 and 3 films are shown in FIG.

The following describes a process for forming a buffer layer on the polymer resin film to enhance the adhesion of the oxide transparent conductive film. In a 250 ml flask, TEOS, GPTMS (3-glycidoxypropyl) trimethoxysilane (3) was added at a weight ratio of 3: 1, ethanol and water were mixed at a ratio of 50:50, and 0.5 M p-TSA (p-tolunesulfonic acid monohydrate) was used as a solvent. The mixture was added at a ratio of 1/10 and stirred at room temperature for 12 hours to cause hydrolysis and polymerization. As a result, a clear solution was obtained. It was found that transparency was maintained even when this transparent solution was aged at room temperature for 2 weeks. This transparent coating solution showed a tendency to slightly increase in viscosity with time, but showed no significant obstacle in coating. The coating solution was coated on a polymer resin film such as PI by a bar coater, roll coating, or dip coating method and heat-treated at 100-300 ^° C.

MTMS 1 mol, TEOS 0-1 mol Acetic Acid 0.1-0.5 mol, water 1.6 mol, ethanol 14-30 mol ratio was mixed to synthesize the MTMS hybrid coating solution, PTMS can be used instead of MTMS . After the aging of the coating solution, it was similarly coated with a bar coater, roll coating, or dip coating and dried to form a hybrid buffer layer. FTO coating on the buffer layer was formed by spray pyrolysis to form a flexible transparent conductive film.

Sample Carrier concentration (cm ^-3 ) Electron mobility (cm ² / Vs) Electrical resistivity (Ohmcm) Electrical sheet resistance (Ohm /) Thickness
nm FTO-1 -5.14E + 20 22.89 5.31E-04 3.4 1000 FTO-2 -4.06E + 20 17.45 8.80E-04 6.8 880 FTO-3 -4.38E + 20 16.53 8.62E-04 14.5 540

Transmission (%) 550 nm 700 nm 900 nm FFTO1 12 42 50 FFTO2 18 48 57 FFTO3 24 53 66

Claims (12)

In the method of physically stabilizing a super-flexible substrate, and forming a transparent conductive film using a vapor phase process on the physically stabilized super-flexible substrate,
Physically stabilize the super flexible substrate,
(1) physical immobilization such as pressing, loading, or physical fastening
(2) Electromagnetic immobilization such as magnetic force and electromagnetic force
(3) chemical immobilization such as adhesives, binders, pastes
(4) A method of forming an FTO film through physical stabilization of a super-flexible thin plate, characterized by forming a transparent conductive film on a super-flexible substrate after stabilizing by any one method of immobilizing the substrate, such as vacuum or vacuum. The method of claim 1,
A method of forming an FTO film through physical stabilization of a super flexible thin plate, characterized in that the super flexible substrate is any one of ceramic, glass, polymer, and fused composite material. The method of claim 2,
A method of forming an FTO film through physical stabilization of a super flexible thin plate, wherein the super flexible glass substrate is any one of an ultra thin glass and a glass ribbon. The method of claim 2, wherein the super flexible polymer substrate is any one of polyimide (PI), Teflon resin (PTFE), polynorbornin (PNB) resin, and clay-containing composite resin. FTO film formation method. The method of claim 1,
Transparent conductive film is FTO, ITO, AZO, ZnO, SnO2, IZO, FTO film formation method through physical stabilization of ultra-thin flexible plate, characterized in that any one. The method of claim 3, wherein
Physically stabilizing the ultrathin glass using any one of the following methods;
(1) physical immobilization such as pressing, loading, physical fastening,
(2) electromagnetic force immobilization such as magnetic force, electromagnetic force,
(3) chemical immobilization such as adhesives, binders, pastes,
(4) hydrodynamic immobilization such as reduced pressure, vacuum,
Heating the physically stabilized ultra thin glass substrate at 300-600 degrees;
Forming a FTO film on the heated and physically stabilized ultra-thin glass substrate by an atmospheric pressure CVD or spray pyrosol method. The method of claim 6,
A method of forming an FTO film through physical stabilization of a super flexible sheet having a roll-to-roll FTO coating step, characterized in that the super flexible sheet is a glass roll. The method of claim 4, wherein
Physically stabilizing the superflexible heat resistant polymer substrate using any one of the following methods;
(1) physical immobilization such as pressing, loading, physical fastening,
(2) electromagnetic force immobilization such as magnetic force, electromagnetic force,
(3) chemical immobilization such as adhesives, binders, pastes,
(4) hydrodynamic immobilization such as reduced pressure, vacuum,
Heating the physically stabilized superflexible heat resistant polymer substrate at 300-600 degrees;
Forming a FTO film on the heated and physically stabilized super-flexible heat-resistant polymer substrate through atmospheric pressure CVD or spray pyrosol method. The method of claim 8,
A method for forming an FTO film through physical stabilization of a super-flexible thin plate, characterized in that it has a roll-to-roll FTO coating step, characterized in that the superflexible heat-resistant polymer substrate is a polyimide roll. The method of claim 1,
The transparent conductive film forming method uses a vapor deposition method such as spray pyrosol, atmospheric CVD, CVD, PVD, sputtering, thermal evaporation, etc. FTO film formation method through physical stabilization of ultra-thin flexible sheet. The method according to any one of claims 3, 6 and 7,
Coating a barrier film on the ultra-flexible glass substrate;
And forming a transparent conductive film on the barrier film. The method according to any one of claims 4, 8 and 9,
Forming an organic-inorganic buffer layer such as an epoxy-based silane, methyltetratriethoxysilane (MTMS), or phenyltetratriethoxysilane (PTMS) on the super flexible polyimide substrate;
And forming a FTO film in the buffer layer.

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