JP2003225964A - Transparent conducting thin film laminate and its use application - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transparent conducting thin film laminate which hardly flocculates a silver atom in a thin silver film layer in the presence of a chloride ion or by applying electric current and for this reason, has the advantage that a dot-like defect due to silver flocculation does not occur, when this laminate is used as a member for a transparent electrode or an electromagnetic wave barrier filter. <P>SOLUTION: This transparent conducting thin film laminate comprises a transparent substrate (A), a transparent thin film layer with high refractive index (a) and a metallic thin film layer (b), with such characteristics that the metallic thin film layer (b) is formed of at least silver, neodymium, gold or copper. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a transparent conductive thin film laminate excellent in durability and its use.

[0002]

2. Description of the Related Art A transparent conductive thin film is a transparent and conductive thin film, and a typical example thereof is a thin film made of an oxide of indium and tin (ITO). Its main uses are for transparent electrodes of display panels and for electromagnetic wave shielding.

As transparent electrode applications for display panels, liquid crystal displays (LCDs), electroluminescence (EL) displays, plasma display panels (PDPs), etc. are now widely used.

Recently, there has been a great demand for a large size and small size portable display panel. In order to realize this, it is necessary to reduce the power consumption of the display element. For this purpose, it is effective to develop a transparent conductive thin film having a low resistance value while maintaining visible light transmittance. In particular, the organic electroluminescent element that has been recently developed is a self-luminous type and is mainly developed for small portable terminals, and therefore, there is great expectation for lowering the resistance of the transparent conductive thin film. In addition, as for plasma display panels (PDPs) that are currently spreading in the market and field emission displays (FEDs) that are being developed as next-generation displays, they have a structure with high power consumption, and therefore have low resistance transparent conductivity. Expectations for thin film development are high.

Electromagnetic wave shielding is an important issue. Electromagnetic waves are known to damage instruments, and recently, it has been reported that electromagnetic waves may also damage human bodies. Therefore, the emission of electromagnetic waves is legally regulated. For example, in Japan, VCCI (Voluntary Control C) is currently used.
onecil for Interference b
y data processing equipment
nt electronic office match
in the US, FCC (Fed
eral Communication Commis
There is a product regulation by sion).

As an electromagnetic wave shielding application, it is widely used as an electromagnetic wave shielding filter for televisions and CRT monitors for computers.

Plasma display panel (PDP)
Emits strong electromagnetic waves from the display portion to the outside due to its light emitting principle. In order to block strong electromagnetic waves, a low-resistance transparent electromagnetic wave blocking filter is required.

In developing a low resistance transparent conductive thin film, it is effective to use a metal thin film layer, particularly a metal thin film layer using silver having the smallest specific resistance among pure substances. Further, for the purpose of increasing the transmittance and improving the stability of the metal thin film layer, it is very effective to sandwich the metal thin film layer between the transparent high refractive index thin film layers to form a transparent conductive thin film laminate. This transparent conductive thin film laminate can be designed to have optimum optical characteristics and electrical characteristics depending on the application by selecting the material and film thickness of each thin film layer.

Silver, which is preferably used as a metal thin film layer material because of its low specific resistance, has a surface on the other hand that it tends to cause aggregation of atoms. For example, aggregation easily occurs in the presence of chloride ions or under an electric field. Aggregation of silver atoms in the silver thin film causes silver white spots, losing their original high transparency and low resistance. As one of the methods for suppressing the aggregation of silver, there is a method of alloying silver. Common metals used for alloying are gold, copper, and palladium. Conventionally, an alloy composed of silver, palladium, and copper has been the most durable silver alloy material. In particular, when a silver alloy containing 1% by weight of palladium and 1% by weight of copper is used, the high transparency and low resistance are not significantly impaired as compared with the case of using pure silver, and the durability of the transparent conductive thin film laminate is improved. Can be improved. However, these transparent conductive thin film laminates are likely to cause aggregation of silver atoms in the silver thin film layer in the presence of chloride ions or by passing an electric current. Therefore, when used as a transparent electrode or a member for electromagnetic wave shielding filters, point defects due to silver aggregation tend to occur.

[0010]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a transparent conductive thin film laminate which does not cause the above-mentioned problem silver agglomeration.

[0011]

As a result of intensive studies to solve the above problems, the inventors of the present invention have contained a metal thin film layer (b) containing silver, neodymium and gold, or copper. It was found that the use of the transparent conductive thin film laminate can significantly suppress the generation of point defects due to silver aggregation when used as a transparent electrode or an electromagnetic wave blocking filter member, as compared with the conventional one. Came to. The present invention is specified by the following matters.

(1) A transparent conductive thin film laminate comprising a transparent substrate (A), a transparent high refractive index thin film layer (a) and a metal thin film layer (b), wherein the metal thin film layer (b) is at least silver. , A transparent conductive thin film laminate comprising neodymium and gold or copper. (2) Neodymium in the metal thin film layer (b) is 0.1 at%
As described above, the transparent conductive thin film laminate is characterized by containing 1.0 at% or less and containing 0.3 at% or more and 2 at% or less of gold. (3) 0.1 at% neodymium in the metal thin film layer (b)
As described above, the transparent electroconductive thin film laminate is characterized by containing 1.0 at% or less and copper by 0.3 at% or more and 2 at% or less. (4) A transparent high refractive index thin film layer (a) and a metal thin film layer (b) are A / A on at least one main surface of the transparent substrate (A).
b / a, A / a / b / a, A / b / a / b / a, A / a
/ B / a / b / a, A / b / a / b / a / b / a, A /
a / b / a / b / a / b / a, A / b / a / b / a / b
/ A / b / a, A / a / b / a / b / a / b / a / b /
The transparent conductive thin film laminate according to any one of (1) to (3) above, wherein the transparent conductive thin film laminate is arranged in any of a. (5) The thickness of the metal thin film layer (b) is 5 nm or more and 20 nm
It is the following, The transparent conductive thin film laminated body in any one of said (1)-(3). (6) The transparent high refractive index thin film layer (a) is indium oxide,
The transparent conductive thin film laminate according to any one of the above (1) to (4), which contains tin oxide, zinc oxide or titanium oxide as a main component. (7) The transparent conductive material according to any one of (1) to (4) above, wherein the transparent high refractive index thin film layer (a) is a metal oxide (ITO) composed of indium oxide and tin oxide. Thin film stack. (8) An optical filter for PDP using the transparent conductive thin film laminate according to any one of (1) to (7) above. (9) A transparent electrode using the transparent conductive thin film laminate according to any one of (1) to (7) above.

BEST MODE FOR CARRYING OUT THE INVENTION The transparent conductive thin film laminate of the present invention comprises a transparent substrate (A), a transparent high refractive index thin film layer (a) and a metal thin film layer (b), and the metal thin film layer (b) is It is characterized by being composed of at least silver, neodymium and gold, or copper. When this is used as a transparent electrode or an electromagnetic wave blocking filter member, generation of point defects due to silver aggregation can be significantly suppressed.

The structure of the transparent electroconductive thin film laminate in the present invention comprises a transparent substrate (A), a transparent high refractive index thin film layer (a),
Assuming that the metal thin film layer (b) is A / b / a, A / a / b /
a, A / b / a / b / a, A / a / b / a / b / a, A
/ B / a / b / a / b / a, A / a / b / a / b / a /
b / a, A / b / a / b / a / b / a / b / a, A / a
One of / b / a / b / a / b / a / b / a is preferable. Various functional layers may be included between the layers. Possible functional layers include an adhesion layer, a gas barrier layer, and a layer for improving environmental resistance.

As the transparent substrate (A) used in the present invention, those in a film state or a plate state are mainly preferably used, which are excellent in transparency and have sufficient mechanical strength depending on the use. It is preferable. Here, “excellent in transparency” means that the luminous transmittance is 40% or more in a thickness in a used state. (Measurement method: JIS
R3106) Further, an antireflection layer or an antiglare layer may be formed on the surface opposite to the main surface of the transparent substrate.

A polymer film is preferably used as the transparent substrate film. Specific examples include polyimide, polysulfone (PSF), polyether sulfone (PES), polyethylene terephthalate (PE).
T), polymethylene methacrylate (PMMA), polycarbonate (PC), polyether ether ketone (PEEK), polypropylene (PP), triacetyl cellulose (TAC) and the like. Among them, polyethylene terephthalate (PET) and triacetyl cellulose (TAC) are particularly preferably used.

There is no particular limitation on the thickness of the transparent substrate film. Usually, it is about 20 to 500 μm. Examples of the plate-shaped transparent substrate include polymer moldings and glass. The transparent polymer molded body is more suitably used because it is lighter and less likely to break than glass. An example of a preferable material is polymethylmethacrylate (PMMA).
Examples thereof include acrylic resins and polycarbonate resins, but are not limited to these resins. Above all, PMMA can be preferably used because of its high transparency in a wide wavelength range and high mechanical strength.
Further, a transparent polymer molded body is often provided with a hard coat layer for the reason of increasing the surface hardness or adhesiveness.

Since glass is less likely to change its shape due to heat and humidity, it is preferably used for optical applications that require delicate precision. In order to have mechanical strength, it is usually used as a semi-tempered glass or a tempered glass by chemically strengthening or wind-cooling strengthening. The thickness of the plate-shaped transparent substrate is not particularly limited as long as it has sufficient mechanical strength and rigidity to maintain flatness without bending. Normally, 0.
It is about 5 to 10 mm.

The material used for the transparent high refractive index thin film layer (a) is preferably as transparent as possible. Here, having excellent transparency means that the film thickness is 100 n.
It means that when a thin film of about m is formed, the luminous transmittance of the thin film is 60% or more, preferably 70% or more. (Measurement method: JIS R3106) Further, the high refractive index material is a material having a refractive index of 1.4 or more, preferably 1.8 or more with respect to light of 550 nm. These include
Impurities may be mixed depending on the application.

Examples of materials that can be preferably used for the transparent high refractive index thin film layer include oxides of indium and tin (ITO) and oxides of cadmium and tin (CT).
O), aluminum oxide (Al ₂ O ₃ ), zinc oxide (Z
nO ₂ ), an oxide of zinc and aluminum (AZO),
Magnesium oxide (MgO), Thorium oxide (Th
O ₂ ), tin oxide (SnO ₂ ), lanthanum oxide (LaO
₂ ), silicon oxide (SiO ₂ ), indium oxide (I
n ₂ O _3), niobium oxide (Nb2O3), antimony oxide _{(Sb 2 O} 3), zirconium oxide _(ZrO 2), cesium oxide _(CeO 2), titanium oxide (TiO2), is a bismuth oxide (BiO ₂₎ etc. . Alternatively, a transparent high refractive index sulfide may be used. Specific examples include zinc sulfide (ZnS), cadmium sulfide (CdS), antimony sulfide (Sb ₂ S ₃ ), and the like.

As the transparent high refractive index thin film material, among others,
ITO, TiO ₂ and AZO are particularly preferable. ITO and AZO have conductivity, have a high refractive index of about 2.0 in the visible region, and have almost no absorption in the visible region. TiO2 is an insulator and has a slight absorption in the visible region, but has a large refractive index of about 2.3 for visible light.

The thickness of the transparent high refractive index thin film layer is determined in consideration of the transparency and electrical conductivity of the entire transparent conductive thin film layer. Usually, it is about 0.5 to 100 nm.
There is no particular limitation on the proportion of tin contained in ITO. Usually, it is 0 to 50% by weight. Moreover, there is no particular limitation on the proportion of aluminum contained in AZO. However, if the content ratio of aluminum is too high, the transmittance of the AZO film, particularly the transmittance of light having a wavelength of 300 to 500 (nm), is lowered, which is not preferable. Therefore, the proportion of aluminum contained in AZO is usually 1 to 5 (% by weight).
It is a degree.

When used as a transparent electrode, the transparent high refractive index thin film layer is preferably ITO. Since the ITO film can be a film having conductivity, it is preferable in terms of producing a transparent electrode having low contact resistance with the outside. The material used for the metal thin film layer (b) used in the present invention is an alloy containing at least silver, neodymium and gold or an alloy containing at least silver, neodymium and copper. Regarding the alloy of silver, neodymium, and gold, the higher the content ratio of neodymium and gold, the higher the durability of the transparent conductive thin film laminate, but the transmittance decreases and the surface resistance increases. It is necessary to determine the content ratios of neodymium and gold after considering the required transmittance and surface resistance according to the application.

The preferred content ratio of neodymium and gold is 0.1 at% or more and 1.0 at% or less of neodymium, and 0.3 at% or more and 2 at% or less of gold. At% means the ratio of the number of each atom to the total number of atoms constituting the alloy. A more preferable content ratio of neodymium and gold is 0.4 at% or more of neodymium,
1.0 at% or less, and gold at 0.3 at% or more,
It is 0.9 at% or less. A more preferable content ratio of neodymium and gold is 0.4 at% or more of neodymium, and 0.1.
7 at% or less, and gold at 0.3 at% or more, 0.6
It is at% or less.

The alloy of silver, neodymium and copper is the same as that of the alloy of silver, neodymium and gold. The higher the content ratio of neodymium and copper, the higher the durability of the transparent conductive thin film laminate, but the lower the transmittance and the higher the sheet resistance. It is necessary to determine the content ratio of neodymium and copper in consideration of the required transmittance and surface resistance according to the application.

The preferred content ratio of neodymium and copper is 0.1 at% or more and 1.0 at% or less of neodymium, and 0.3 at% or more and 2 at% or less of copper. More preferable content ratios of neodymium and copper are 0.4 at% or more and 1.0 at% or less for neodymium, and 0.3 at% or more and 0.9 at% or less for copper. A more preferable content ratio of neodymium and copper is neodymium of 0.
4 at% or more and 0.7 at% or less, and copper is 0.3
It is at% or more and 0.6 at% or less. Regarding the thickness of the metal thin film layer (b), the thicker it is, the higher the durability of the transparent conductive thin film laminate is, but the lower the transmittance is. It is necessary to determine the thickness of the metal thin film layer (b) in consideration of the required transmittance and sheet resistance depending on the application. The thickness of the metal thin film layer (b) is usually 5 nm or more and 20 nm or less.
It is more preferably 7 nm or more and 15 nm or less, and further preferably 9 nm or more and 12 nm or less.

Ion plating or reactive sputtering is preferably used for forming the transparent high refractive index thin film layer (a). In the ion plating method, vacuum evaporation is performed by resistance heating a desired metal or sintered body in a reaction gas plasma or by heating with an electron beam. In the reactive sputtering method, a desired metal or sintered body is used as a target, an inert gas such as argon or neon is used as a sputtering gas, and a gas necessary for the reaction is added to perform sputtering. For example, I
When forming a TO thin film, direct current magnetron sputtering is performed in oxygen gas using an oxide of indium and tin as a sputtering target.

A vacuum deposition method or a sputtering method is preferably used for forming the metal thin film layer (b). In the vacuum evaporation method, a desired metal is used as an evaporation source, and resistance heating, electron beam heating, or the like is performed to heat evaporation,
The metal thin film can be easily formed. When a sputtering method is used, a desired metal material is used as a target, an inert gas such as argon or neon is used as a sputtering gas, and a metal thin film is formed by using a direct current sputtering method or a high frequency sputtering method. You can A direct current magnetron sputtering method and a high frequency magnetron sputtering method are often used to increase the film formation rate.

(Use as transparent electrode) The optical characteristics and electrical characteristics of the transparent conductive thin film laminate of the present invention are selected as desired under certain constraint conditions. Regarding the optical characteristics, when the transparent conductive thin film laminate of the present invention is used as the transparent electrode of the light emitting element, it is preferable that it has a high luminous average transmittance. The average luminous transmittance is preferably 50% or more, more preferably 60% or more, still more preferably 70% or more. Moreover, it is preferable to have a low sheet resistance in terms of electrical characteristics. The preferred sheet resistance is 0.
1Ω / □ or more, 15Ω / □ or less, more preferably 0.1
Ω / □ or more, 9Ω / □ or less, more preferably 0.1Ω
/ □ or more and 7Ω / □ or less.

(Use as PDP optical filter)
In the examples of the present invention, the transparent conductive thin film laminate was evaluated with three layers, but in an actual optical filter for PDP, since it is used as five layers, seven layers, and nine layers, by optimizing the conditions, It can have a high average luminous transmittance and a low sheet resistance. The average luminous transmittance of the seven layers is preferably 50.
% Or more, more preferably 60% or more, and further preferably 70% or more. Further, the preferable sheet resistance of the 7 layers is 0.2 Ω / □ or more and 10 Ω / □ or less, more preferably 0.2 Ω / □ or more and 3 Ω / □ or less, further preferably 0.2 Ω / □ or more, 0.5 Ω / □. □ Below.

The atomic composition on the surface of the thin film layer of the transparent conductive thin film laminate produced by the above method is Auger electron spectroscopy (AES), fluorescent X-ray method (XRF), X-ray microanalysis method (XMA). , Charged particle excitation X-ray analysis (R
BS), X-ray photoelectron spectroscopy (XPS), vacuum ultraviolet photoelectron spectroscopy (UPS), infrared absorption spectroscopy (IR), Raman spectroscopy, secondary ion mass spectrometry (SIMS), low energy ion scattering spectroscopy (ISS) and the like. Further, the atomic composition and the film thickness in the film can be examined by performing Auger electron spectroscopy (AES) or secondary ion mass spectrometry (SIMS) in the depth direction.

The structure of the transparent conductive thin film laminate and the state of each layer are measured by an optical microscope for a cross section and a scanning electron microscope (SE).
M) Measurement, transmission electron microscope measurement (TEM) can be used for examination. When the transparent conductive thin film laminate is used as an optical filter for PDP, it is necessary to endure chloride ions contained in the atmosphere or contained in human sweat.
Therefore, durability against chloride ions is required. The durability against chloride ions can be examined by a sodium chloride aqueous solution immersion test.

(Sodium Chloride Aqueous Solution Immersion Test) The sodium chloride aqueous solution immersion test is a test for immersing the transparent conductive thin film in the sodium chloride aqueous solution and examining the silver aggregation state of the silver alloy thin film layer of the transparent conductive thin film by chloride ions. . There is no particular limitation on the method of immersing the transparent conductive thin film in the aqueous sodium chloride solution. Usually, the transparent substrate is submerged in a container containing an aqueous sodium chloride solution.

The concentration of the aqueous sodium chloride solution used in the test may be selected at an appropriate value depending on the application of the transparent conductive thin film laminate. The transparent conductive thin film is usually used in a state where the atmosphere is cut off, because the thin film often undergoes agglomeration or a chemical change to deteriorate when exposed to the atmosphere for a long time. Therefore, in the manufacturing stage, a sodium chloride aqueous solution having a concentration capable of reproducing a state comparable to the amount of chloride ions reaching the transparent conductive thin film in a short time when the transparent conductive thin film is exposed to the atmosphere. It is possible to determine whether or not it has the ability to withstand practical use by conducting a test using. Normally, the concentration is 0.5mo
It can be determined by immersing in an aqueous solution of 1 / l and 20 ° C. for about 9 hours. Quantitative determination of corrosion resistance to chloride ions by a sodium chloride aqueous solution immersion test can be performed by examining the rate of decrease in transmittance of the transparent conductive thin film. As an index, the transmittance T after immersion
The ratio of the pre-immersion transmittance T ₀ = T / T ₀ may be used.

The frequency of product defects due to point defects due to silver agglomeration is determined by bonding the transparent conductive thin film laminate to a transparent glass substrate via an adhesive on the transparent substrate side. A PET film bonded to the opposite side of the transparent substrate via an adhesive material is subjected to high temperature and high humidity treatment,
It can be examined by the frequency of point defects caused by silver aggregation that occurs at that time.

It is preferable that T / T ₀ is closer to 1 because the frequency of occurrence of point defects due to silver aggregation is reduced. Where T / T
_{For 0} , a value when immersed in a sodium chloride aqueous solution having a concentration of 0.5 mol / l and a temperature of 20 ° C. for 9 hours is adopted. In general, T / T ₀ is preferably 0.8 or more, and more preferably 0.9 or more. When the transparent conductive thin film laminate is used as a transparent electrode for organic EL, deterioration occurs due to the flow of current. Therefore, durability against electric current is required. The durability against electric current can be examined by a withstand current test.

(Withstand Current Test) The withstand current test is carried out by the method described below. A transparent substrate (A) having a size of 50 mm × 25 mm is prepared. A transparent conductive thin film laminate having a width of 3 mm is formed on the surface of the transparent substrate (A) so as to be parallel to one side. The transparent conductive thin film laminate has a rectangular shape with a long side of 50 mm and a short side of 3 mm. 2 on transparent conductive thin film stack
A conductive foil tape is attached in the vicinity of the short side so as to cover up to a portion 10 mm away from the end to form two external extraction electrodes.

A DC voltage is applied between the two external extraction electrodes, and a desired current is passed for 1 minute. Then, the state of the transparent conductive thin film is observed with an optical microscope. Observation magnification is 3
000 times. As a result of the observation, a dot pattern having a diameter of 0.1 μm or more may be observed on the surface. When the transparent electroconductive thin film laminate is used as a transparent electrode of an organic electroluminescence element to emit electricity by energization, the above-mentioned dot pattern has a correlation with the occurrence of a non-light emitting portion. That is, as a result of carrying out the test, although the current flowing is small,
The transparent electroconductive thin film laminate in which a pattern is observed on the surface after energization is not practical because the organic electroluminescence element easily produces a non-luminous portion when energized to emit light. On the other hand, a transparent conductive thin film laminate in which no pattern is observed on the surface after energization even when a large current value is passed in the test is non-luminous when used as a transparent electrode of an organic electroluminescence device. It is practical because it is difficult to produce parts.

In the present invention, the current value suitable for determining the presence or absence of the non-light emitting portion in the element using the pattern by judging the pattern generation when the current is applied is 0.20 A. . In addition, when it is assumed that the target organic electroluminescent element is used by flowing a larger current, it is preferable to make the determination with a higher current value. For example, the threshold may be set to 0.25A. When it is preferable to use a higher current value as the threshold value, for example, 0.30 A may be set as the threshold value. It should be noted that the higher the above-mentioned threshold value, the more excellent the withstand current characteristic of the transparent conductive thin film is, and the less likely it is that a light emission defect will occur when the device is made to emit light.

[0039]

EXAMPLES Next, the present invention will be specifically described by way of examples. (Example 1) (Preparation of transparent conductive thin film laminate) A polyethylene terephthalate (PET) film [thickness 75 µm] as a transparent substrate (A), and a glass plate [manufactured by Corning Incorporated, model number 705]
9, size 50 mm × 25 mm, thickness 1.1 mm] were prepared. A PET film was used for the transparent substrate (A) for the sample for the sodium chloride aqueous solution immersion test, and a glass plate was used for the transparent substrate (A) for the sample for the withstand current test. Kapton tape is used as a mask on the glass substrate, and the width is 3 m so that it is parallel to one side of the transparent substrate (A).
A transparent conductive thin film having a length of m and a length of 50 mm was formed. The film formation was performed under the following conditions. Using a direct current magnetron sputtering method, a thin film layer (a) made of an oxide of indium and tin and an alloy thin film layer (b) of silver, neodymium and gold were formed on the transparent substrate (A) at A / a [thickness]. 40 nm] / b
The layers were laminated in the order of [thickness 10 nm] / a [thickness 40 nm] to form a transparent conductive thin film. The thin film layer made of an oxide of indium and tin constitutes a transparent high refractive index thin film layer, and the alloy thin film layer of silver, neodymium and gold constitutes a metal thin film layer. To form a thin film layer made of an oxide of indium and tin, as a target, an indium oxide-tin oxide sintered body [In ₂ O ₃ : SnO ₂ = 90: 10 (weight ratio)],
Argon / oxygen mixed gas (total pressure 266 mPa, oxygen partial pressure 8 mPa) was used as the sputtering gas. Also,
To form an alloy thin film layer of silver, neodymium, and gold, an alloy of silver, neodymium, and gold [Ag: Nd: Au] is used as a target.
= 99.6: 0.1: 0.3 (ratio of atoms)],
Argon gas (total pressure 186 mPa) was used as the sputtering gas. A cross-sectional view of the formed transparent conductive thin film is shown in FIG.

In this example, the luminous transmittance of the transparent electroconductive thin film laminate produced as described above [manufactured by Hitachi spectrophotometer U
-3400 was used to measure the total light transmittance to determine the luminous transmittance. ] And surface resistance [measured using a Kyowa Riken four-end needle surface resistance measuring device]. ] Was measured. In the sodium chloride aqueous solution immersion test, T / T ₀ was added at a concentration of 0.5 mol /
1 and the value when immersed in an aqueous sodium chloride solution at a temperature of 20 ° C. for 9 hours. In the withstand current test, the magnitude of the applied current was increased from 0.20 A by 0.01 A every minute, and it was examined at what current value the dot pattern was generated.

(Example 2) For forming the alloy thin film layer (b) composed of silver, neodymium and gold, a target of an alloy of silver, neodymium and gold [Ag: Nd: Au = 98.7:
0.1: 1.2 (atomic ratio)] was used, and the same procedure as in Example 1 was performed.

(Example 3) For forming the alloy thin film layer (b) consisting of silver, neodymium and gold, a target of an alloy of silver, neodymium and gold [Ag: Nd: Au = 97.9:
0.1: 2.0 (ratio of the number of atoms)] was used, and the same procedure as in Example 1 was performed.

Example 4 For the formation of the alloy thin film layer (b) consisting of silver, neodymium and gold, an alloy of silver, neodymium and gold [Ag: Nd: Au = 99.1: 1] was used as a target.
0.6: 0.3 (ratio of number of atoms)] was used, and the same procedure as in Example 1 was performed.

Example 5 For the formation of the alloy thin film layer (b) consisting of silver, neodymium and gold, a target of an alloy of silver, neodymium and gold [Ag: Nd: Au = 98.2:
0.6: 1.2 (ratio of the number of atoms)] was used.

(Example 6) For forming the alloy thin film layer (b) consisting of silver, neodymium and gold, an alloy of silver, neodymium and gold [Ag: Nd: Au = 97.4:
0.6: 2.0 (ratio of the number of atoms)] was used, and the same procedure as in Example 1 was performed.

Example 7 For the formation of the alloy thin film layer (b) consisting of silver, neodymium and gold, an alloy of silver, neodymium and gold [Ag: Nd: Au = 98.7:
1.0: 0.3 (ratio of the number of atoms)] was used, and the same procedure as in Example 1 was performed.

Example 8 For the formation of the alloy thin film layer (b) consisting of silver, neodymium and gold, a target of an alloy of silver, neodymium and gold [Ag: Nd: Au = 97.8:
1.0: 1.2 (ratio of the number of atoms)] was used.

(Example 9) For forming the alloy thin film layer (b) consisting of silver, neodymium and gold, an alloy of silver, neodymium and gold [Ag: Nd: Au = 97.0:
1.0: 2.0 (ratio of the number of atoms)] was used, and the same procedure as in Example 1 was performed.

Example 10 The transparent substrate (A) was prepared in the same manner as in Example 1, and the film formation was carried out under the following conditions. A thin film layer (a) made of an oxide of indium and tin, and an alloy thin film layer of silver, neodymium, and gold (b) on a transparent substrate (A) by using a DC magnetron sputtering method.
A / a [thickness 40 nm] / b [thickness 10 nm] / a
The layers were laminated in the order of [thickness 40 nm] to form a transparent conductive thin film. The thin film layer made of an oxide of indium and tin constitutes a transparent high refractive index thin film layer, and the alloy thin film layer of silver, neodymium and copper constitutes a metal thin film layer. To form a thin film layer made of an oxide of indium and tin, an indium oxide-tin oxide sintered body [In ₂ O ₃ : Sn was used as a target.
O ₂ = 90: 10 (weight ratio)], and an argon / oxygen mixed gas (total pressure 266 mPa, oxygen partial pressure 8 mPa) was used as the sputtering gas. Further, in forming the alloy thin film layer of silver, neodymium and copper, an alloy of silver, neodymium and copper [Ag: Nd: Cu = 99.6: 0.1:
0.3 (atomic ratio)] and argon gas (total pressure 186 mPa) was used as the sputtering gas. A cross-sectional view of the formed transparent conductive thin film is shown in FIG.

(Example 11) For forming the alloy thin film layer (b) consisting of silver, neodymium and copper, an alloy of silver, neodymium and copper [Ag: Nd: Cu = 98.7:
0.1: 1.2 (ratio of the number of atoms)] was used, and the same procedure as in Example 10 was performed.

Example 12 An alloy thin film layer (b) made of silver, neodymium, and copper was formed with a target of an alloy of silver, neodymium, and copper [Ag: Nd: Cu = 97.9:
0.1: 2.0 (ratio of the number of atoms)] was used, and the same procedure as in Example 10 was performed.

(Example 13) For forming the alloy thin film layer (b) consisting of silver, neodymium and copper, an alloy of silver, neodymium and copper [Ag: Nd: Cu = 99.1: 1] was used as a target.
0.6: 0.3 (ratio of the number of atoms)] was used, and the same procedure as in Example 10 was performed.

(Example 14) For forming the alloy thin film layer (b) consisting of silver, neodymium and copper, an alloy of silver, neodymium and copper [Ag: Nd: Cu = 98.2:
0.6: 1.2 (ratio of the number of atoms)] was used.

(Example 15) For forming the alloy thin film layer (b) consisting of silver, neodymium and copper, an alloy of silver, neodymium and copper [Ag: Nd: Cu = 97.4:
0.6: 2.0 (atomic ratio)] was used, and the same procedure as in Example 10 was performed.

(Example 16) For forming an alloy thin film layer (b) composed of silver, neodymium and copper, a target of an alloy of silver, neodymium and copper [Ag: Nd: Cu = 98.7:
1.0: 0.3 (ratio of number of atoms)] was used, and the same procedure as in Example 10 was performed.

(Example 17) For forming an alloy thin film layer (b) composed of silver, neodymium and copper, an alloy of silver, neodymium and copper [Ag: Nd: Cu = 97.8:
1.0: 1.2 (atom number ratio)] was used, and the same procedure as in Example 10 was performed.

(Example 18) For the formation of the alloy thin film layer (b) consisting of silver, neodymium and copper, an alloy of silver, neodymium and copper [Ag: Nd: Cu = 97.0:
1.0: 2.0 (atomic ratio)] was used, and the same procedure as in Example 10 was performed.

(Example 19) An alloy thin film layer (b) made of silver, neodymium and gold was used as a target for an alloy of silver, neodymium and gold [Ag: Nd: Au = 98.7].
2: 0.08: 1.2 (atomic ratio)] was used, and the same procedure as in Example 1 was performed.

(Example 20) For the formation of the alloy thin film layer (b) consisting of silver, neodymium and gold, an alloy of silver, neodymium and gold [Ag: Nd: Au = 97.6:
1.2: 1.2 (atomic ratio)] was used, and the same procedure as in Example 1 was performed.

(Example 21) For forming an alloy thin film layer (b) composed of silver, neodymium and gold, an alloy of silver, neodymium and gold [Ag: Nd: Au = 99.3:
0.6: 0.1 (ratio of atoms)] was used, and the same procedure as in Example 1 was performed.

(Example 22) For the formation of the alloy thin film layer (b) consisting of silver, neodymium and gold, an alloy of silver, neodymium and gold [Ag: Nd: Au = 97.2:
0.6: 2.2 (atomic ratio)] was used, and the same procedure as in Example 1 was performed.

(Example 23) For forming the alloy thin film layer (b) consisting of silver, neodymium and copper, an alloy of silver, neodymium and copper [Ag: Nd: Cu = 98.7] was used as a target.
2: 0.08: 1.2 (atomic ratio)] was used, and the same procedure as in Example 1 was performed.

(Example 24) For forming an alloy thin film layer (b) made of silver, neodymium and copper, an alloy of silver, neodymium and copper [Ag: Nd: Cu = 97.6:
1.2: 1.2 (atomic ratio)] was used, and the same procedure as in Example 1 was performed.

(Example 25) For forming the alloy thin film layer (b) consisting of silver, neodymium and copper, an alloy of silver, neodymium and copper [Ag: Nd: Cu = 99.3:
0.6: 0.1 (ratio of atoms)] was used, and the same procedure as in Example 1 was performed.

(Example 26) For forming the alloy thin film layer (b) composed of silver, neodymium and copper, an alloy of silver, neodymium and copper [Ag: Nd: Cu = 97.2:
0.6: 2.2 (atomic ratio)] was used, and the same procedure as in Example 1 was performed.

(Comparative Example 1) The alloy thin film layer (b) is a thin film layer made of silver, palladium and copper, and the alloy thin film layer is formed by using an alloy of silver, palladium and copper [A] as a target.
g: Pd: Cu = 99: 1: 1 (weight ratio)], and the same procedure as in Example 1 was performed.

(Comparative Example 2) The procedure of Example 1 was repeated except that the alloy thin film layer (b) was a silver thin film layer, and silver was used as a target for forming the silver thin film layer.

The above results are shown in Table 1.

[0069]

[Table 1]

As can be seen from Table 1, in all of the examples, a significant luminous average transmittance was obtained as compared with the alloy of silver, palladium and copper which had the highest durability in the past (Comparative Example 1). Without causing a decrease in
It can be seen that the durability against chloride ions or electric current is improved.

[0071]

INDUSTRIAL APPLICABILITY According to the present invention, as the performance of the transparent conductive thin film laminate, the corrosion resistance against chloride ions and the durability against electric current can be greatly improved.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing an example of a transparent conductive thin film laminate.

[Explanation of symbols]

10 Transparent substrate (A) 20 Transparent high refractive index thin film layer (a) 30 metal thin film layer (b)

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) // C23C 14/06 G02B 1/10 Z F term (reference) 2K009 AA03 BB28 CC03 CC14 DD04 EE03 4F100 AA17B AA21B AA25B AA28B AA33B AB01C AB17C AB24C AB31 AB33C AG00A AK01A AK42 AR00A BA03 BA04 BA05 BA10A BA10C BA25C EH662 JB02 JM02B JN01A JN01B JN18B YY00C 4K029 A07FA02 BC01 BA02 BA01 BA02 BA01 BA02 BA01 BA02 BA01 BA02 BA45 BA02 BA45 BA47 BA02 BA45 BA02 BA45 BA02

Claims (9)

[Claims] 1. A transparent conductive thin film laminate comprising a transparent substrate (A), a transparent high refractive index thin film layer (a) and a metal thin film layer (b), wherein the metal thin film layer (b) is at least silver, A transparent conductive thin film laminate comprising neodymium and gold or copper. 2. The metal thin film layer (b) contains neodymium in an amount of 0.1 at% or more and 1.0 at% or less, and gold of 0.
3 at% or more and 2 at% or less are contained, The transparent conductive thin film laminated body of Claim 1 characterized by the above-mentioned. 3. The metal thin film layer (b) contains 0.1 at% or more and 1.0 at% or less of neodymium, and has a copper content of 0.
3 at% or more and 2 at% or less are contained, The transparent conductive thin film laminated body of Claim 1 characterized by the above-mentioned. 4. A transparent high refractive index thin film layer (a) and a metal thin film layer (b) on at least one main surface of the transparent substrate (A).
And A / b / a, A / a / b / a, A / b / a / b /
a, A / a / b / a / b / a, A / b / a / b / a / b
/ A, A / a / b / a / b / a / b / a, A / b / a /
b / a / b / a / b / a, A / a / b / a / b / a / b
It is arrange | positioned in either / a / b / a, The transparent conductive thin film laminated body in any one of Claims 1-3 characterized by the above-mentioned. 5. The metal thin film layer (b) has a thickness of 5 nm or more and 20 nm or less.
The transparent conductive thin film laminate according to any one of 1. 6. The transparent high refractive index thin film layer (a) contains at least one of indium oxide, tin oxide, zinc oxide and titanium oxide as a main component. The transparent conductive thin film laminate of. 7. The transparent conductive thin film according to claim 1, wherein the transparent high refractive index thin film layer (a) is a metal oxide (ITO) composed of indium oxide and tin oxide. Laminate. 8. An optical filter for PDP, which uses the transparent conductive thin film laminate according to claim 1. Description: 9. A transparent electrode using the transparent conductive thin film laminate according to claim 1.