KR101816972B1 - Transparent electrode with TiO2/Ag/TiO2 multilayered structure and method for preparing the same - Google Patents

Transparent electrode with TiO2/Ag/TiO2 multilayered structure and method for preparing the same Download PDF

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KR101816972B1
KR101816972B1 KR1020150120150A KR20150120150A KR101816972B1 KR 101816972 B1 KR101816972 B1 KR 101816972B1 KR 1020150120150 A KR1020150120150 A KR 1020150120150A KR 20150120150 A KR20150120150 A KR 20150120150A KR 101816972 B1 KR101816972 B1 KR 101816972B1
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tio
layer
thickness
transparent electrode
metal layer
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KR20170024751A (en
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김준호
성태연
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고려대학교 산학협력단
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/04Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08Oxides
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14Metallic material, boron or silicon
    • C23C14/18Metallic material, boron or silicon on other inorganic substrates
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00Apparatus or processes specially adapted for manufacturing conductors or cables
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00Non-insulated conductors or conductive bodies characterised by their form
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/36Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the electrodes
    • H01L33/40Materials therefor

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Abstract

The present invention relates to a flexible transparent electrode having a TiO 2 / Ag / TiO 2 multilayer thin film structure, and more specifically, And a TiO 2 layer laminated on the upper and lower surfaces of the Ag metal layer, wherein the Ag metal layer has a thickness of 11 nm to 25 nm and the TiO 2 layer has a thickness of 20 nm to 80 nm The present invention relates to a flexible transparent electrode.
According to the present invention, it is possible to provide a flexible transparent electrode having a high transparency comparable to that of the conventional ITO electrode, having a low sheet resistance, being manufactured by a room temperature deposition process and without being subjected to a high temperature heat treatment, have.

Description

Transparent electrode with TiO2 / Ag / TiO2 multilayered structure and method for preparing the same [0002]

The present invention relates to a flexible transparent electrode having a TiO 2 / Ag / TiO 2 multilayer thin film structure.

The flexible transparent electrode is an electrode in which a conductive pattern is formed on a flexible substrate, and is an electronic device that is usefully used in various fields such as displays, transistors, touch panels, and solar cells.

Indium tin oxide (ITO), which is a kind of transparent conductive oxide, is known among transparent conductive oxides, carbon nanotubes, graphenes and polymer conductors as the most widely used materials for flexible transparent electrodes. Are widely used for most transparent electrodes due to their high light transmittance and conductivity.

However, since the ITO electrode material requires a high-temperature heat treatment process in the manufacturing process, and there is a limit to the supply of indium, which is a rare metal used in the production of ITO, and the difficulty in securing flexible characteristics, As a variety of alternative materials for research, development and research on conductive oxides, carbon nanotubes, graphenes, silver nanowires and conductive polymers have been actively conducted.

As one example, studies have been made to replace ITO by doping ZnO and SnO 2 , which are conductive oxides, with other materials, but they are disadvantageous in that they lack flexible characteristics and have poor electrical and optical properties compared to ITO. In addition, carbon nanotubes, which have undergone considerable research and are commercially viable in various fields, require various improvements related to doping, purification and synthesis. Furthermore, graphene can be produced using low cost graphite and has an advantage in that it has a surface roughness superior to that of carbon nanotubes, but has a limitation in manufacturing a high crystallinity large area graphene film. In addition, silver nanowires have a disadvantage that they are not easy to apply to displays because they have poor surface roughness and high haze compared to other materials. Finally, the conductive polymer has been studied for a long time as a transparent electrode for the past 20 years, but basically organic film has a distinctive color and lacks atmospheric stability.

On the other hand, a transparent electrode having an oxide / metal / oxide multilayer structure has been proposed as a material showing the closest property to ITO. This is because a heat treatment process is not required as compared with an ITO transparent electrode requiring a high temperature heat treatment, It has an advantage that it can be applied to manufacturing, is economical in process, and is large in area.

(Patent Document 1), a multilayer transparent electrode having a multilayer structure of a first transparent oxide layer / silver / second transparent oxide layer (refer to Patent Document 1), a multilayer transparent electrode having a multilayer structure of silicon oxynitride / silver / silicon oxynitride Patent Document 2) have been known. In addition, as a layer forming material of multilayer transparent electrodes having such a multi-layer structure of oxide / metal / oxide, applicability of various materials has been tested, and in particular, in the case of a TiO 2 / Ag / TiO 2 multilayer structure, It has various advantages such as high transparency, low sheet resistance, high temperature heat treatment, and so on.

Therefore, studies on optical properties of TiO 2 / Ag / TiO 2 thin films according to Ag interlayer thickness have been disclosed (Non-Patent Document 1), and a high quality transparent TiO 2 / Ag / TiO 2 thin film deposited on a flexible substrate by a sputtering method at room temperature A study on an Ag / TiO 2 composite electrode film has also been disclosed (Non-Patent Document 2).

However, in order to successfully apply such a TiO 2 / Ag / TiO 2 multi-layer structure to a flexible transparent electrode, various factors must be taken into consideration, and sufficient light transmittance, low sheet resistance value, and high flexibility property are required. These properties should also be maintained in the bending test.

Patent Document 1: Korean Patent Publication No. 10-2012-0028506 Patent Document 2: Korean Patent Laid-Open Publication No. 10-1996-0035092

Non-Patent Document 1: Kim, So Young et al., Optical Properties of TiO2 / Ag / TiO2 Thin Films Dependent on Ag Intermediate Layer Thickness, Heat Treatment Engineering Journal, Vol.28, Non-Patent Document 2: Aritra Dhar and T. L. Alford, High quality transparent TiO2 / Ag / TiO2 composite electrode films deposited on flexible substrates at room temperature by sputtering,

Therefore, in the present invention, TiO 2 / Ag / TiO 2 multilayer to the light transmission, properties such as sheet resistance and flexibility to be essentially satisfied to apply the TiO 2 / Ag / TiO 2 multilayer structure on a flexible transparent electrode comprehensively satisfy the Structure-based flexible transparent electrode.

In order to solve the above problems,

Ag metal layer; And

A flexible transparent electrode comprising a TiO 2 layer stacked on the upper and lower surfaces of the Ag metal layer,

The Ag metal layer has a thickness of 11 nm to 25 nm,

And the thickness of the TiO 2 layer is 20 nm to 80 nm.

According to an embodiment of the present invention, the thickness of the Ag metal layer is 19 nm, and the thickness of the TiO 2 layer stacked on the upper and lower surfaces of the Ag metal layer may be 40 nm, respectively.

According to another embodiment of the present invention, the ratio of the thickness of the Ag metal layer to the thickness of the TiO 2 layer may be 1: 1 to 1: 7.

According to another embodiment of the present invention, the ratio of the thickness of the Ag metal layer to the thickness of the TiO 2 layer may be 1: 2.

According to another embodiment of the present invention, the flexible transparent electrode has a light transmittance of 80% or more at a visible light wavelength band and has a transmittance of 10 Ω / sq. The following sheet resistance values and a figure of merit of at least one.

According to another embodiment of the present invention, the Ag metal layer and the TiO 2 layer are laminated on a flexible substrate selected from the group consisting of polyethersulfone, polyethylene terephthalate, polycarbonate, polyimide, polyethylene naphthalate and glass materials .

Further, in order to solve the above problems,

a) forming a TiO 2 layer on the substrate to a thickness of 20 nm to 80 nm;

b) forming an Ag metal layer on the TiO 2 layer to a thickness of 11 nm to 25 nm; And

c) forming a TiO 2 layer on the Ag metal layer to a thickness of 20 nm to 80 nm.

According to an embodiment of the present invention, the thickness of the Ag metal layer is 19 nm, and the thickness of the TiO 2 layer stacked on the upper and lower surfaces of the Ag metal layer may be 40 nm, respectively.

According to another embodiment of the present invention, the ratio of the thickness of the Ag metal layer to the thickness of the TiO 2 layer may be 1: 1 to 1: 7.

According to another embodiment of the present invention, the ratio of the thickness of the Ag metal layer to the thickness of the TiO 2 layer may be 1: 2.

According to another embodiment of the present invention, the steps a) to c) may be performed by any one process selected from the group consisting of a sputtering method, an electron beam evaporation method, and a continuous evaporation deposition method.

According to another embodiment of the present invention, the steps a) to c) may be carried out by a batch process.

Further, the present invention provides a solar cell including the flexible transparent electrode.

Further, the present invention provides a light emitting diode including the flexible transparent electrode.

According to the present invention, it is possible to provide a flexible transparent electrode having a high transparency comparable to that of the conventional ITO electrode, having a low sheet resistance, being manufactured by a room temperature deposition process and without being subjected to a high temperature heat treatment, have.

FIGS. 1A and 1B are graphs showing bending test photographs and results of the transparent electrode 1a and the conventional ITO electrode 1b according to the first embodiment.
2A and 2B are graphs showing the results of measurement of transmittance at 200 nm to 1100 nm using a polymer and a glass substrate as a base for the samples according to Example 1 and commercial ITO electrodes (thickness: 100 nm).
3 is a graph showing the results of calculation of the figure of merit of the electrode and the commercial ITO electrode (thickness: 100 nm) according to Example 1 on a PET substrate.
FIG. 4 is a graph showing a comparison result of electrical characteristics between the electrode according to Example 1 and a commercial ITO electrode.

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

Many studies have been made on transparent electrodes of an oxide / metal / oxide multi-layer structure, which are known to exhibit properties most similar to ITO. In particular, the transparent electrode of TiO 2 / Ag / TiO 2 multilayer structure has various advantages such as excellent light transmittance, low sheet resistance value, and no need of high temperature heat treatment in the manufacturing process.

The transparent electrodes of the TiO 2 / Ag / TiO 2 multi-layer structure are easy to be large-sized, and the surface resistance is required to be minimized for the large area, and at the same time, it is necessary to prevent the decrease of the light transmittance. However, one of the well known disadvantages of TiO 2 / Ag / TiO 2 multi-layered transparent electrodes is that the sheet resistance is lower than that of ITO, but the light transmittance is lowered due to the Ag layer interposed between the TiO 2 layer and the TiO 2 layer . Therefore, although the sheet resistance decreases as the thickness of the Ag layer becomes thicker, the light transmittance becomes lower at the same time, which is one of the important problems to be overcome in the prior art.

In the present invention, in order to solve the above-described problems, the present inventors have found that when the thicknesses of the TiO 2 layer and the Ag layer are controlled within a predetermined range, and the thickness ratio of the TiO 2 layer and the Ag layer is controlled within a predetermined range It is possible to achieve excellent sheet resistance characteristics and light transmission characteristics at the same time, and the present invention has been completed.

Therefore, in the present invention,

Ag metal layer; And

A flexible transparent electrode comprising a TiO 2 layer stacked on the upper and lower surfaces of the Ag metal layer,

The Ag metal layer has a thickness of 11 nm to 25 nm,

And the thickness of the TiO 2 layer is 20 nm to 80 nm.

In the present invention, when the thickness of the Ag metal layer is 11 nm to 25 nm and the thickness of the TiO 2 layer is 20 nm to 80 nm in the TiO 2 / Ag / TiO 2 multilayer structure, excellent sheet resistance and light transmission characteristics Can be achieved at the same time. In particular, as can be seen from the data of the following examples, it can be seen that optimal characteristics can be achieved when the thickness of the Ag metal layer is 19 nm and the thickness of the TiO 2 layer is 40 nm He said. That is, the thickness of the Ag metal layer and the thickness of the TiO 2 layer must also be within a predetermined range in order to simultaneously satisfy the physical flexibility, electrical characteristics, and optical characteristics required for the flexible transparent electrode. Ratio, and it is most preferable when the ratio is about 1: 2.

When the above-described thickness range and thickness ratio are satisfied, the flexible transparent electrode according to the present invention has a light transmittance of 80% or more in the visible light wavelength band and has a transmittance of 10 Ω / sq. The following sheet resistance value and a figure of merit of 1 or more.

The TiO 2 / Ag / TiO 2 multilayer structure according to the present invention can be fabricated as a flexible transparent electrode by being laminated on a flexible substrate selected from the group consisting of polyethersulfone, polyethylene terephthalate, polycarbonate, polyimide, polyethylene naphthalate and glass materials .

On the other hand,

a) forming a TiO 2 layer on the substrate to a thickness of 20 nm to 80 nm;

b) forming an Ag metal layer on the TiO 2 layer to a thickness of 11 nm to 25 nm; And

c) forming a TiO 2 layer on the Ag metal layer to a thickness of 20 nm to 80 nm.

In the method according to the present invention, the thicknesses of the Ag metal layer and the TiO 2 layer, and the ratio of the thickness between the two layers are as described above.

In the method according to the present invention, the deposition of the Ag metal layer and the TiO 2 layer may be performed using a conventional flexible transparent electrode manufacturing method such as, but not limited to, sputtering, electron beam evaporation, and continuous evaporation deposition , It is compatible with existing ITO processes, which is one of the most important advantages in practical industrial applications. In addition, the steps a) to c) may be performed by a batch type process.

The flexible transparent electrode manufactured according to the present invention can be usefully used for manufacturing solar cells, light emitting diodes, and the like that require excellent light transmittance, electrical conductivity, and flexibility. In particular, the flexible transparent electrode according to the present invention can be manufactured with a flat and stable surface having a large area without a high-temperature heat treatment, which has a great effect on the active layer of the organic material formed on the transparent electrode. Can be improved.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are intended to assist the understanding of the present invention and should not be construed as limiting the scope of the present invention.

Example  1. Preparation of transparent electrode according to the present invention

The PET flexible substrate was cleaned and a TiO 2 thin film was deposited on the substrate at room temperature using rf sputtering method to a thickness of 40 nm. The TiO 2 target was prepared by high temperature sintering. The rf output applied to the target was 90 W, the working vacuum was maintained at 10 mTorr, the distance between the target and the substrate was maintained at about 10 cm, and the sputtering gas used was Ar gas at 30 sccm.

Next, an Ag layer was deposited to a thickness of 19 nm on the TiO 2 thin film under the conditions of an rf output of 30 W, a deposition pressure of 10 mTorr, and an Ar gas flow rate of 13 sccm using an Ag target. Under the same conditions as described above A 40 nm thick TiO 2 thin film was deposited on the Ag layer. On the other hand, a transparent electrode was prepared by the same method, except that the thickness of the TiO 2 layer was 10, 20, 30, 50 and 70 nm, respectively.

Evaluation example  1. Bending test

The bending test was performed for 1000 cycles on the transparent electrode (TiO 2 layer thickness: 40 nm) and the conventional ITO electrode (thickness: 100 nm) manufactured according to Example 1 and the resistance change rate (ΔR / R 0 : ΔR - resistance change value, R 0 - initial resistance value). Figs. 1A (Example 1) and 1b (conventional conventional ITO electrode) show graphs of bending test photographs and the results thereof. The bending test was performed by fixing one side of the sample to the fixing device and narrowing the distance to the other side, and this process was repeated 1000 times. Referring to FIGS. 1A and 1B, the electrode according to Example 1 showed a bending test result similar to that of a conventional ITO electrode, and the rate of resistance change remained almost constant.

Evaluation example  2. Electrical measurement

The carrier concentration, mobility, resistivity and sheet resistance of the transparent electrode (TiO 2 layer thickness: 40 nm) prepared according to Example 1 and the conventional ITO electrode were measured. The results are shown in Fig.

Referring to FIG. 4, the resistivity and sheet resistance values of the sample according to Example 1 were much lower than those of the conventional ITO electrode (before heat treatment), the mobility was slightly lower than that of the conventional ITO electrode, It can be seen that the carrier concentration shows a significantly higher value.

Evaluation example  3. Measurement of permeability

The transmittance of each of the samples according to Example 1 and the commercial ITO electrode (thickness: 100 nm) was measured at 200 nm to 1100 nm using a polymer and a glass substrate as the base. The results are shown in FIG. 2A (40 nm TiO 2 (The electrode according to Example 1 having a layer thickness and the commercially available ITO electrode as a base of a polymer substrate) and Fig. 2b (the six electrodes according to Example 1 were measured with a glass substrate base and the transmittance of the pure Ag electrode was also measured) Respectively.

Referring to FIG. 2A, it can be seen that the sample according to Example 1 exhibits a transmittance comparable to that of commercial ITO in the visible light region. Referring to FIG. 2B, it can be seen that the transmittance of the samples tends to decrease as the thickness of the TiO 2 layer increases in the visible light region.

Evaluation example  4. Performance index ( figure of merit ) Calculation

As can be seen from the evaluation examples 2 and 3, in the case of the transparent electrode, it can be seen that the electric conductivity and the light transmittance are in conflict with each other depending on the thickness of the thin film. Therefore, in order to compare the characteristics of each transparent electrode, , The corresponding figure of merit (Φ TC ) is defined by the following equation (1): Φ TC =

<Formula 1>

TC = T 10 / R sh

Where T is the transmittance of the sample and R sh is the sheet resistance value.

3 shows the results of calculating the figure of merit of an electrode according to Example 1 having a thickness of 40 nm TiO 2 layer and a commercially available ITO electrode (thickness: 100 nm) on a PET substrate.

Referring to FIG. 3, it can be seen that the sample according to Example 1 exhibits a value that is about 70 higher than that of commercial ITO in terms of its performance index.

Claims (14)

Ag metal layer; And
A flexible transparent electrode comprising a TiO 2 layer stacked on the upper and lower surfaces of the Ag metal layer,
The Ag metal layer had a thickness of 19 nm,
The thickness of the TiO 2 layer is 40 nm,
Has a light transmittance of 90% or more at a visible light wavelength band of 600 to 700 nm and has a transmittance of 10 Ω / sq. And a figure of merit, wherein the figure of merit is calculated according to the following formula (1): &quot; (1) &quot;
[Equation 1]
TC = T 10 / R sh
TC is a figure of merit, T is permeability, and R sh is a sheet resistance)
delete delete delete delete The method according to claim 1,
Wherein the Ag metal layer and the TiO 2 layer are laminated on a flexible substrate selected from the group consisting of polyethersulfone, polyethylene terephthalate, polycarbonate, polyimide, polyethylene naphthalate and a glass material.
a) forming a TiO 2 layer on the substrate to a thickness of 40 nm;
b) forming an Ag metal layer on the TiO 2 layer to a thickness of 19 nm; And
c) forming a TiO 2 layer on the Ag metal layer to a thickness of 40 nm,
Has a light transmittance of 90% or more at a visible light wavelength band of 600 to 700 nm and has a transmittance of 10 Ω / sq. And a figure of merit, wherein the figure of merit is calculated according to the following formula (1): &quot; (1) &quot;
[Equation 1]
TC = T 10 / R sh
TC is a figure of merit, T is permeability, and R sh is a sheet resistance)
delete delete delete 8. The method of claim 7,
Wherein the steps a) to c) are performed by any one selected from the group consisting of a sputtering method, an electron beam evaporation method, and a continuous evaporation deposition method.
8. The method of claim 7,
Wherein the steps a) to c) are performed by a batch process.
A solar cell comprising the flexible transparent electrode according to any one of claims 1 to 6. 7. A light emitting diode comprising a flexible transparent electrode according to any one of claims 1 to 6.
KR1020150120150A 2015-08-26 2015-08-26 Transparent electrode with TiO2/Ag/TiO2 multilayered structure and method for preparing the same KR101816972B1 (en)

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JP2015115180A (en) 2013-12-11 2015-06-22 コニカミノルタ株式会社 Transparent conductive body
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JP2015060728A (en) 2013-09-19 2015-03-30 コニカミノルタ株式会社 Transparent electrode and organic electroluminescent element
JP2015115180A (en) 2013-12-11 2015-06-22 コニカミノルタ株式会社 Transparent conductive body
JP2016091071A (en) 2014-10-30 2016-05-23 コニカミノルタ株式会社 Transparent conductive film and method for producing the same

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