KR20090077367A - Transparent conductive laminate with organic-inorganic hybrid buffer layer - Google Patents

Abstract

The present invention is a plastic substrate; Organic-inorganic hybrid buffer layer; And it provides a transparent conductive laminate comprising a transparent conductive film and a method for manufacturing the same, and provides a display device and a photoelectric conversion device having the transparent conductive laminate.

The present invention is a plastic substrate; By providing a transparent conductive laminate composed of an organic-inorganic hybrid buffer layer and a transparent conductive film, it improves the surface hardness of the plastic substrate, flatness and adhesion to the inorganic thin film, and suppresses crack generation and durability of the transparent conductive film layer, thereby improving transparency. The resistivity of the entire film can be improved, and the uniformity of electrical properties can be improved.

Description

Transparent conductive laminate with organic-inorganic hybrid buffer layer {TRANSPARENT CONDUCTIVE MULTILAYERED BODY HAVING ORGANIC-INORGANIC HYBRID BUFFER LAYER}

The present invention relates to a transparent conductive laminate comprising a plastic substrate, a buffer layer and a transparent conductive film, wherein the organic-inorganic hybrid buffer layer improves the surface hardness, flatness, and adhesion of the plastic substrate to the electrical properties of the transparent conductive film. It relates to a transparent conductive laminate that can improve the.

Transparent electrodes are used in various types of electrodes of various displays, photoelectric conversion elements such as solar cells, touch panels, and the like, and are manufactured by forming transparent conductive thin films on transparent substrates such as glass and transparent films. Currently, the transparent conductive material mainly used is indium tin oxide (ITO) doped with tin, and has excellent transparency and low specific resistance (1 × 10 ⁻⁴ to 2 × 10 ⁻⁴ Ωcm). Known.

The method of manufacturing a transparent conductive thin film includes vacuum deposition methods such as sputtering, chemical vapor deposition (CVD), ion beam deposition, and pulsed laser deposition, and spray coating. There are various methods, such as coating, spin coating, and wet methods such as dip coating. Among these methods, a vacuum deposition method such as sputtering is more preferred, and since the vacuum deposition method uses plasma, it is possible to grow a film having high particle energy, thereby obtaining a high quality film having a higher density than other methods. . In addition, there is an advantage that the thin film of good quality can be grown at low temperature without additional heat treatment.

Recently, the demand for ITO is increasing rapidly as the flat display market grows. However, due to supply and demand instability due to high price of indium and harmfulness to human body, development of low-cost transparent conductive material that can replace ITO is required. to be.

Such substitutes include tin oxide (SnO ₂ ), zinc oxide (ZnO), and the like. In this regard, attempts have been made to produce a conductive thin film having a low specific resistance (2 × 10 ⁻⁴ to 3 × 10 ⁻⁴ Ωcm) by doping aluminum (Al) to zinc oxide. It is known that zinc oxide (ZnO) is a semiconductor material having a wide bandgap (~ 3.3ev), and can have excellent transmittance (more than 85%) and low resistivity through doping, and is relatively inexpensive for doped zinc oxide. And, since it is a material harmless to the human body, it is receiving great attention as a material that can replace ITO. Currently, research is mainly focused on materials for transparent electrodes made of zinc oxide (ZnO) to which aluminum (Al), gallium (Ga), silicon (Si) and / or indium (In) are added.

Meanwhile, glass has been mainly used as a base of a transparent conductive film, but as the use of the transparent conductive film is diversified and interest in flexible displays is increasing, in particular, it is excellent in workability, light weight, and flexibility. Attention has been paid to plastic substrates having the following properties. Such plastic substrates include polyethylene terephthalate (PET), polycarbonate (PC), polyethylene naphthalate (Polyethylene 2,6-naphthalate (PEN)), polymethylmethacrylate (PMMA), polyether Sulfone (Polyether sulfone (PES), polyether imide (PEI)) and the like are known.

Plastic substrates generally have low surface hardness and are easily damaged by small impacts or scratches, so the surface flatness is not very good, and this surface state of the plastic substrate may adversely affect the electrical properties of the transparent conductive film deposited thereon. . In general, the better the smoothness of the substrate is, the better the conductivity of the transparent conductive film is. Therefore, the conventional plastic substrate has been dealt with the above problems by applying a primer or a protective film on the surface, but the inorganic layer thereon When coating, there is a problem that it is difficult to form a coating layer having excellent physical properties due to poor adhesion between the substrate and the coating layer.

The inventors of the present invention, while studying a transparent conductive plate having a transparent conductive film formed on the plastic substrate, by inserting the organic-inorganic hybrid coating layer between the plastic substrate and the transparent conductive film to improve the surface hardness of the plastic substrate, flatness and adhesion to the inorganic thin film The organic-inorganic hybrid coating layer may serve as a buffer layer between the organic plastic substrate and the inorganic transparent conductive film, thereby preventing crack generation of the transparent conductive film layer and improving durability due to the difference in modulus and internal stress of the two substrates. I found out that it can play a big role. In addition, it has been found that the specific resistance of the transparent conductive film laminated on the substrate can be improved as well as the uniformity of the electrical properties can be improved.

The present invention is based on this.

The present invention is a plastic substrate; Organic-inorganic hybrid buffer layer; And it provides a transparent conductive laminate comprising a transparent conductive film.

In addition, the present invention comprises the steps of: a) partially hydrolyzing a precursor composition comprising a compound represented by Formula 1 and a compound represented by Formula 2 to prepare a sol (sol) solution; b) coating the solution on a plastic substrate; c) curing the coating solution on the substrate to form an organic-inorganic hybrid buffer layer; And d) laminating a transparent conductive film on the plastic substrate having the organic-inorganic hybrid buffer layer formed thereon.

[Formula 1]

(R ¹ ) _m -Si-X _(4-m)

Wherein X may be the same or different from each other, and hydrogen, halogen, alkoxy having 1 to 12 carbon atoms, acyloxy, alkylcarbonyl, alkoxycarbonyl, or -N (R ² ) ₂ , wherein R ² is H, Or alkyl having 1 to 12 carbon atoms,

R ¹ may be the same or different from each other, alkyl, alkenyl, alkynyl, aryl, arylalkyl, alkylaryl, arylalkenyl, alkenylaryl, arylalkynyl, alkynylaryl group, halogen, Substituted amino, amide, aldehyde, keto, alkylcarbonyl, carboxy, mercapto, cyano, hydroxy, alkoxy having 1 to 12 carbon atoms, alkoxycarbonyl having 1 to 12 carbon atoms, sulfonic acid, phosphoric acid, acryloxy, meta Krilloxy, epoxy or vinyl,

Wherein oxygen or —NR ² (wherein R ² is H, or alkyl having 1 to 12 carbon atoms) is inserted between the radicals R ¹ and Si to form — (R ¹ ) _m —O—Si—X _(4-m) or (R ¹ ) _m -NR ² -Si-X _(4-m) , m is an integer of 1 to 3.)

[Formula 2]

M- (R ³ ) _z

(Wherein M represents a metal selected from the group consisting of aluminum, zirconium, and titanium, R ³ may be the same or different from each other, halogen, alkyl, alkoxy, acyloxy, or hydroxy group having 1 to 12 carbon atoms) Z is an integer of 3 or 4.

In addition, the present invention provides a display device and a photoelectric conversion device having the transparent conductive laminate.

The present invention is a plastic substrate; By providing a transparent conductive laminate composed of an organic-inorganic hybrid buffer layer and a transparent conductive film, it improves the surface hardness of the plastic substrate, flatness and adhesion to the inorganic thin film, and suppresses crack generation and durability of the transparent conductive film layer, thereby improving transparency. The resistivity of the entire film can be improved, and the uniformity of electrical properties can be improved.

The transparent conductive laminate of the present invention is a plastic substrate; Organic-inorganic hybrid buffer layer; And a transparent conductive film.

The organic-inorganic hybrid buffer layer of the present invention is not a simple mixture of organic and inorganic substances, but is a thin film layer made of a material bonded on a molecular or nano scale, and has a chain or network structure, such as crosslinking between organic molecules, on a periodic table. A chemical bond between a metal (or metalloid) element and an organic molecule (monomer or polymer), and an inorganic metal (including metal oxides and metal hydrates) are mixed and bonded on a molecular or nano scale.

The organic-inorganic hybrid buffer layer formed on the plastic substrate (eg, film or sheet) may serve as a surface protective layer of the plastic substrate, such as to impart high surface hardness and excellent planarization function to the plastic substrate, and to provide a transparent conductive thereon. In the case of forming a film or the like, the flatness of the substrate may be improved, thereby achieving a low specific resistance value and minimizing the variation of electrical properties according to the position on the substrate.

In addition, since the buffer layer has a composition of an organic-inorganic hybrid, when the buffer layer is positioned between an organic plastic substrate and an inorganic transparent conductive film, the buffer layer may serve as a buffer for a difference in characteristics between the organic and inorganic materials. That is, it is possible to minimize the stress due to the difference in the coefficient of linear expansion when the organic material and the inorganic material adhesion, and to improve the overall physical properties of the laminate, such as to improve the adhesion between the layers.

①plastic base material

The plastic substrate used in the present invention may be used in the form of a polymer film or sheet, and may be selected from the group consisting of a single polymer or a polymer composite material containing a blend of one or more polymers and an organic or inorganic additive. .

Non-limiting examples of the polymer film include polynorbornene, aromatic florene polyester, polyesulfone, bisphenol A polysulfone, polyimide, polyethylene terephthalate, polyethylene naphthalene, polyarylate, polycarbonate, cyclic olefin air There are polymers such as copolymers and methacrylates, and these may be used alone or in combination of two or more thereof.

In addition, the present invention may use a polymer substrate in which nanomaterials are dispersed in a polymer. Polymer-clay nanocomposites include polymer-clay nanocomposites, which have a smaller amount of clay than composites such as glass fibers, which have been used due to the small particle size (<1 micron) and the large aspect ratio of clay. It is useful for improving physical properties such as mechanical properties, heat resistance, gas barrier properties, and dimensional stability. In order to improve the properties, it is important to disperse the platelets stripped of the layered clay layer well in the polymer matrix. Polymers that can be used in such polymer-clay composites include polystyrene, polymethacrylate, polyethylene terephthalate, polyethylenenaphthalene, polyarylate, polycarbonate, cyclic olefin copolymer, polynorbornene, aromatic florene polyester, poly Susulfone, polyimide, epoxy resin, polyfunctional acrylate, and the like, and the clay may be used laponite, montmorillonite, megadite and the like.

The plastic substrate of the present invention may be in the form of a film or sheet having a thickness in the range of 10 to 1000 μm, and may be manufactured by a solution casting method or an extrusion process. When the thickness of the substrate is thinner than the above range, it may be difficult to maintain the shape of the substrate and the laminate, and when the substrate is thicker than the above range, flexibility and light transmittance may be deteriorated.

In order to improve the coating property and adhesion of the plastic substrate, a primer coating may be applied to the surface of the substrate, or surface treatment may be performed by corona, oxygen or carbon dioxide plasma, ultraviolet-ozone, reactive gas inlet ion beam, or the like.

②organic-inorganic hybrid buffer layer

In the transparent conductive laminate of the present invention, the organic-inorganic hybrid buffer layer may be formed from a partial hydrolyzate of the precursor composition comprising a compound such as an organosilane and a metal alkoxide. It may further include a solvent and a polymerization catalyst.

The organosilane may be used by selecting one or more from the group consisting of compounds represented by the following formula (1), and in this case, when one type of organosilane compound is used, crosslinking is preferable.

[Formula 1]

(R ¹ ) _m -Si-X _(4-m)

Wherein X may be the same or different from each other, and hydrogen, halogen, alkoxy having 1 to 12 carbon atoms, acyloxy, alkylcarbonyl, alkoxycarbonyl, or -N (R ² ) ₂ , wherein R ² is H, Or alkyl having 1 to 12 carbon atoms,

R ¹ may be the same or different from each other, alkyl, alkenyl, alkynyl, aryl, arylalkyl, alkylaryl, arylalkenyl, alkenylaryl, arylalkynyl, alkynylaryl group, halogen, Substituted amino, amide, aldehyde, keto, alkylcarbonyl, carboxy, mercapto, cyano, hydroxy, alkoxy having 1 to 12 carbon atoms, alkoxycarbonyl having 1 to 12 carbon atoms, sulfonic acid, phosphoric acid, acryloxy, meta Krilloxy, epoxy or vinyl,

Wherein oxygen or —NR ² (wherein R ² is H, or alkyl having 1 to 12 carbon atoms) is inserted between the radicals R ¹ and Si to form — (R ¹ ) _m —O—Si—X _(4-m) or (R ¹ ) _m -NR ² -Si-X _(4-m) , m is an integer of 1 to 3.)

Examples of the organosilane include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxy Silane, phenyldimethoxysilane, phenyldiethoxysilane, methyldimethoxysilane, methyldiethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, triphenylmethoxysilane, Triphenylethoxysilane, phenyldimethylmethoxysilane, phenyldimethylethoxysilane, diphenylmethylmethoxysilane, diphenylmethylethoxysilane, dimethylethoxysilane, dimethylethoxysilane, diphenylmethoxysilane, diphenyl Ethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, p-aminophenylsilane, allyltrimethoxysilane, n- (2-aminoethyl) -3-aminopropyltri Methoxysilane, 3-amine Propyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyldiisopropylethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, 3-glycidoxypropyltrimethoxy Silane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxy Propyltrimethoxysilane, n-phenylaminopropyltrimethoxysilane, vinylmethyldiethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, and mixtures thereof.

Compounds, such as the said metal alkoxide, can be selected 1 or more types from the group which consists of a compound represented by following formula (2).

[Formula 2]

M- (R ³ ) _z

(Wherein M represents a metal selected from the group consisting of aluminum, zirconium, and titanium, R ³ may be the same or different from each other, halogen, alkyl, alkoxy, acyloxy, or hydroxy group having 1 to 12 carbon atoms) Z is an integer of 3 or 4.

The filler may be mixed with the organic-inorganic hybrid buffer layer to further improve the surface hardness of the buffer layer. Non-limiting examples of the filler include metal, glass powder diamond powder, and silicon oxide (SiO _x , where x is an integer of 2-4), clay (bentonite, smectite, kaolin, etc.), calcium phosphate, magnesium phosphate, barium sulfate, aluminum fluoride, calcium silicate, magnesium silicate, barium silicate, barium carbonate, barium hydroxide, Aluminum silicates, mixtures thereof, and the like.

The solvent is not particularly limited as long as it is a non-aqueous solvent that does not contain water as a solvent used in a conventional partial hydrolysis reaction, and those known to those skilled in the art can be used, and non-limiting examples thereof include saturated hydrocarbons such as hexane, toluene, Aromatic hydrocarbons such as xylene, alcohols such as methanol, ethanol, propanol and butanol, ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone and diisobutyl ketone, esters such as ethyl acetate and butyl acetate, tetra Ethers such as hydrofuran (THF), dioxane and diethyl ether, amides such as N-dimethyl formamide, N-methyl pyrrolidone (NMP) and N, N-dimethyl acetamide, ethylene chloride And halogenated hydrocarbons such as chlorbenzene.

The polymerization catalyst is also not particularly limited as long as it is known to those skilled in the art as promoting a conventional hydrolysis reaction, and non-limiting examples thereof include hydrochloric acid (HCl), nitric acid (HNO ₃ ), sulfuric acid (H ₂ SO ₄ ), acetic acid (CH ₃ COOH) and ammonia water (NH ₄ OH).

The content of the organosilane in the precursor composition is preferably 20 to 99.99% by weight, more preferably 50 to 99% by weight, most preferably 70 to 99% by weight. In addition, the content of the compound such as the metal alkoxide may be used in 0.01 to 80% by weight, more preferably less than 70% by weight, most preferably less than 20% by weight.

In general, the organosilane has four bonds at the time of crosslinking, whereas the compounds such as metal alkoxides vary depending on the type (for example, 2 to 4), and thus a more dense crosslinking structure than when using only organosilanes. Can be formed.

In addition, by using a compound such as a metal alkoxide, by adding an inorganic element of another element to the organic-inorganic hybrid composition of silane only to form a hybrid composition having a hetero atom, more various physical properties can be realized. have.

In addition, the compound such as a metal alkoxide may also serve as a catalyst in preparing a sol solution for organic-inorganic hybrid coating.

The organic-inorganic hybrid buffer layer is formed from a partial hydrolyzate of a precursor composition comprising a compound such as organosilane and metal alkoxide, which is partially hydrolyzed by adding a certain amount of water to the precursor composition. It can be obtained by inducing a reaction.

At this time, the degree of partial hydrolysis can be adjusted by adjusting the amount of water, reaction time, pH, or reaction temperature, or other reaction conditions, and thus the degree of change in the characteristics of organic-inorganic properties. Can be controlled. For example, the change in the organic-inorganic properties can be controlled by adjusting the amount and ratio of the first compound introduced such as organic silane and metal alkoxide, and the degree of hydrolysis reaction. The larger, the more the hydrolysis reaction proceeds, the more the inorganic material becomes superior.

On the other hand, when adjusting the degree of hydrolysis reaction, for example, when adjusting the amount of water relative to the equivalent of compounds such as organosilane and metal alkoxide in the range of 1: 0.1 ~ 1: 0.99 can be prepared a partial hydrolyzate, In the case of the partial hydrolyzate prepared as described above, there is an advantage that it can play a role as a stress relaxation layer between the inorganic layer and the organic layer, compared to the fully hydrolyzed inorganic material.

Meanwhile, the thickness of the organic-inorganic hybrid buffer layer may be in the range of 0.5 to 20 μm, preferably in the range of 2 to 10 μm, and more preferably in the range of 1 to 5 μm.

In addition, the surface roughness of the organic-inorganic hybrid buffer layer is preferably about 1 nm, and more preferably has a surface roughness within 1 nm.

③ Transparent conductive film

In the transparent conductive laminate of the present invention, the transparent conductive film is not particularly limited so long as it is known to those skilled in the art as having transparency and electrical conductivity, and non-limiting examples thereof include indium tin oxide (ITO) or Zinc oxide and the like.

In particular, when the transparent conductive film is zinc oxide, it may be pure zinc oxide, but preferably zinc oxide doped with 0.05 to 15 wt% of aluminum (Al) or gallium (Ga).

On the other hand, the thickness of the transparent conductive film may be in the range of 10 to 300 nm. If the thickness of the transparent conductive film is thinner than the above range, the electrical conductivity is not good. If the thickness of the transparent conductive film is thicker than the above range, there is a problem in that the permeability is lowered, and the deposition time becomes longer when the thin film is manufactured.

④ Manufacturing method of transparent conductive laminate

The organic-inorganic hybrid buffer layer is formed on the plastic substrate, and the method of manufacturing the transparent conductive laminate of the present invention by laminating a transparent conductive film is as follows.

a) partially hydrolyzing a precursor composition comprising a compound represented by Formula 1 and a compound represented by Formula 2 to prepare a sol solution;

b) coating the solution on a plastic substrate;

c) curing the coating solution on the substrate to form an organic-inorganic hybrid buffer layer; And

d) laminating a transparent conductive film on the plastic substrate on which the organic-inorganic hybrid buffer layer is formed.

 [Formula 1]

(R ¹ ) _m -Si-X _(4-m)

Wherein X may be the same or different from each other, and hydrogen, halogen, alkoxy having 1 to 12 carbon atoms, acyloxy, alkylcarbonyl, alkoxycarbonyl, or -N (R ² ) ₂ , wherein R ² is H, Or alkyl having 1 to 12 carbon atoms,

R ¹ may be the same or different from each other, alkyl, alkenyl, alkynyl, aryl, arylalkyl, alkylaryl, arylalkenyl, alkenylaryl, arylalkynyl, alkynylaryl group, halogen, Substituted amino, amide, aldehyde, keto, alkylcarbonyl, carboxy, mercapto, cyano, hydroxy, alkoxy having 1 to 12 carbon atoms, alkoxycarbonyl having 1 to 12 carbon atoms, sulfonic acid, phosphoric acid, acryloxy, meta Krilloxy, epoxy or vinyl,

Wherein oxygen or —NR ² (wherein R ² is H, or alkyl having 1 to 12 carbon atoms) is inserted between the radicals R ¹ and Si to form — (R ¹ ) _m —O—Si—X _(4-m) or (R ¹ ) _m -NR ² -Si-X _(4-m) , m is an integer of 1 to 3.)

[Formula 2]

M- (R ³ ) _z

(Wherein M represents a metal selected from the group consisting of aluminum, zirconium, and titanium, R ³ may be the same or different from each other, halogen, alkyl, alkoxy, acyloxy, or hydroxy group having 1 to 12 carbon atoms) Z is an integer of 3 or 4.

In step a), the precursor composition for forming the organic-inorganic hybrid buffer layer includes a compound such as an organosilane and a metal alkoxide, and may further include an appropriate filler, a solvent and a polymerization catalyst, as described above. Same as one.

The coating method in step b) is not particularly limited, and methods known to those skilled in the art can be used, and non-limiting examples thereof include spin coating, roll coating, bar coating, dip coating, gravure coating and spray coating.

The method of curing the solution coated in step c) is not particularly limited, and methods known to those skilled in the art may be used, and non-limiting examples thereof include thermosetting, UV curing, infrared curing, and high frequency heat treatment.

The transparent conductive film laminated in step d) may include indium tin oxide (ITO) or zinc oxide (Zinc Oxide), and the film forming method is not particularly limited, and a method known to those skilled in the art may be used. Non-limiting examples include sputtering, molecular beam deposition (MBE), pulsed laser deposition (PLD), sol-gel method and chemical vapor deposition (CVD).

The display device having the transparent conductive laminate of the present invention includes, for example, a liquid crystal display (LCD), an organic light emitting diode (OLED), an electronic paper (E-paper), and the like. Except for including this laminated substrate, it has a structure known to those skilled in the art, and can be manufactured by a method known to those skilled in the art.

The photoelectric conversion device having the transparent conductive laminate of the present invention includes, for example, a solar cell, and has a structure known to those skilled in the art, except that the transparent conductive laminate of the present invention is included as a substrate on which transparent electrodes are laminated. It may be prepared by a method known to the. For example, a plurality of unit cells may be connected in series on a transparent substrate to have a modular structure, and the module may include a transparent electrode formed in a band shape that is disconnected (insulated) from an upper portion of the transparent substrate as an insulator. The unit solar cell (semiconductor) layer formed in a band shape covering the transparent electrode, and the metal formed in the band shape covering the solar cell layer may be composed of an electrode layer, and a plurality of cut (insulated) unit cells are connected in series. It may be If the back protective film layer made of resin is a metal for the purpose of preventing and protecting an electric short circuit of the solar cell, the electrode may be formed by covering the electrode.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited thereto.

[Production Example 1]

As a precursor composition for forming the organic-inorganic hybrid buffer layer, 40 parts by weight of tetraethoxysilane, 55 parts by weight of glycidyloxypropyltrimethoxysilane, 1 part by weight of aminopropyltrimethoxysilane, and 2 parts by weight of aluminum butoxide 1 part by weight of zirconium propoxide was used, and 100 parts by weight of distilled water was added thereto to partially hydrolyze at 25 ° C. for 24 hours to prepare a sol coating solution.

Example 1 PET Substrate / Organic-Inorganic Hybrid Buffer Layer / Gallium Doped Zinc oxide

As a plastic substrate, a polyethylene terephthalate (PET) film was used without further treatment. The coating solution prepared in Preparation Example 1 was bar-coated on a PET film and dried for 24 hours in a convection oven at 120 ℃, the physical properties of the film after coating is shown in Table 1 below.

TABLE 1

Light transmittance (400nm) Haze (%) Surface roughness (nm) Pencil hardness Coating thickness (㎛) 89% 0.4 0.3 3H One

The measuring method of each physical property of the said Table 2 is as follows.

-Light transmittance: Varian UV spectrometer based on ASTM D1003

-Haze: measured by Hazemeter TC-H3DPK of Tokyo Denshoku by ASTM D1003

-Surface roughness: measured by Ra value with LS AFM system (EQC-0067)

-Pencil hardness: Measured by pencil hardness based on JIS K 5400

A gallium (Ga) -doped zinc oxide-based transparent conductive film deposited on the organic-inorganic hybrid buffer layer coated with 7 wt% of Ga was deposited to a thickness of about 150 nm by using an RF magnetron sputtering method to prepare a transparent conductive laminate.

At this time, a zinc oxide (ZnO) target containing 7 wt% of gallium (Ga) was used as the sputtering target. Argon was used as the sputtering gas, the bias voltage applied to the target was about -100 V, the pressure in the sputtering chamber was 3 × 10 ^-3 torr, and the flow rate of argon (Ar) gas was 50 sccm. The temperature of the substrate at the time of vapor deposition was 200 degreeC.

Example 2 PET Substrate / Organic-Inorganic Hybrid Buffer layer / ITO membrane

A transparent conductive laminate was prepared in the same manner as in Example 1 except that an ITO thin film having a thickness of 30 nm was laminated with a transparent conductive thin film using an indium tin oxide (ITO) target.

Comparative Example 1 PET substrate / gallium doped Zinc oxide

A transparent conductive laminate was prepared in the same manner as in Example 1, except that the gallium-doped zinc oxide film was directly stacked without forming an organic-inorganic hybrid buffer layer on the PET film.

Comparative Example 2 PET substrate / ITO film

A transparent conductive laminate was prepared in the same manner as in Example 2, except that the ITO film was directly stacked without forming an organic-inorganic hybrid buffer layer on the PET film.

<Consideration>

2 is a graph showing the results of measuring the sheet resistance of the transparent conductive laminates prepared in Example 1 and Comparative Example 1 for each position on the surface of the conductive film.

In Comparative Example 1, in which the organic-inorganic hybrid buffer layer was not used, the uniformity of the specific resistance according to the measurement position was very bad. However, in Example 1 manufactured using the organic-inorganic hybrid buffer layer, the uniformity of the sheet resistance was greatly improved compared to Comparative Example 1. In addition to the uniformity, the overall sheet resistance values were also improved.

3 is a graph showing the results of measuring the sheet resistance of the transparent conductive laminates prepared in Example 2 and Comparative Example 2 for each position on the surface of the conductive film. In Comparative Example 2 without using the organic-inorganic hybrid buffer layer, the uniformity of the specific resistance according to the measurement position was poor. The sheet resistance of the center part (position 0) was smaller than that of the other parts. However, in Example 2 prepared using the organic-inorganic hybrid buffer layer, the uniformity of the sheet resistance was improved compared to Comparative Example 2, and the overall sheet resistance value as well as the uniformity was improved.

1 is a cross-sectional structure of a transparent conductive laminate in accordance with an embodiment of the present invention.

2 is a graph showing the results of measuring the sheet resistance of the transparent conductive laminates prepared in Example 1 and Comparative Example 1 for each position on the surface of the conductive film.

3 is a graph showing the results of measuring the sheet resistance of the transparent conductive laminates prepared in Example 2 and Comparative Example 2 for each position on the surface of the conductive film.

<Description of Drawing>

1: plastic base material 2: organic-inorganic hybrid buffer layer

3: transparent conductive film

Claims (10)

Plastic substrates; Organic-inorganic hybrid buffer layer; And a transparent conductive film. According to claim 1, wherein the organic-inorganic hybrid buffer layer, 20 to 99.99% by weight of the compound represented by the formula 1, and 0.01 to 80% by weight of the compound represented by the formula (2) from the partial hydrolyzate of the precursor composition Transparent conductive laminate, characterized in that formed. [Formula 1] (R ¹ ) _m -Si-X _(4-m) Wherein X may be the same or different from each other, and hydrogen, halogen, alkoxy having 1 to 12 carbon atoms, acyloxy, alkylcarbonyl, alkoxycarbonyl, or -N (R ² ) ₂ , wherein R ² is H, Or alkyl having 1 to 12 carbon atoms, R ¹ may be the same or different from each other, alkyl, alkenyl, alkynyl, aryl, arylalkyl, alkylaryl, arylalkenyl, alkenylaryl, arylalkynyl, alkynylaryl group, halogen, Substituted amino, amide, aldehyde, keto, alkylcarbonyl, carboxy, mercapto, cyano, hydroxy, alkoxy having 1 to 12 carbon atoms, alkoxycarbonyl having 1 to 12 carbon atoms, sulfonic acid, phosphoric acid, acryloxy, Methacryloxy, epoxy or vinyl group, Wherein oxygen or —NR ² (wherein R ² is H, or alkyl having 1 to 12 carbon atoms) is inserted between the radicals R ¹ and Si to form — (R ¹ ) _m —O—Si—X _(4-m) or (R ¹ ) _m -NR ² -Si-X _(4-m) , m is an integer of 1 to 3.) [Formula 2] M- (R ³ ) _z (Wherein M represents a metal selected from the group consisting of aluminum, zirconium, and titanium, R ³ may be the same or different from each other, halogen, alkyl, alkoxy, acyloxy, or hydroxy group having 1 to 12 carbon atoms) Z is an integer of 3 or 4. The method of claim 2, wherein the precursor composition is a metal, glass powder, diamond powder, silicon oxide, clay, calcium phosphate, magnesium phosphate, barium sulfate, aluminum fluoride, calcium silicate, magnesium silicate, barium silicate, barium carbonate, barium Transparent conductive laminate, characterized in that it further comprises a filler selected from the group consisting of hydroxide and aluminum silicate. The transparent conductive laminate according to claim 1, wherein the plastic substrate is selected from the group consisting of a single polymer, at least one polymer blend, and a polymer composite material containing an organic or inorganic additive. The transparent conductive laminate of claim 1, wherein the organic-inorganic hybrid buffer layer has a thickness in a range of 0.5 to 20 μm. The method of claim 1, wherein the transparent conductive film comprises indium tin oxide (ITO) or zinc oxide doped with aluminum (Al) or gallium (Ga) 0.05 to 15 wt%. Transparent conductive laminate characterized by the above-mentioned. The transparent conductive laminate according to claim 1, wherein the transparent conductive film has a thickness in the range of 10 to 300 nm. a) partially hydrolyzing a precursor composition comprising a compound represented by Formula 1 and a compound represented by Formula 2 to prepare a sol solution; b) coating the solution on a plastic substrate; c) curing the coating solution on the substrate to form an organic-inorganic hybrid buffer layer; And d) laminating a transparent conductive film on the plastic substrate on which the organic-inorganic hybrid buffer layer is formed A method for producing the transparent conductive laminate according to any one of claims 1 to 8, including. [Formula 1] (R ¹ ) _m -Si-X _(4-m) Wherein X may be the same or different from each other, and hydrogen, halogen, alkoxy having 1 to 12 carbon atoms, acyloxy, alkylcarbonyl, alkoxycarbonyl, or -N (R ² ) ₂ , wherein R ² is H, Or alkyl having 1 to 12 carbon atoms, R ¹ may be the same or different from each other, alkyl, alkenyl, alkynyl, aryl, arylalkyl, alkylaryl, arylalkenyl, alkenylaryl, arylalkynyl, alkynylaryl group, halogen, Substituted amino, amide, aldehyde, keto, alkylcarbonyl, carboxy, mercapto, cyano, hydroxy, alkoxy having 1 to 12 carbon atoms, alkoxycarbonyl having 1 to 12 carbon atoms, sulfonic acid, phosphoric acid, acryloxy, meta Krilloxy, epoxy or vinyl, Wherein oxygen or —NR ² (wherein R ² is H, or alkyl having 1 to 12 carbon atoms) is inserted between the radicals R ¹ and Si to form — (R ¹ ) _m —O—Si—X _(4-m) or (R ¹ ) _m -NR ² -Si-X _(4-m) , m is an integer of 1 to 3.) [Formula 2] M- (R ³ ) _z (Wherein M represents a metal selected from the group consisting of aluminum, zirconium, and titanium, R ³ may be the same or different from each other, halogen, alkyl, alkoxy, acyloxy, or hydroxy group having 1 to 12 carbon atoms) Z is an integer of 3 or 4. The display element provided with the transparent conductive laminated body in any one of Claims 1-7. The photoelectric conversion element provided with the transparent conductive laminated body in any one of Claims 1-7.

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