JPWO2006132411A1 - Silver alloy for electrode, wiring and electromagnetic shielding - Google Patents

Abstract

The present invention is mainly composed of silver, and at least nickel, molybdenum, copper, cobalt, titanium, scandium, yttrium, manganese, silicon, iron, zirconium, niobium, tantalum, tungsten, chromium, and carbon as a first additive element group. A silver alloy for shielding an electromagnetic wave, an electrode, a wiring, and one kind. Here, the first additive element group is preferably copper, titanium, zirconium, manganese, and yttrium, and it is preferable to add at least one of gallium, palladium, and dysprosium as the second additive element group. The total concentration of these additive elements is preferably 0.01 to 20.0 atomic%.

Description

  The present invention relates to a silver alloy useful as an electrode and wiring material, and further to an electromagnetic wave shielding material, and relates to a silver alloy having significantly improved environmental resistance and a low specific resistance value.

Silver is the metal material that has the lowest specific resistance among metals and is excellent in electrical conductivity, and can be expected to be applicable as an electrode material or a wiring material. In particular, application as an electrode material for solar cells, a display device such as an organic light emitting display or a liquid crystal display, a thin film electrode material for various electronic components, and a wiring material is being studied. This is because refractory metal materials such as tantalum, chromium, molybdenum, and titanium that have been conventionally used as wiring materials respond to the problem of signal delay due to their relatively high electrical resistance. .
Japanese Patent Laid-Open No. 10-48650 JP 2003-328184 A

In recent years, with the widespread use of electronic devices such as personal computers and word processors, the necessity of shielding electromagnetic waves has been highlighted in view of the influence on devices and human bodies caused by electromagnetic noise generated by these electronic devices. Silver is a material that can be expected as a constituent material of an electromagnetic wave shield because of its low specific resistance. This is because attenuation (absorption) when electromagnetic waves pass through an object depends on the frequency of the electromagnetic waves and the specific resistance of the object, but attenuation tends to increase as the specific resistance decreases.
JP-A-6-164186 Japanese Patent Laid-Open No. 11-97885 JP 2003-152389 A

  Furthermore, the low specific resistance leads to the ability to form as thin a film as possible while suppressing the resistance value. Therefore, silver is also useful for forming a light-transmitting film having electrical conductivity (having an electromagnetic wave shielding effect). In the above electrode / wiring material and electromagnetic wave shielding material, electromagnetic waves are applied to transparent bodies such as transparent electrodes and glass. It can be expected as a material for imparting a shielding effect.

  On the other hand, there is a problem that silver is poor in environmental resistance and easily corroded. The change in silver due to corrosion is remarkable in terms of the appearance of blackening, but at the same time, the specific resistance increases and the transmittance deteriorates. The cause of this silver corrosion is basically due to moisture and heat in the environment of use, although the details differ depending on the application. And the problem of the characteristic deterioration by such corrosion of silver will affect the reliability of an apparatus.

  Therefore, an object of the present invention is to provide a material suitable as an electrode / wiring material or an electromagnetic wave shielding material while greatly improving the environmental resistance and maintaining a low specific resistance. In the present invention, the environmental resistance refers to a property that suppresses deterioration of specific resistance and transmittance due to the influence of the environment in which the silver alloy is placed, such as a heated atmosphere, a humidified atmosphere, and a sulfurized atmosphere. And sometimes referred to as sulfidation resistance.

  In order to solve the above-described problems, the present inventors have selected a suitable additive element for improving environmental resistance while mainly using silver. As a result, addition of nickel, molybdenum, copper, cobalt, titanium, scandium, yttrium, manganese, silicon, iron, zirconium, niobium, tantalum, tungsten, chromium, and carbon, which are higher melting points than silver Thus, the inventors have found that there is an effect of improving the environmental resistance, and have come to the present invention.

  That is, the present invention is mainly composed of silver, and the first additive element group is nickel, molybdenum, copper, cobalt, titanium, scandium, yttrium, manganese, silicon, iron, zirconium, niobium, tantalum, tungsten, chromium, carbon. Is a silver alloy for shielding an electromagnetic wave, an electrode comprising at least one kind.

  According to the study by the present inventors, among the high melting point elements listed as the first additive element group, in the silver alloy added with copper, titanium, zirconium, manganese, yttrium, the moisture resistance required for the reflection / transmission film It has been confirmed that the property is maintained at a particularly high dimension. Moisture resistance can be significantly improved by using these elements alone or by selecting 2 elements, 3 elements or more elements from the group and using them in combination as a “first additive element group”. . The first additive elements other than copper, titanium, zirconium, manganese, and yttrium are also effective in improving moisture resistance.

  In the present invention, the second additive element group includes gallium, thulium, dysprosium, platinum, palladium, magnesium, zinc, terbium, gadolinium, erbium, europium, gold, aluminum, neodymium, holmium, tin, bismuth, praseodymium, germanium. Indium, samarium, ytterbium, strontium, boron, rhodium, iridium, ruthenium, calcium, lead, antimony, hafnium, lanthanum, cerium, europium, lithium, and phosphorus are preferably further added. These elements together with the first additive element group further act to improve the environmental resistance.

  In particular, a silver alloy to which gallium, palladium, dysprosium, indium, tin, zinc, magnesium, aluminum, gadolinium, erbium, praseodymium, samarium, lanthanum is added as a second additive element group is generated in a thin film material in a heating environment It is a preferable alloy that can effectively suppress the agglomeration phenomenon.

  The component consisting of the second additive element group is added mainly for the purpose of improving the heat resistance of the alloy. That is, in order to ensure the heat resistance required for the thin film, these elements are added alone, or two elements, three elements, or more multi-elements are selected and added.

  Here, the concentration of the additive element group is preferably 0.01 to 20.0 atomic%. This is because if the addition amount is less than 0.01 atomic%, there is no effect of improving the environmental resistance, and if the additive element concentration exceeds 20.0 atomic%, the specific resistance of the alloy increases. Here, there are actually various products using the thin film made of the silver alloy according to the present invention, and there are various required characteristic specifications. In this respect, the present invention basically has a high transmittance and a low specific resistance, but there are many products that require a thin film having a maximum environmental resistance. In such a case, the maximum value of the additive element concentration is 20.0 atomic%. On the other hand, the concentration of the additive element in the case of improving the transmittance and specific resistance while emphasizing environmental resistance performance is 10.0 atomic% or less. Furthermore, when giving the highest priority to transmittance and specific resistance, the concentration of the additive element is 5.0 atomic% or less. In this way, the type and amount of additive element can be adjusted in consideration of the required specifications for each product to which the thin film is applied.

  The silver alloy as the reflective / transmissive film material according to the present invention described above can be manufactured by a melt casting method or a sintering method. There is no particular difficulty in the production by the melt casting method, and it can be produced by a general method in which each raw material is weighed, melted and mixed and cast. In addition, the production by the sintering method is not particularly difficult, and can be produced by a general method in which each raw material is weighed and sintered.

  The silver alloy according to the present invention is suitable as various electric / electronic devices, electrode materials for parts, and wiring materials. Moreover, the silver alloy which concerns on this invention also becomes favorable for light transmittance by adjusting a film thickness suitably. Therefore, it is also useful as a wiring material for transparent electrodes such as ITO. When applied to applications of these electrode materials and wiring materials, the film thickness is preferably 40 to 1500 mm. This is to ensure fine workability while considering reliability and durability. Further, in this film thickness range, when it is used as a wiring material for a transparent electrode in which transmittance is important, it is preferably 40 to 150 mm, but for electrodes and wiring in which transmittance is not important, 1000 to 1200 mm. It is preferable.

  Moreover, the silver alloy which concerns on this invention is suitable also as a constituent material of an electromagnetic wave shielding body. When applying this invention to an electromagnetic wave shielding body, it can be set as an electromagnetic wave shielding body by vapor-depositing or joining the silver alloy which concerns on this invention on the surface of a suitable support body. As the support, plate-like or sheet-like rubber or fiber can be applied. Further, the silver alloy according to the present invention can be thinned while maintaining the electromagnetic wave attenuation capability, and the transmittance can be improved, so that light shielding is achieved using glass as a support. It can be a material. In plasma displays, a coating for shielding electromagnetic waves may be applied to the light emitting surface, but the present invention having excellent light transmittance can also be applied to such applications.

  In addition, the form of the silver alloy in the electromagnetic wave shielding application may be any of a thin film, a plate material, a net, and a powder, but a thin film is preferable. The film thickness is preferably 400 to 150 mm, particularly 50 to 120 mm. This is because the transmittance is 80% or more while maintaining the electromagnetic wave shielding effect by ensuring conductivity.

  And when forming the thin film which consists of a silver alloy based on this invention with respect to the said use, sputtering method is applicable. Therefore, the sputtering target made of a silver alloy according to the present invention can produce electrodes, wirings, and electromagnetic wave shielding materials made of an alloy film having desirable characteristics.

  As described above, the environment resistance of the silver alloy according to the present invention is remarkably improved with respect to pure silver, and characteristics such as transmittance and specific resistance can be maintained even when used for a long time. The present invention is useful as an electromagnetic shielding material in addition to an electrode material and a wiring material. In addition, the silver alloy which concerns on this invention has the favorable adhesiveness in a thin film state, and is suitable for the said use also from this viewpoint.

  Hereinafter, preferred embodiments of the present invention will be described together with comparative examples. Here, silver alloys having various compositions of binary system to quinary system containing silver as a main component were manufactured, and a target was manufactured therefrom, and a thin film was formed by a sputtering method. The thin film was subjected to corrosion tests (acceleration tests) under various environments, and changes in properties after the corrosion tests were examined. In addition, the alloy which concerns on this invention is not restricted to the binary type | system | group-quinary type alloy which this embodiment makes object, It is good also as the thing of more than that. Depending on the product specifications, multi-component alloys of 6-component or higher can also be manufactured. And in the manufacture, there is no special problem and mass production is possible.

  In the production of a silver alloy, each metal is weighed to a predetermined concentration, melted in a high frequency melting furnace, and mixed to obtain an alloy. This was cast into a mold and solidified to form an ingot, which was forged, rolled, and heat treated, and then molded into a sputtering target. Moreover, target production by a powder sintering method is also possible.

The thin film was produced by placing a slide glass substrate (borosilicate glass) and a target in a sputtering apparatus, and evacuating the apparatus to 5.0 × 10 ⁻³ Pa, and then adding argon gas to 5.0 × 10 ^−1. Introduced up to Pa. As sputtering conditions, a film was formed for 8 seconds at a direct current of 0.4 kW, and the film thickness was 120 mm. The film thickness distribution was within ± 10%.

  The evaluation and examination of the properties of the manufactured thin film were conducted by conducting corrosion tests in which the thin film was exposed to various environments and evaluating the properties of the thin film before and after the test. In this embodiment, the various silver alloy thin films produced were tested for compositions that place importance on environmental performance and on compositions that place importance on transmittance and specific resistance.

A: Composition emphasizing environmental resistance performance As a test for a composition emphasizing environmental resistance performance, a salt water drop test and an adhesion test were performed. As for the practicality of a product including a silver alloy thin film, priority is given to ensuring durability in a human living environment. That is, a product having a silver thin film needs to be maintained without deterioration in performance even if there is a corrosive factor such as a person touching it directly or a food or food. The salt water drop test and the adhesion test conducted this time consider such a use environment.

The salt water drop test is an accelerated deterioration test on the assumption of adhesion of seasonings such as human sweat, soy sauce, and miso. A 10.0% NaCl aqueous solution (25 ° C.) is prepared, and 2 to 3 drops are dropped on a silver alloy thin film 120 直 後 immediately after film formation on a slide glass, and the change is observed to determine the durability performance. Evaluation was determined by the following 0-5 grade evaluation.
“5”: Best… No peeling “4”: Good… Partial peeling “3”: Normal… Half peeling “1”: Evil… Some remaining “0”: Worst ... Peeling off the entire surface

In the above-mentioned salt water drop test, a test for evaluating the adhesion of the thin film to the substrate was performed for those having an evaluation of 3 or more. The adhesion test was performed on three types of samples after being exposed to the following environment using thin film samples (film thickness of 120 mm) on a glass slide of each composition.
(1) Sample immediately after film formation (2) Sample after heating test heated at 250 ° C. for 1 hour in air on a hot plate after film formation (3) After film formation, atmosphere at temperature of 100 ° C. and humidity of 100% Sample after humidification test exposed for 24 hours

For each sample, eleven score lines were put in a thin film on a substrate using a metal mask dedicated jig with a cutter knife at a pitch of 1 mm at a pitch of 1 mm, and 100 mm squares (10 × 10 × 10 × 10) ) Formed. Then, a commercially available cellophane tape was applied so as to cover the cross-cut portion, and after sufficiently pressing and adhering, it was peeled off at right angles to the surface. After peeling off the tape, the number of remaining squares was counted and evaluated in five stages.
“5”: Best… No peeling “4”: Good… Partial peeling “3”: Normal… Half peeling “1”: Evil… Some remaining “0”: Worst ... Peeling off the entire surface

  Table 1 shows the evaluation results of the above salt water drop test and adhesion test. In the table, the test results for pure silver thin films are also shown for comparison.

  From these test results, it was confirmed that all of the silver alloy thin films produced in the present embodiment were superior in durability to salt water, better in adhesion than pure silver thin films, and had high environmental resistance. This environmental resistance improves as the concentration of the additive element increases.

B: Composition with emphasis on transmittance and specific resistance Next, a silver alloy having a composition giving priority to transmittance and specific resistance was evaluated. In this evaluation as well, a thin film sample (thickness 120 mm) formed on a slide glass was placed on a hot plate, heated in the atmosphere at 250 ° C. for 1 hour, and the characteristics after heating were evaluated (heating test). In addition, as a humidification test for examining the moisture resistance of the thin film, the thin film was exposed to an atmosphere at a temperature of 100 ° C. and a humidity of 100%, and the characteristics after humidification were evaluated. In the humidification test, the exposure time was 24 hours.

  The characteristics evaluated before and after the corrosion test are transmittance and specific resistance. The transmittance was measured with a spectrophotometer, and the transmittance of each thin film was evaluated relative to the transmittance of a substrate (borosilicate glass) on which a thin film was not formed as 100.

  First, Table 2 shows the evaluation results of the transmittance before and after the corrosion test. Each measurement value is a value at wavelengths of 400 nm, 550 nm, and 650 nm (corresponding to blue, yellow, and red wavelengths in the visible light region). The table also shows test results for a thin film manufactured from a target made of pure silver for comparison.

  In the evaluation of the transmittance, the thin film made of the silver alloy according to the present invention is compared with the rate of change immediately after the film formation and after the corrosion test. It was confirmed that the alloy was superior to pure silver. In general, the transmittance is high in the short wavelength region, but the difference between the transmittance at the short wavelength of 400 nm and the transmittance at the long wavelength of 650 nm is as large as 28% in the case of pure silver. In the case of a silver alloy, it is smaller than this value. Such a low difference in transmittance due to wavelength is a great advantage when obtaining white light as transmitted light.

  Next, Table 3 shows the evaluation results of the specific resistance of each silver alloy thin film before and after the corrosion test.

  In the evaluation of specific resistance, the specific resistance of pure silver before the corrosion test is the lowest, but increased by 29% after the heating test and increased by 24% after the humidification test. On the other hand, in the case of the silver alloy according to the present invention, the increase rate of the specific resistance is within 2% to 12%. These results are consistent with the fact that in the case of a silver alloy, the transmittance is hardly changed by an environmental test, and shows that the silver alloy is also electrically stable.

  Next, an adhesion test was performed on the thin film before and after the corrosion test. In this test, similarly to the above-described adhesion test, the thin film was cross-cut to form 100 squares of 1 mm squares. Then, cellophane tape was affixed and brought into close contact and peeled off at once. The evaluation method was evaluated in five steps as described above. Table 4 shows the results of this adhesion test.

  As a result, in the case of a pure silver thin film, it can be seen that the thin film peels off the entire surface after the corrosion test. On the other hand, in the case of the silver alloy according to the present invention, the adhesion is greatly improved, and in particular, it is possible to obtain a strong adhesion that does not peel off at all after the environmental test as well as immediately after the film formation. This is very effective for practical purposes of creating electrodes and wiring patterns.

  In the present embodiment, the etching property of each thin film was also evaluated. Here again, the thin film before and after the corrosion test was used as a sample. Photoresist was applied to the thin film on the substrate with a spin coater and dried, and a dedicated pattern (100 μm line and space) was exposed with a photomask, then held for a certain time, and then developed and dried. Then, the thin film was etched in the silver etching solution for about 30 seconds (depending on the type of the additive element, the etching rate was appropriately adjusted). Thereafter, the resist was peeled, washed, and dried to obtain a substrate on which patterning was completed. The substrate was observed using an optical microscope and an electron microscope of 100 to 400 times. For measurement of the amount of overetching and taper, a substrate with a resist was used, and the cross section was observed and measured after cutting. Evaluation was made in 5 stages by combining each item. The “0” and “1” judgments were unsuitable for practical use, and the “4” and “5” judgments were judged as being recommended for practical use. The evaluation results are shown in Table 5.

  From the evaluation results, in the case of a pure silver thin film, the linearity was good and the residue after etching was small, but the amount of over-etching in the cross-sectional pattern was large, and this was unsuitable for practical use where the taper resulting from this was tight. On the other hand, in the case of the silver alloy thin film according to the present invention, it is greatly improved by the effect of various additive elements and has reached a practical level.

  The present invention is useful as an electrode / wiring material for various display devices such as a thin film transistor type liquid crystal display (TFT-LCD), an organic EL display, and a plasma display.

  A TFT-LCD has a structure in which a liquid crystal material is sealed between two glass substrates. A filter is formed on the upper glass substrate, and a thin transistor (TFT) is formed on the lower glass substrate. A gate electrode, a source electrode, and a drain electrode are formed on the electrode on the TFT substrate side. The silver alloy according to the present invention is useful as a wiring material for these electrode materials and ITO transparent electrodes. For example, an insulating film or the like is formed on a transparent substrate of borosilicate glass, and Ag-1.7% Cu is formed with a thickness of 120 mm as an example of a silver alloy thin film according to the present invention, and etching is performed to obtain a specific resistance value. As a result of evaluation, the resistivity was as low as 3.421 μΩ · cm, the environment resistance was excellent, and its usefulness could be confirmed.

  An organic EL display is a display using an electroluminescence phenomenon, and the EL element itself emits light. Generally, a glass substrate / ITO transparent electrode / first dielectric layer / phosphor layer / second dielectric layer / back electrode phosphor is sandwiched between a pair of dielectrics. The silver alloy according to the present invention is effective as a wiring material for the electrode material and the ITO transparent conductive film. For example, an ITO transparent conductive film is formed on a transparent substrate of borosilicate glass, and then Ag-1.7% Cu-1.2% Ga-7.0 Mg is used as an example of a silver alloy thin film according to the present invention. When the specific resistance was evaluated as a wiring material, it was excellent in environmental resistance, and its usefulness was confirmed.

  In general, a plasma display has a structure in which a data electrode and a display electrode (scan / sustain electrode) are mounted in parallel in a glass substrate, and a neon-based gas is sealed in the gap. Then, the neon-dominated gas sealed in each pixel is turned into plasma by a voltage and discharged to emit ultraviolet rays from the gas, and this is irradiated to the red, blue and green phosphors applied to the inside of the glass substrate. Make it emit light. The silver alloy according to the present invention is effective as an electrode for various electrodes. For example, a protective film, a dielectric layer, and the like are formed on a transparent substrate of borosilicate glass, Ag-1.2% Y is formed as an electrode material with a film thickness of 120 mm as an example of the silver alloy thin film according to the present invention, and evaluation is performed. As a result, the specific resistance was as low as 5.302 μΩ · cm, and the environment resistance was excellent, and its usefulness was confirmed.

The silver alloy which concerns on this invention is suitable also as a constituent material of an electromagnetic wave shielding body. When applying to an electromagnetic wave shielding body, it can be set as an electromagnetic wave shielding body by vapor-depositing or joining the silver alloy concerning this invention on the surface of a suitable support body. As the support, plate-like acrylic, polycarbonate, sheet-like rubber, or fiber can be applied. Moreover, it can be set as the light-shielding shielding material by using glass as a support. Therefore, even if a coating for shielding electromagnetic waves is applied to the light emitting surface of the plasma display panel, high light transmittance is obtained and image quality is not deteriorated, so that high reliability can be obtained. For example, as a practical example of a transparent dielectric layer and a silver alloy thin film according to the present invention on a transparent substrate of borosilicate glass, an Ag-1.7% Cu-1.5% Ga-1.5% Dy thin film (film) When a thickness of 120 mm) was formed and evaluated as a multilayer structure, it was excellent in environmental resistance and its usefulness was confirmed. This transparent dielectric layer had good adhesion to the silver alloy thin film, and a high transmittance exceeding 50% was obtained over all wavelengths.

Claims (15)

It contains silver as a main component and contains at least one kind of nickel, molybdenum, copper, cobalt, titanium, scandium, yttrium, manganese, silicon, iron, zirconium, niobium, tantalum, tungsten, chromium, and carbon as a first additive element group. A silver alloy for shielding electrodes, wiring and electromagnetic waves. The silver alloy according to claim 1, wherein the first additive element group is copper, titanium, zirconium, manganese, or yttrium. Furthermore, as the second additive element group, gallium, thulium, dysprosium, platinum, palladium, magnesium, zinc, terbium, gadolinium, erbium, gold, aluminum, neodymium, holmium, tin, bismuth, praseodymium, germanium, indium, samarium, The silver alloy according to claim 1 or 2, wherein at least one of ytterbium, strontium, boron, rhodium, iridium, ruthenium, calcium, lead, antimony, hafnium, lanthanum, cerium, europium, lithium, and phosphorus is added. The silver alloy according to claim 3, wherein the second additive element group is at least one of gallium, palladium, dysprosium, indium, tin, zinc, magnesium, aluminum, gadolinium, erbium, praseodymium, samarium and lanthanum. The silver alloy according to any one of claims 1 to 4, wherein the total concentration of the additive elements is 0.01 to 20.0 atomic%. The silver alloy according to claim 5, wherein the total concentration of the additive elements is 0.01 to 10.0 atomic%. An electronic component provided with the electrode or wiring which consists of a silver alloy of any one of Claims 1-6. A display device provided with the electrode or wiring which consists of a silver alloy of any one of Claims 1-6. The electromagnetic wave shielding body which consists of a thin film which consists of a silver alloy of any one of Claims 1-6, and a support body which supports this thin film. A liquid crystal display provided with the thin film which consists of a silver alloy of any one of Claims 1-6. An EL display comprising a thin film made of the silver alloy according to any one of claims 1 to 6. A plasma display provided with the thin film which consists of a silver alloy of any one of Claims 1-6. An SED display provided with the thin film which consists of a silver alloy of any one of Claims 1-6. An antireflective film provided with the thin film which consists of a silver alloy of any one of Claims 1-6. The target which consists of a silver alloy of any one of Claims 1-6.