KR101644038B1 - Transparent conductive film, method for manufacturing the same and touch panel containing the same - Google Patents

Abstract

A transparent conductive film is disclosed, wherein the transparent conductive film is a non-coated substrate comprising plastic; A first laminate formed on the non-coated substrate by high density plasma enhanced chemical vapor deposition (HD-PECVD), the inorganic laminate comprising an inorganic oxide, having a refractive index of 1.6 to 2.0 and a thickness of 0.4 to 1.0 mu m; Wherein the first laminate has an inorganic oxide different from the inorganic oxide contained in the first laminate and has a refractive index of 1.3 to 1.5 and a thickness of 30 nm to 80 nm, the second inorganic oxide being formed on the first laminate by a high density plasma enhanced chemical vapor deposition 2 laminate; And a transparent conductive layer formed on the second laminate and having a thickness of 15 nm to 50 nm.

Description

TECHNICAL FIELD [0001] The present invention relates to a transparent conductive film, a method of manufacturing the same, and a touch panel including the transparent conductive film.

The present invention relates to a transparent conductive film, a method of manufacturing the same, and a touch panel including the transparent conductive film.

The touch panel is mounted on a surface of a display device and converts physical contact of a user's finger or touch pen into an electrical signal and outputs the electrical signal. The touch panel is a liquid crystal display, a plasma display panel, an EL (electro-luminescence) devices.

As a kind of such a touch panel, there is a capacitive type. In the case of a transparent conductive film used in a capacitive touch panel, the visible light transmittance is high and the transmission coloring is low, Visibility should be good. In particular, a transparent conductive film used in a capacitive touch panel must have a low transparency and coloring in order to display the color of a displayed screen without distortion. In view of the touch panel product structure, the electrode pattern generated after the transparent electrode pattern etching process is good do. In order to obtain low transmittance and high visibility of the electrode pattern, the electrode pattern must be penetrated to minimize the visible phenomenon, and a laminated structure is needed to reduce the amount of reflected light and increase the amount of the transmitted light.

Accordingly, conventionally, in order to produce a transparent conductive film (IMO-coated PET) of a capacitance type, a hard coating (wet type) for hardness improvement is formed on an uncoated film, and a high refractive index layer A low refractive index layer was formed to realize a refractive index combination (index matching), and then a transparent conductive layer (ITO) was formed on the index matching. Alternatively, a hard coating (wet type) for hardness improvement is applied to the uncoated film, and a high refractive index layer and a low refractive index thin film are formed on the upper layer by a dry method to realize a refractive index combination (index matching) ITO).

In this conventional method, a hard coating is formed on a non-coated film by a wet process, a drying process is performed, and an index matching process is performed in the wet, high refractive and low refractive order, and then a curing (drying) Then, the transparent conductive layer was formed, and the time consumed, the number of steps, and the defect rate were large.

Further, even if the index matching is formed by dry etching, an index matching is formed by dry (vacuum coating) on a film having a hard coating formed on a non-coated film by a wet method, and a separate hard coating forming process can be performed The time consumed, the number of processes, and the defect rate are still large in producing the transparent conductive film.

The present invention has been made to solve the above problems of the prior art, and it is an object of the present invention to provide a transparent conductive film having improved surface hardness, scratch resistance and abrasion resistance without a wet hard coating film, And to provide the above objects.

As a technical means for achieving the above technical object, the transparent conductive film according to the first aspect of the present invention comprises: a non-coated substrate including plastic; A first laminate formed on the non-coated substrate by high density plasma enhanced chemical vapor deposition (HD-PECVD), the inorganic laminate comprising an inorganic oxide, having a refractive index of 1.6 to 2.0 and a thickness of 0.4 to 1.0 mu m; Wherein the first laminate has an inorganic oxide different from the inorganic oxide contained in the first laminate and has a refractive index of 1.3 to 1.5 and a thickness of 30 nm to 80 nm, the second inorganic oxide being formed on the first laminate by a high density plasma enhanced chemical vapor deposition 2 laminate; And a transparent conductive layer formed on the second laminate and having a thickness of 15 nm to 50 nm.

According to a second aspect of the present invention, there is provided a method of manufacturing a transparent conductive film, comprising: preparing a non-coated substrate comprising plastic; Forming a first laminate including an inorganic oxide and having a refractive index of 1.6 to 2.0 and a thickness of 0.4 to 1.0 mu m on the non-coated substrate using a high-density plasma enhanced chemical vapor deposition method; A second laminate including an inorganic oxide different from the inorganic oxide included in the first laminate and having a refractive index of 1.3 to 1.5 and a thickness of 30 nm to 80 nm on the first laminate using high density plasma enhanced chemical vapor deposition Forming a sieve; And forming a transparent conductive layer having a thickness of 15 nm to 50 nm on the second laminate.

Meanwhile, the touch panel according to the third aspect of the present invention may include the transparent conductive film according to the first aspect of the present invention.

According to the above-mentioned problem solving means of the present invention, by providing the function of hardness enhancement to the first laminate formed by the high density plasma enhanced chemical vapor deposition method as one of the laminate constituting the refractive index combination structure, the surface hardness, scratch resistance, , The transmittance and visible visibility of the visible light are improved, the production efficiency of the manufacturing process is maximized, and the production time, process number, defective ratio and the like are reduced.

Further, according to the present invention, it is possible to realize a transparent conductive film having an improved hardness by forming a laminate having a refractive index combination structure and a transparent conductive layer on a non-coated substrate, Since the transparent conductive film can be produced using a non-coated film without using a film, the manufacturing cost of the transparent conductive film can be drastically reduced, contributing to the localization of the component material.

In addition, since the touch panel includes a transparent conductive film which can be produced with high efficiency while having an improved surface hardness, scratch resistance, abrasion resistance, transparency of visible light and pattern visibility, it is possible to have resistance against scratches And can be produced with high efficiency.

1 is a schematic cross-sectional view for explaining a transparent conductive film according to an embodiment of the present invention.
2 is a schematic diagram for explaining a roll-to-roll deposition apparatus.
3 is a schematic flow chart for explaining a method of manufacturing a transparent conductive film according to an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention. It should be understood, however, that the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. In the drawings, the same reference numbers are used throughout the specification to refer to the same or like parts.

Throughout this specification, when a part is referred to as being "connected" to another part, it is not limited to a case where it is "directly connected" but also includes the case where it is "electrically connected" do.

Throughout this specification, when a member is " on " another member, it includes not only when the member is in contact with the other member, but also when there is another member between the two members.

Throughout this specification, when an element is referred to as "including " an element, it is understood that the element may include other elements as well, without departing from the other elements unless specifically stated otherwise. The terms "about "," substantially ", etc. used to the extent that they are used throughout the specification are intended to be taken to mean the approximation of the manufacturing and material tolerances inherent in the stated sense, Accurate or absolute numbers are used to help prevent unauthorized exploitation by unauthorized intruders of the referenced disclosure. The word " step (or step) "or" step "used to the extent that it is used throughout the specification does not mean" step for.

The present invention relates to a transparent conductive film, a method of manufacturing the same, and a touch panel including the transparent conductive film.

First, a transparent conductive film (hereinafter referred to as 'the present transparent conductive film') according to one embodiment of the present invention will be described.

1 is a schematic cross-sectional view for explaining the present transparent conductive film.

Referring to FIG. 1, the transparent conductive film 100 includes a non-coated substrate 110; A first laminate 120, a second laminate 130, and a transparent conductive layer 150.

The non-coated substrate 110 includes plastic.

Further, the first laminate 120 is formed on the non-coated substrate 110 by plasma enhanced chemical vapor deposition (PECVD) and includes an inorganic oxide. In addition, the first laminate 120 may have a refractive index of 1.6 to 2.0 and a thickness of 0.4 to 1.0 占 퐉.

The second laminate 130 includes an inorganic oxide different from the inorganic oxide included in the first laminate 120 and formed on the first laminate 120 by the plasma enhanced chemical vapor deposition method. In addition, the second laminate 130 has a refractive index of 1.3 to 1.5 and a thickness of 30 nm to 80 nm.

In the present transparent conductive film 100, the first layered product 120 and the second layered product 130 may have an index matching structure.

In addition, the plasma enhanced chemical vapor deposition method applied in forming the first layered body 120 and the second layered body 130 may be a high density plasma enhanced chemical vapor deposition method.

Further, the transparent conductive layer 150 is formed on the second laminate 130 and has a thickness of 15 nm to 50 nm.

The hardness of the present transparent conductive film (100) can be improved by the first laminate (120).

That is, the transparent conductive film 100 may provide the first layered body 120, which is one of the layered bodies 120 and 130 having a refractive index combination (index matching) structure, as a hardness improving function. Accordingly, a transparent conductive film having improved surface hardness, scratch resistance and abrasion resistance can be realized while reducing the production time, process number, defect rate, etc. consumed in manufacturing the transparent conductive film.

In general, the surface properties of the transparent conductive film are improved, so that resistance to scratches (scratches) that may occur during a process of manufacturing a touch panel to which a transparent conductive film is applied is increased by an input tool such as a touch pen To form a film. Illustratively, the hard coat layer was formed through a separate wet coating process in the production of the transparent conductive film.

However, according to the transparent conductive film 100 of the present invention, since the first layered body 120 having a refractive index combination (index matching) structure has a hardness improving function, it can function as a hard coating layer of a conventional transparent conductive film have. Further, since the first laminate 120 is formed by the plasma enhanced chemical vapor deposition method, the number of processes and time which have been increased by the wet coating process which is conventionally performed separately to form the hard coating layer, can be shortened.

That is, according to the present transparent conductive film 100, a transparent conductive film having a high surface hardness and improved scratch resistance and abrasion resistance can be realized, and at the same time, the production efficiency of the manufacturing process can be maximized, The production time, the process number, the defect rate, and the like can be reduced.

The structure related to the transparent conductive film 100 will be described in detail as follows.

The first stack body 120 can be formed (film-formed) by a plasma enhanced chemical vapor deposition method. For example, it can be formed by a plasma enhanced chemical vapor deposition method of Roll to Roll type.

2 is a schematic diagram for explaining a roll-to-roll deposition apparatus.

Referring to FIG. 2, the roll-to-roll deposition apparatus is configured to form an oxide thin film on the non-coated substrate 110. Winding rollers and unwinding rollers for winding and uncoating the non-coated substrate 110 are provided on the upper part of the chamber. Further, a tension control device for controlling the tension of the non-coated substrate 110 and a tension sense may be provided.

Referring to FIG. 2, the uncoated substrate 110 uncoated on the unwinding rollers reaches the cooling drum via the guide rollers, and the cooling and deposition process of the uncoated substrate 110 can be performed in the cooling drum. The uncoated base material 110 after the film formation is wound on a winding roller through a guide roller.

At this time, the deposition may proceed through generation of plasma by a linear HD-PECVD reactor so that the uniformity of the first stack body 120 formed on the non-coated substrate 110 is improved. Also, in this process, the temperature of the cooling drum is maintained at 8 DEG C, so that deformation of the uncoated substrate 120 due to plasma exposure can be minimized.

More specifically, the roll-to-roll type plasma enhanced chemical vapor deposition can be implemented as follows.

The non-coated substrate 110 is loaded in a roll-to-roll driven vacuum chamber equipped with a large area linear HD-PECVD reactor, and the degree of vacuum of the vacuum chamber can be formed to 10 ^-5 torr by a low vacuum and a high vacuum pump. Thereafter, argon (Ar), which is an activation gas, may be injected by a mass flow controller (MFC), which is an automatic gas injection device, for the plasma ignition for chemical reaction, Can be injected in an amount optimized to the intensity of the power value applied by the AC oscillator.

After formation of the plasma, a precursor stored in a Precursor injector (one of TMA cabinet and TMDSO cabinet as shown in FIG. 2) is vaporized and fed into the interior of the vacuum chamber by an MFC, O2, which is a reaction gas, can be injected at an optimized amount of gas to form a thin film through the MFC so that the best molecular bonding with the precursor can be achieved.

At this time, the power applied to the HD-PECVD reactor may be applied by an AC generator of 40 to 60 kHz (MF). Also, the power value may be a predetermined power value that is optimized to dissociate the precursor and dissociate the dissociated radicals.

The deposition rate DR of the first layered body 110 varies depending on the applied AC power (power value) in the same process conditions (working vacuum degree, TMA amount, O2 amount, etc.) And hardness may be affected.

Specifically, the lower the AC power applied to the PECVD reactor under the same process conditions, the slower the deposition rate, the more compact the particles, the higher the density, the higher the refractive index, and the higher the hardness.

Therefore, the AC power value applied to the HD-PECVD reactor at the time of forming the first laminated body 120 is such that the density of the thin film becomes higher as the power is lowered under the same process conditions of the first laminated body 120 except for the power, Can be improved.

The predetermined power value can be determined according to the molecular binding energy, melting point, and refractive index of the thin film to be formed. Typically, a thin film having a high molecular binding energy, a high melting point, and a high refractive index has a unit application power value w / cm < 2 >) may be large, so that this point is taken into account and a predetermined power value can be determined.

Further, in order to form the first laminate 120 (thin film) with the uniform and dense optimum, the power value applied to the plasma generating source can be set optimally to the amount of the precursor to be injected, The gas partial pressure ratio such as the amount of reactive gas can be set, and the optimal environmental conditions such that the injected gases can smoothly flow in the vacuum chamber can also be set. Further, with this optimum condition being set, the working vacuum degree can be maintained at 10 ^-4 torr.

Also, an initial vacuum pressure may be maintained to maintain a working pressure that may have a mean free path. Illustratively, the initial degree of vacuum may be 10 ^-5 torr.

2, the unreacted gases that have not participated in the chemical reaction during the film formation are absorbed through a high vacuum pump (TMP) installed on the back of the PECVD reactor and discharged through the exhaust pipe to the atmosphere through a gas neutralizer .

Also, in the plasma enhanced chemical vapor deposition method, a high density plasma (HDP) reactor can be used. In other words, high-density plasma enhanced chemical vapor deposition (HD-PECVD) may be used in the formation of the first laminate 120.

Generally, the CVD (Chemical Vapor Deposition) method refers to a method of decomposing a gaseous compound and forming a thin film on a substrate using a chemical reaction. In the case of general chemical vapor deposition (CVD), since the deposition occurs at a high temperature, a phase change occurs on the surface of the substrate and the electrical and mechanical properties are deteriorated. Thus, there is a limitation in selection of the substrate and a difficulty in applying it to a large- .

Among these CVD methods, plasma enhanced chemical vapor deposition (CVD) is a process of depositing these reactants on a substrate by forming a plasma using organic or inorganic vapor capable of being polymerized. The plasma enhanced chemical vapor deposition is a process of depositing these reactants on a substrate, Organic hybrids having intermediate characteristics of organic and inorganic materials, and it is possible to deposit materials having various properties by copolymerization. In addition, when inserting a functional group, it has an advantage of being excellent in surface adhesion as well as being less influenced by characteristics of the substrate.

Recently, a low temperature process for a flexible display and a touch panel is required. Accordingly, there is a growing interest in plasma enhanced chemical vapor deposition (PECVD), which has advantages such as low process temperature, high deposition rate and the like, which can assist the reaction mechanism with the energy of the plasma in the CVD method.

Plasma enhanced chemical vapor deposition (CVD) generates glow discharge using direct current or high frequency to cause electrons with high energy to collide with reactant gas containing atoms of thin film structure to generate reactant gas as activated ions or radicals It is possible to deposit at a relatively low temperature as compared with the conventional chemical vapor deposition method and to obtain a rapid deposition rate which can not be obtained by the physical vapor deposition method and to obtain a uniform vapor deposition layer Have.

The inventors of the present application have found that a high-density PECVD (HD-PECVD) method in which a high density and energy of plasma production is used in the plasma enhanced chemical vapor deposition method forms a laminate having a predetermined thickness, refractive index, hardness, The present invention is applied to the production of the transparent conductive film.

Since HD-PECVD (High Density-Plasma Enhanced Chemical Vapor Deposition) is advantageous for low-temperature deposition and can be applied to a large-area substrate, a laminate is deposited on a large area using a base material including plastic, Which is an effective method for forming a thin film.

According to HD-PECVD, the thickness, refractive index, hardness, and the like of each layer to be formed can be adjusted more easily and precisely by adjusting the respective parameters, so that the transparent conductive film 100 can be easily manufactured.

In the production of the transparent conductive film 100, the HD-PECVD is not only easy to form a high refractive index thin film having a high molecular binding energy and a melting point of a high melting point, The density of the thin film can be improved and the deposition rate (DR-Deposition Rate) is advantageous.

In other words, according to HD-PECVD, the effect of index matching can be improved when multi-layers are stacked due to the possibility of forming a high-density plasma and a low-temperature process (60 ° C or less) and excellent gap-filling ability. Also, the deposition time of the laminate formed by the high-speed deposition (high DR) can be reduced, so that the productivity can be improved and the density of the laminate (thin film) formed through the ion bombardment effect by the generated ions . Accordingly, when the inorganic / metal oxide thin film is formed, the refractive index of the thin film can be changed by adjusting the oxygen partial pressure and controlling the applied power.

Meanwhile, the first laminate 120 may include alumina (Al 2 O 3).

Alumina is a material having a sapphire molecular structure and has high thermal stability due to its high melting point, high mechanical strength and hardness, excellent electrical insulation, and excellent corrosion resistance. By including such alumina in the first laminate 120, the transparent conductive film 100 can secure a high surface hardness.

In addition, the first layered body 120 may be formed by a plasma-enhanced chemical vapor deposition method using a TMA (Tri-Methyl-Aluminum) precursor.

The TMA precursor has a molecular formula of C3H9Al, and aluminum is linked to three methyl groups (-CH3). Such a TMA precursor has a relatively low vapor pressure and boiling point in the aluminum compound and is easily dissociated by the plasma, so that the first layered body 120 including alumina can be formed more easily.

More specifically, the TMA precursor is dissociated by the plasma to leave hydrocarbons, and the ionized Al ions are ion-bonded to the oxygen injected into the reactive gas, so that the first laminate 120 containing alumina is bonded to the non- (Not shown).

In other words, the TMA precursor may implement a process suitable for forming the first laminate 120 comprising alumina.

However, in the present invention, the first layered product 120 may be formed of an ATI (Aluminum-Tri-Isopropoxide) precursor, a TIA (Tri-Isobutyl-Aluminum) precursor, an Aluminum-s-butoxide precursor, a TIPA -i-propoxide) precursor or the like.

The first laminate 120 may be formed by a DC power ion bombarder in the plasma enhanced chemical vapor deposition (hereinafter referred to as " plasma enhanced chemical vapor deposition " By supplying the activation energy on the surface, it can be formed with a high density.

In addition, the activation energies are such that a uniform magnetic field is formed by the magnets installed inside the DC power ion bombarder, and ions ionized by the electric field effect by the DC power are applied to the glass substrate May be supplied on the surface of the non-coated substrate 110 on which the first laminate is formed by bombarding the particles to be laminated on the substrate 110.

The first layered body 120 is formed by applying a sub-bias (Bias) to a magnetic field formed by a large area linear HD-PECVD reactor in the plasma enhanced chemical vapor deposition method and generating an electric field perpendicular to the magnetic field And the direction of the plasma ions generated inside the vacuum chamber is focused toward the non-coated substrate 110 disposed inside the vacuum chamber, so that the plasma can be formed with a high density.

On the other hand, the second laminate 130 may include an inorganic oxide different from the inorganic oxide included in the first laminate 120, as described above. Illustratively, the second stack 130 may comprise SiO2.

Further, the second stack body 130 may be formed by a plasma enhanced chemical vapor deposition method. Illustratively, the second laminate 130 can be formed by the plasma enhanced chemical vapor deposition method of the Roll to Roll method described above.

Further, in the plasma enhanced chemical vapor deposition method for forming the second stack body 130, the precursor may be TMDSO (tetramethyldisiloxane). The method of forming the second layered body 130 will be described in detail in a method of manufacturing the transparent conductive film 100 to be described later.

The inorganic oxide of the first laminate 120 and the inorganic oxide of the second laminate 130 may be aluminum oxide, zirconium oxide, titanium oxide, zinc oxide oxide, yttrium oxide, ytterbium oxide, and silicon oxide. In the present invention, the metal oxide may be at least one selected from the group consisting of cerium oxide, cerium oxide, tantalum oxide, yttrium oxide, ytterbium oxide, . Illustratively, as described above, the first laminate 120 may comprise alumina. Further, the second stack body 130 may include SiO2.

The transparent conductive layer 150 may be formed of at least one selected from the group consisting of indium tin oxide (ITO), antimony tin oxide (ATO), gallium oxide zinc oxide (GZO), zinc oxide AZO, indium zinc oxide (IZO) Tubes, and graphenes. ≪ RTI ID = 0.0 > [0040] < / RTI >

Also, illustratively, the transparent conductive layer 150 may have a metal mesh structure. Alternatively, the transparent conductive layer 150 may be provided in the form of a layer in which silver nanowires are dispersed.

The transparent conductive layer 150 may be formed by immersing the non-coated substrate 110 in which the second layered body 130 is formed in the sputter chamber and performing RF magretron sputtering. The method for forming the transparent conductive layer 150 will be described in detail in a method for producing the transparent conductive film 100 to be described later.

In addition, the non-coated substrate 110 may include at least one of polycarbonate (PC), polyethylene terephthalate (PET), polyethersulfone (PES), polyethylene naphthalate (PEN), polyarylate have.

The transparent conductive film 100 may further include a protective film (not shown) provided on the opposite side of the surface of the non-coated substrate 110 on which the first layered body 120 is formed.

The surface of the non-coated substrate 110 on which the first layered body 120 is formed can be protected through the first layered body 120 having a high hardness, The surface can be exposed uncoated. Thus, the opposite side of the non-coated substrate 110 can be protected through this protective film. Illustratively, the protective film may be attached to the opposite side of the non-coated substrate 110 in a laminated manner. Such a protective film may be variously constructed by those skilled in the art, so that detailed description thereof will be omitted.

Hereinafter, a method for manufacturing a transparent conductive film according to one embodiment of the present invention (hereinafter referred to as "the present manufacturing method") for producing a transparent conductive film according to an embodiment of the present invention will be described. It should be noted that the same reference numerals are used for the same or similar components as those of the transparent conductive film according to one embodiment of the present invention, and redundant explanations will be simplified or omitted.

3 is a schematic flowchart for explaining the method of manufacturing the present transparent conductive film.

3, the manufacturing method includes a step S110 of preparing a non-coated substrate 110, a step S120 of forming a first laminated body 120 on the non-coated substrate 110, A step S130 of forming a second laminate 130 on the laminate 120 and a step S150 of forming a transparent conductive layer 150 on the second laminate 130. [

In step S110, the uncoated substrate 110 includes plastic.

In step S120, a first laminate 120 containing an inorganic oxide and having a refractive index of 1.6 to 2.0 and a thickness of 0.4 to 1.0 mu m is formed on the non-coated substrate 110 by plasma enhanced chemical vapor deposition . The plasma enhanced chemical vapor deposition method applied in step S120 may be a high density plasma enhanced chemical vapor deposition method.

In step S130, the second laminate 130 includes an inorganic oxide different from the inorganic oxide included in the first laminate 120 using a plasma enhanced chemical vapor deposition method, and has a refractive index of from 3 to 1.5, 30 nm to 80 nm. The plasma enhanced chemical vapor deposition method applied in step S130 may be a high density plasma enhanced chemical vapor deposition method.

In step S150, the transparent conductive layer 150 is formed to a thickness of 15 nm to 50 nm.

The construction related to the present manufacturing method will be described in detail as follows.

 The first laminate 120 may comprise alumina.

Further, in step S120, the first laminate 120 may be formed by a plasma enhanced chemical vapor deposition method. For example, it can be formed by a plasma enhanced chemical vapor deposition method using a TMA (Tri-Methyl-Aluminum) precursor.

As described above, the TMA precursor has a molecular formula of C3H9Al, and aluminum is connected to three methyl groups (-CH3). The TMA precursor has relatively low vapor pressure and boiling point in the aluminum compound and is easily dissociated by the plasma, so that the first laminate 120 including alumina can be formed more easily.

In general, the TMA used as the precursor has a lower vapor pressure and a higher boiling point at 1 atm than the TMDSO used as the precursor for forming the SiO2 oxide layer. In performing the step S120, the vaporized TMA gas is used as the precursor vessel It can be condensed and formed into powder during the process of being transferred from the canister to the chamber piping. To prevent this, the temperature of the piping line from the canister to the inside of the gas cabinet and to the PECVD reactor can be maintained at 60 ° C.

In addition, in step S120, the first laminate 120 may be formed by a plasma enhanced chemical vapor deposition method using a roll-to-roll method. The roll-to-roll type plasma enhanced chemical vapor deposition may be performed by a roll-to-roll deposition apparatus.

Also, before step S120, the heater installed between the winding / unwinding rollers of the roll-to-roll type evaporation apparatus and the guide roll was heated to 120 DEG C and the degree of vacuum in the chamber was maintained at 10 ^-6 torr, By passing the substrate 110, a pretreatment process (Out-Gassing) for removing the organic gases contained in the non-coated substrate 110 can be performed.

In step S120, the precursor stored in the precursor injecting apparatus is supplied to the inside of the vacuum chamber by using a mass flow controller (MFC), which is an automatic gas charging apparatus, by HD-PECVD using a roll- . Thereafter, the Al 2 O 3 first laminate 110 is injected by injecting O 2, which is a reaction gas, with MFC at a gas amount set to achieve the best molecular bonding with the precursor, thereby inducing a phase change on the non- Can be formed. As a result, the first laminate 110 can be formed in a uniform and dense manner. The set gas volume of O2 can be calculated from the precursor and stoichiometric amount calculations.

Also, the power value (power) applied to the large area linear PECVD reactor can be applied by an AC generator of 40 to 60 kHz (MF). Also, the power value may be preset and applied with an optimized value such that the precursor is dissociated and the dissociated radicals are recombined.

The deposition rate DR of the first layered body 110 varies depending on the applied AC power (power value) in the same process conditions (working vacuum degree, TMA amount, O2 amount, etc.) And hardness may be affected.

Specifically, the lower the AC power applied to the PECVD reactor under the same process conditions, the slower the deposition rate, the more compact the particles, the higher the density, the higher the refractive index, and the higher the hardness.

Also, the refractive index may vary depending on the partial pressure ratio of the gases participating in the process reaction. Illustratively, when the gas partial pressure ratio of O2: TMA is equal to the gas partial pressure ratio of Ar: O2: TMA, The refractive index can be increased by the Assist effect by the activated plasma ion (Ar +). Also, for the same process conditions and gas partial pressure ratio, the deposition rate (DR) changes depending on the applied AC power value, and the densities of the stacked particles change and the surface hardness may also vary due to the change of the refractive index value.

Therefore, the predetermined power value can be set to a value obtained through repeated experience according to a desired forming condition and environment of the first laminate 110. [

In step S120, the AC power value applied to the HD-PECVD Reactor for forming the first laminated body 120 is set such that the first laminated body 120 is formed to have a higher diameter than the second laminated body 130, It is preferable that the AC power value applied to the HD-PECVD Reactor is smaller than that of the AC-power applied to the HD-PECVD Reactor for the formation of the second stack body 130. [

In addition, in step S120, when the first layered body 120 is formed, the density of the first layered body 110 can be increased by forming the deposited particles into a dense grain boundary structure. To do this, in step S120, it is possible to induce a bombardment of ions generated in the vacuum chamber.

More specifically, a DC power ion bombarder can be used to supply activation energy (surface activation energy) to the surface of the non-coated substrate 110. A uniform magnetic field is formed by a magnet installed inside the DC Power Ion Bombarder, and ions that are ionized (for example, Ar + ions) are bombarded by the electric field effect by the DC power, so that the first stack body 120 The activation energy can be supplied on the surface of the non-coated substrate 110 to be formed. Thus, the first laminated body 120 having a stable film structure can be formed.

In addition, a sub-bias (Bias) may be applied in a magnetic field formed by the large area linear HD-PECVD Reactor so that the direction of the plasma ions generated inside the vacuum chamber can be focused toward the non-coated substrate 110 disposed inside the vacuum chamber. Accordingly, the surface activation energy can be supplied to improve the density and the refractive index of the first laminate 120.

The surface hardness of the first layered body 120 including the formed Al2O3 is increased by the surface roughness of the first layered body 120 formed by the grain size to be laminated even under the conditions of the best molecular bonding, Can be influenced. For example, the surface hardness can be measured to be low as the surface roughness is increased under conditions having the same thickness, thin film density and refractive index. Therefore, it is preferable that the first layered body 120 is formed in consideration of these points.

For reference, when forming the first laminate 120 containing Al 2 O 3 by PECVD, the AC power value applied to the PECVD reactor, the amount of the TMA precursor to be injected, the partial pressure of the O 2 gas and the Ar gases reacting therewith, DC power of the DC Power Ion Bombarder, and the voltage applied to the sub-bias, and the surface roughness varies from 0.2 ㎛ to 0.8 ㎛ even with a slight change of each of these factors. Respectively.

Further, in step S130, the second stack body 130 may be formed by a plasma enhanced chemical vapor deposition method. Illustratively, the second laminate 130 may be formed by a plasma enhanced chemical vapor deposition (CVD) process using a roll-to-roll process.

At the time of forming the second stack body 130, the cooling drum of the roll-to-roll type deposition apparatus can be maintained at 8 캜.

Further, in the plasma enhanced chemical vapor deposition method for forming the second stack body 130, the precursor may be TMDSO (tetramethyldisiloxane).

The TMDSO used as a precursor has a higher vapor pressure than TiCl 4 and a boiling point of 25 ° C at 1 atmospheric pressure, so that no separate heating process is required to the inside of the canister and the gas cylinder and the PECVD reactor, so that the step S130 can be easily performed.

TMDSO is a complex organic compound in which the molecular formula is C4H14OSi2 and Si inorganic material, Ch3 methyl group and hydrogen molecule are bonded by a radical polymerization process. This TMDSO can be deposited in the second stack body 130 by dissociation by electrons generated in the PECVD reactor and then recombining with the reactor gas.

In performing step S130, the power value and the gas mixture ratio may be set to optimum values for the optimum process. Illustratively, the power value and the gas mixture ratio can be set by analyzing characteristics of the second laminate 130 formed according to process conditions such as power value, gas mixture ratio, and the like. Illustratively, in order to supply plasma energy that can control the sufficient dissociation process of the TMDSO used as a precursor, an Ar gas, which is an activation gas, is further injected while a reactive gas and a partial pressure ratio of O 2 Can be determined.

Illustratively, for the formation of the second laminate 130 with optimal properties, when an AC power source value of 6.2 w / cm 2 is applied to the PECVD reactor, the gas partial pressures of Ar and O 2 are 1: 4 Lt; / RTI > The gas partial pressures of Ar and O2 can be controlled by adjusting the gas mixture ratio of the gas mixture based on the stoichiometric formula to find the process conditions for forming the second laminate 130 containing SiO2 having the optimum characteristics The thickness and refractive index of the thin film according to the change can be found by referring to the data measured using an ellipsometer.

Also, in the step of S130, when the mixing ratio of Ar and O2 is 1: 4, the DDR value shows a linear proportional relationship, but the refractive index of the SiO2 thin film may vary depending on the supply amount of TMDSO, For the implementation of the thickness and the refractive index according to the optical design of the conductive film 100, the TMDSO amount and the mixed gas ratio may be TMDSO: Ar: O 2 = 1: 1: 4 in the step S130.

When the change of the deposition rate is observed while changing the TMDSO amount and the AC power value (power value) applied to the PECVD reactor while maintaining the gas partial pressure ratio, the same gas partial pressure ratio A change in the refractive index and a linear thickness change of the second laminate 130 including SiO 2 may occur due to the power value. By applying the process conditions of the linear result change to the optical design of the refractive index combination structure, the production efficiency and the yield can be improved.

On the other hand, in the step S130, the precursor is not limited to TMDSO. Illustratively, in addition to TMDSO, HMDSO, TMOS, SiH4, etc. may be applied as precursors.

In step S150, the non-coated substrate 110 on which the second stacked body 130 is formed is dipped in the sputter chamber, and the transparent conductive layer 150 is formed on the second stacked body 130 through RF magretron sputtering . At this time, the transparent conductive layer 150 to be formed may include indium tin oxide (ITO).

In step S150, the process parameters influencing the characteristics of the transparent conductive layer 150 include pulse DC power, gas amount and gas flow rate of Ar: O2, roll wind speed of the non-coated substrate 110, (T / S distance), initial vacuum, working pressure, and pre-treatment process conditions between the substrate 110 and the substrate 110. These process parameters can be obtained by comparing the surface resistance value with the thickness of the transparent conductive layer 150 formed through repetitive experiments.

Illustratively, in performing step S150, the target may comprise a 95 wt% indium oxide sintered body containing 5 wt% of tin monoxide. Also, the chamber initial vacuum can be set to 4.0 x 10 ^-5 torr, the argon gas partial pressure can be set to 80%, the oxygen gas partial pressure can be set to 20%, the Pulse DC Power can be set to 50 kHz, 0.8 Kw And the roll wind speed can be set to 2.5 m / min. The ArO 2 gas amount and the gas flow rate ratio can be set to 90.3%: 1.7% The distance (T / S distance) can be set to 80 mm and the working pressure can be set to 9.0 x 10 ^-3 torr. According to this, the transparent conductive layer 150 having a refractive index of 2.05 can be formed.

The resistance value of the transparent conductive layer 150 is related to the thickness of the transparent conductive layer 150, the weight% of the target structure material, and the oxygen partial pressure.

Also, the resistance value of the transparent conductive layer 150 can be controlled by the process performed before the step S150, that is, the degree of contamination of the impurity contained in the surface of the second layered body 130 and the degree of De- And so on. This is because the impurities remaining on the surface of the second layered body 130 can bond with the particles deposited for forming the transparent conductive layer 150. More specifically, when the transparent conductive layer 150 includes ITO, the impurities remaining on the surface of the second layered body 130 are bonded to the O2 of the ITO molecules stacked for the formation of the transparent conductive layer 150 It can affect the carrier concentration that determines the resistance of the ITO.

Therefore, in order to block such influence, the surface of the second laminate 130 can be surface-treated with an ion bombarder using DC power. For example, when a magnetic field is formed by a magnet installed inside the DC Power Ion Bombarder, Ar + ions ionized by the electric field effect by DC power are moved by the magnetic field to remove impurity gas or the like on the surface of the second stack body 130 Can be removed. Accordingly, the influence on the resistance value of the transparent conductive layer 150 in the process performed before the step S150 can be minimized. In addition, according to this, the adhesion between the second stack body 130 and the transparent conductive layer 150 can be improved.

In addition, a protective film may be provided on the opposite side of the surface of the non-coated substrate 110 on which the first layered body 120 is formed. Illustratively, this protective film may be provided together, but is not limited to, performing step S110, i.e., preparing the non-coated substrate 110.

Hereinafter, the effects of the present invention will be specifically confirmed through the examples. However, the present invention is not limited by the following examples.

Using a roll-to-roll PECVD apparatus equipped with a Linear HD-PECVD Reactor, Al2O3 was included on one side of the uncoated substrate having a thickness of 125 mu m using TMA (Tri-Methyl-Aluminum) precursor according to the above step S120 And a first laminate having the characteristics recorded in Table 1 was formed. At this time, the partial pressure ratio of the injected gas was injected by using an MFC (mass flow controller) as an automatic gas injection device with precursor: Ar: O2 = 8%: 11%: 1% w / cm < 2 > power was applied to the PECVD Reactor.

Further, a second laminate having the characteristics recorded in Table 1 was formed using the TMDSO (Tetramethyldisiloxane) precursor according to the above step S130 on the formed first laminate. At this time, the AC power applied to the PECVD reactor was 6.2 w / cm 2.

The transparent conductive layer 150 was formed by RF magretron sputtering using a 95 wt% indium oxide sintered body containing 5 wt% of tin monoxide as a target, using a film in which the second layered product was formed, and sputtering. At this time, the initial vacuum degree of the chamber was maintained at 4.0 x 10 ^-5 torr, the argon gas partial pressure was 80% and the oxygen gas partial pressure was 20%, the pulse DC power was set to 50 kHz and 0.8 Kw, The distance between the ITO target and the non-coated substrate 110 (T / S distance) was set at 80 mm, and the working pressure (working pressure) was set at 90.3% ) Was set to 9.0 x 10 ^-3 torr to form a transparent conductive layer containing ITO having a refractive index of 2.05 and a surface resistance of 150 Ω / cm 2 (resistance after heat treatment at 150 ° C. for 60 minutes) after heat treatment.

In forming the transparent conductive layer, one of the important factors for determining the surface resistance is the impurity remaining on the surface of the second layered body, which is bound to the O2 molecule of the ITO molecule in which the impurity is deposited to determine the resistance of the ITO The surface of the second laminate was surface-treated with an ion bombarder using DC power to prepare a transparent conductive film according to one embodiment of the present invention.

In order to investigate the difference in the pencil hardness, curl and scratch resistance of the transparent conductive film according to the refractive index change of the first laminate, the value of AC power applied to the PECVD reactor in the formation of the first laminate was set to 10.3 w / cm < 2 >, respectively.

In order to investigate the difference in the pencil hardness, curl and scratch resistance of the transparent conductive film according to the change in the thickness of the first layered body, the ratio of the amount of the injected gas in the formation of the first layered body was maintained The transparent conductive film (100) was prepared in the same manner as in Example 1, except that the amounts of the respective components were increased by 1.6 times.

[Comparative Example 1]

In order to investigate the visible light transmittance and transmittance hue characteristics of the transparent conductive film having a laminate having a one-layer structure as compared with the transparent conductive film having the two-layered laminate realized in Examples 1 to 3, To prepare a conductive film.

Using a roll-to-roll PECVD apparatus equipped with a Linear HD-PECVD Reactor, a TMA (Tri-Methyl-Aluminum) precursor was formed on one side of a non-coated PET film having a thickness of 125 탆 according to the above step S120, And a first layered body containing Al2O3 was formed. At this time, the partial pressure ratio of the injected gas was injected by using an MFC (mass flow controller) as an automatic gas injection device with precursor: Ar: O2 = 8%: 11%: 1% w / cm < 2 > power was applied to the PECVD Reactor.

Further, a film in which the first laminate was formed was immersed in a sputter chamber, and a transparent conductive layer was formed by RF magretron sputtering using a 95 wt% indium oxide sintered body containing 5 wt% of tin monoxide as a target. At this time, the initial vacuum degree of the chamber was maintained at 4.0 x 10 ^-5 torr, the argon gas partial pressure was 80% and the oxygen gas partial pressure was 20%, the pulse DC power was set to 50 kHz and 0.8 Kw, The flow rate was set at 90.3%: 1.7%, the roll winding speed was set at 2.5m / min, the distance between the ITO target and the non-coated substrate (T / S distance) was set at 80mm, 9.0 × 10 ^-3 torr to form a transparent conductive layer containing ITO having a refractive index of 2.05 and a surface resistance of 150 Ω / cm 2 (resistance after heat treatment at 150 ° C. for 60 minutes) after the heat treatment.

In forming the transparent conductive layer, one of the important factors for determining the surface resistance is the impurity remaining on the surface of the first layered body, which is bonded to the O2 molecule of the ITO molecule in which the impurity is deposited to determine the resistance of the ITO The surface of the first layered product was surface-treated with an ion bombarder using DC power to prevent the carrier concentration. Thus, a transparent conductive film was prepared.

The results of pencil hardness and scratch characteristics of the transparent conductive films according to Examples 1 to 3 are shown in Table 1 below.

[Table 1]

[Table 2]

≪ Thickness measurement method &

The thickness and the refractive index of the laminate including Al2O3 formed in Examples 1 to 3 and Comparative Example 1 of the present application were measured using an ellipsometer (ELLi-SE) of Ellipsote.

≪ Visible light average transmittance and transmission color value (b *) measurement method >

The average transmittance of the laminate including Al2O3 formed in Examples 1 to 3 and Comparative Example 1 herein was measured using a U430 Spectrophotometer manufactured by Hitachi, Ltd., and the color value (color coordinate value ) Were measured using a CIE chromaticity coordinate method and a D 75 optical source.

≪ Method of measuring pencil hardness &

A transparent conductive film was made into a sample having a size of 150 mm x 100 mm and the pencil hardness was measured five times under a load of 750 g in accordance with the pencil hardness test standard of JIS K 5600-5-4, Respectively. The pencil was used for a pencil scratch test manufactured by Mitsubishi Pencil Co., In pencil hardness, the symbols H, F, and B indicate the hardness and density, respectively, and are hard, firm, and black initials, and the higher the number H, the harder the harder. That is, 9H has the highest hardness, which means a lower hardness toward 8H, 7H, 6H, 5H, 4H, 3H, 2H, H, F, B, 2B, 3B, 4B, 5B, 6B, 7B, 8B and 9B do.

≪ Scratch resistance - How to measure scratch resistance >

A transparent conductive film was made into a sample having a size of 200 mm x 200 mm and uniformly adhered to a flat surface of a circumference of 25 mm in diameter with a steel wool # 0000. The sample surface was subjected to a load of 0.5 kg at a speed of about 100 mm per second (I), the number of scratches is 11 to 20 (II), the number of scratches is 21 (I), and the number of scratches is 21 (III) and more than 31 (IV).

The results of Table 1 are summarized as follows.

First, Example 1 and Example 2 show different refractive index values depending on the difference of AC power applied to the PECVD Reactor under the same laminates and process conditions. The lower the power value, the lower the deposition rate (DR-Deposition Rate), and the lower the deposition rate, the denser the deposited particles, the higher the refractive index of the thin film, the higher the density of the thin film, .

In Example 1 and Example 2, the pencil hardness characteristics were measured in the same manner as in Table 1, but in the scratch resistance, the laminate including Al2O3 of Example 2 had a refractive index of 1.99, which was relatively higher than that of Al2O3 of Example 1 Is superior to the laminated body. Comparing Example 1 and Example 3, it can be seen that surface hardness and scratch resistance are improved as the thickness of the laminate including Al3O3, which depends on the hardness characteristic, is increased.

In addition, referring to Table 2, it can be seen that the transmittance of the visible light ray is higher and the transmittance color value (b *) value is lower than that of Comparative Example 1, in which the number of the stacked bodies is larger than that of Comparative Example 1. [ This is in agreement with the optical result that the surface reflectance becomes lower as the transmittance becomes higher as the number of low refractive index and high refractive index layers are alternately increased as the optical layer is designed.

Hereinafter, a touch panel according to an embodiment of the present invention will be described. It should be noted, however, that the same reference numerals are used for the same or similar components as those of the present application, and redundant explanations thereof will be simplified or omitted.

The touch panel according to one embodiment of the present invention includes the transparent conductive film 100 according to one embodiment of the present invention.

The touch panel according to one embodiment of the present invention includes the transparent conductive film 100 according to one embodiment of the present invention, so that the surface hardness, scratch resistance and abrasion resistance can be improved. In addition, the production efficiency can be improved.

It will be understood by those of ordinary skill in the art that the foregoing description of the embodiments is for illustrative purposes and that those skilled in the art can easily modify the invention without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is defined by the appended claims rather than the detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included within the scope of the present invention.

100: transparent conductive film 110: non-coated substrate
120: first laminate 130: second laminate
150: transparent conductive layer

Claims (16)

In the transparent conductive film,
A non-coated substrate comprising plastic;
(HD-PECVD) comprising a DC power ion bombarder with a magnet mounted thereon, and comprising an inorganic oxide, having a refractive index of 1.6 to 2.0 and a thickness of 0.4 to 1.0 Mu m;
And an inorganic oxide which is formed on the first laminate by the high density plasma enhanced chemical vapor deposition and is different from the inorganic oxide contained in the first laminate and has a refractive index of 1.3 to 1.5 and a thickness of 30 nm to 80 nm A second laminate; And
A transparent conductive layer formed on the second laminate and having a thickness of 15 nm to 50 nm,
Wherein the first laminate is formed by supplying an activation energy formed by the uniform magnetic field and electric field effect supplied by the DC power ion bombarder onto the surface of the non-coated substrate. The method according to claim 1,
Wherein the first laminate comprises alumina (Al2O3). The method according to claim 1,
Wherein the first laminate is formed by a plasma-enhanced chemical vapor deposition method using a TMA (Tri-Methyl-Aluminum) precursor. delete The method according to claim 1,
Wherein the activation energy is such that a uniform magnetic field is formed by a magnet disposed inside the DC power ion spring bass, and ions ionized by the electric field effect by the DC power are applied to the non-coated substrate Wherein the first laminate is supplied onto the surface of the non-coated substrate on which the first laminate is formed. The method according to claim 1,
In the first laminated body, in performing the plasma enhanced chemical vapor deposition method, a sub-bias (Bias) is applied in a magnetic field formed by a large area linear HD-PECVD Reactor, and the direction of the plasma ions generated in the vacuum chamber is changed to the vacuum Wherein the transparent conductive film is formed by being converged toward the non-coated substrate disposed inside the chamber. The method according to claim 1,
Wherein each of the inorganic oxide of the first laminate and the inorganic oxide of the second laminate comprises
Aluminum oxide, zirconium oxide, titanium oxide, zinc oxide, cerium oxide, tantalum oxide, yttrium oxide, yttrium oxide, zirconium oxide, Wherein the transparent conductive film comprises at least one selected from the group consisting of yttrium oxide and silicon oxide. The method according to claim 1,
And a protective film provided on the opposite side of the surface of the non-coated substrate on which the first laminate is formed. In the transparent conductive film production method,
Preparing a non-coated substrate comprising plastic;
A first laminate comprising inorganic oxide and having a refractive index of 1.6 to 2.0 and a thickness of 0.4 to 1.0 mu m is formed by using a high density plasma enhanced chemical vapor deposition method including a DC power ion bombarder having magnets on the non- ;
A second laminate including an inorganic oxide different from the inorganic oxide included in the first laminate and having a refractive index of 1.3 to 1.5 and a thickness of 30 nm to 80 nm on the first laminate using high density plasma enhanced chemical vapor deposition Forming a sieve; And
And forming a transparent conductive layer having a thickness of 15 nm to 50 nm on the second laminate,
Wherein forming the first laminate comprises forming the first laminate by supplying activation energy formed by the uniform magnetic field and electric field effects provided by the DC power ion spring baffle onto the surface of the non- By weight based on the total weight of the transparent conductive film. 10. The method of claim 9,
In the step of forming the first laminate,
Wherein the first laminate is formed to include alumina (Al2O3). 10. The method of claim 9,
In the step of forming the first laminate,
Wherein the first laminate is formed by a plasma-enhanced chemical vapor deposition method using a TMA (Tri-Methyl-Aluminum) precursor. delete 10. The method of claim 9,
In the step of forming the first laminate,
Wherein the activation energy is such that a uniform magnetic field is formed by a magnet disposed inside the DC power ion spring bass, and ions ionized by the electric field effect by the DC power are applied to the non-coated substrate Wherein the first laminate is supplied onto the surface of the non-coated substrate on which the first laminate is formed. 10. The method of claim 9,
In the step of forming the first laminate,
In performing the high density plasma enhanced chemical vapor deposition method, a sub-bias (Bias) is applied in a magnetic field formed by a large area linear HDPECVD reactor, and the direction of the plasma ions generated inside the vacuum chamber is detected by a non- The first layered product is formed. 10. The method of claim 9,
Wherein each of the inorganic oxide of the first laminate and the inorganic oxide of the second laminate comprises
Aluminum oxide, zirconium oxide, titanium oxide, zinc oxide, cerium oxide, tantalum oxide, yttrium oxide, yttrium oxide, zirconium oxide, Wherein the transparent conductive film comprises at least one selected from the group consisting of yttrium oxide, silicon oxide, ytterbium oxide, and silicon oxide. In the touch panel,
A touch panel comprising the transparent conductive film according to claim 1.

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