CN103524119A - Sintered compact and amorphous film - Google Patents

Sintered compact and amorphous film Download PDF

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Publication number
CN103524119A
CN103524119A CN201310276943.2A CN201310276943A CN103524119A CN 103524119 A CN103524119 A CN 103524119A CN 201310276943 A CN201310276943 A CN 201310276943A CN 103524119 A CN103524119 A CN 103524119A
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sintered compact
film
powder
scaled
mole
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奈良淳史
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JX Nippon Mining and Metals Corp
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JX Nippon Mining and Metals Corp
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Priority claimed from JP2013119611A external-priority patent/JP5550768B1/en
Application filed by JX Nippon Mining and Metals Corp filed Critical JX Nippon Mining and Metals Corp
Priority to CN201610702480.5A priority Critical patent/CN106380188A/en
Priority to CN202010396262.XA priority patent/CN111620687A/en
Publication of CN103524119A publication Critical patent/CN103524119A/en
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    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
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    • C23—COATING 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
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
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Abstract

The invention provides a sintered compact and an amorphous film. The sintered compact is characterized by comprising zinc (Zn), trivalent metal elements, germanium (Ge) and/or silicon (Si), and oxygen (O), wherein, if the total content of the trivalent metal elements is A mol% in terms of oxides and the total content of Ge and or Si is B mol% in terms of GeO2 and/or SiO2, 15<=A+B<=70. According to the invention, the sintered compact has low bulk resistance and is capable of performing DC sputtering. The sintered compact can be used to form the amorphous film with a low refractive index.

Description

Sintered compact and amorphous film
Technical field
The amorphous film with low-refraction that the present invention relates to access the sintered compact of the nesa coating that possesses good transmission of visible light and electroconductibility and use this sintered compact to make.
Background technology
In the past, as nesa coating, the film obtaining to adding tin in Indium sesquioxide was that ITO (Indium-Tin-oxide, indium tin oxide) film transparent and electrically conductive is good, was used to the purposes of the wide scopes such as various indicating meters.But because the indium as main component is expensive, so this ITO has the problem that has inferior position aspect manufacturing cost.
In view of the foregoing, as the substitute of ITO, proposed for example to use the film of zinc oxide (ZnO).The zinc oxide of usining has advantages of cheap as the film of main component.There is the phenomenon that causes electroconductibility enhancing due to the oxygen defect of the ZnO as main component in known this film, if the membrane properties such as electroconductibility and transmitance and ITO are approximate, the application of this material has the possibility of increase.
The in the situation that of utilizing visible ray in indicating meter etc., this material require is transparent, particularly preferably in whole visible-range, has high-transmission rate.In addition, when specific refractory power is high, optical loss increases or makes the view angle dependency variation of indicating meter, therefore also expects that specific refractory power is low, and in order to improve crackle and the etching performance of film, is also contemplated to be amorphous film.
The stress of amorphous film is little, therefore compares and is difficult for cracking with crystalline film, from now on, thinks and in the display applications towards flexibility, requires as amorphous film.In addition, for ITO before, in order to improve resistance value and transmissivity, need to make its crystallization, and, while being made into amorphous, in short wavelength range, having and absorb and can not form transparent film, be therefore not suitable for this purposes.
As the material that uses zinc oxide, known IZO (Indium sesquioxide-zinc oxide), GZO (gallium oxide/zinc oxide), AZO (aluminum oxide-zinc oxide) etc. (patent documentation 1～3).But, although IZO can form low-resistance amorphous film, exist also to have in short wavelength range to absorb and the high problem of specific refractory power.In addition, GZO, AZO are due to ZnO easily along c-axis orientation and easily form crystalline film, and the stress of this crystalline film increases, and therefore exist film to peel off and the problem such as film rupture.
In addition, in patent documentation 4, disclose take ZnO and alkali fluoride earth metal compound as main component, realized the light transmission electro-conductive material of wide cut specific refractory power.But this material is crystalline film, can not get the effect of the such amorphous film of the present invention described later.In addition, disclose specific refractory power little and less and be the nesa coating of amorphous than resistance, but they are different from compositional system of the present invention in patent documentation 5, existence can not regulate the problem of specific refractory power and resistance value simultaneously.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2007-008780 communique
Patent documentation 2: TOHKEMY 2009-184876 communique
Patent documentation 3: TOHKEMY 2007-238375 communique
Patent documentation 4: TOHKEMY 2005-219982 communique
Patent documentation 5: TOHKEMY 2007-035342 communique
Summary of the invention
Invent problem to be solved
Problem of the present invention is to provide the sintered compact of the amorphous film of nesa coating, the particularly low-refraction that can access the transmission of visible light that can remain good and electroconductibility.The transmissivity of this film is high and mechanical characteristics is good, therefore, useful as the nesa coating of indicating meter or the protective membrane of optical device.Thus, the object of the invention is to improve optical device characteristic, reduce equipment cost, significantly improve the characteristic of film forming.
For the means of dealing with problems
In order to address the above problem, the inventor conducts in-depth research, result is found as follows: by the nesa coatings such as ITO are in the past replaced to material system as follows, at random regulating resistance rate and specific refractory power, can guarantee to utilize sputter or ion plating to carry out stable film forming with peer-level in the past or in higher than optical characteristics in the past, and then by forming amorphous film, can improve the characteristic of the optical device that possesses this film and boost productivity.
The present invention is based on this discovery and following invention is provided.
1) a kind of sintered compact, it is characterized in that, zinc (Zn), trivalent metallic element, germanium (Ge) and/or silicon (Si), oxygen (O), consist of, the total content that the total content of establishing trivalent metallic element is scaled A % by mole, Ge and/or Si with oxide compound is with GeO 2and/or SiO 2while being scaled B % by mole, 15≤A+B≤70.
2) as above-mentioned 1) as described in sintered compact, it is characterized in that, the total content of above-mentioned Ge and/or Si is 5≤B≤30.
3) as above-mentioned 1) or 2) as described in sintered compact, it is characterized in that, the total content of above-mentioned trivalent metallic element is counted more than 0.1 with the atomicity ratio of trivalent metallic element/(Zn+ trivalent metallic element).
4) as above-mentioned 1)～3) in sintered compact as described in any one, it is characterized in that, above-mentioned trivalent metallic element is for selecting more than one elements in the group of free aluminium (Al), gallium (Ga), boron (B), yttrium (Y) and indium (In) composition.
5), it is characterized in that, by the oxide compound formation of zinc (Zn), gallium (Ga), germanium (Ge), establish the content of Ga with Ga 2o 3be scaled A % by mole, the content of Ge with GeO 2when being scaled B % by mole and surplus and being ZnO, meet the condition of 15≤A+B≤50 and A>=3B/2.
6) as above-mentioned 1)～5) in sintered compact as described in any one, it is characterized in that, also contain take oxide weight be scaled 0.1～5 % by weight, form the metal that fusing point is the oxide compound below 1000 ℃.
7) as above-mentioned 6) as described in sintered compact, it is characterized in that, above-mentioned fusing point is that 1000 ℃ of following oxide compounds are for selecting free B 2o 3, P 2o 5, K 2o, V 2o 5, Sb 2o 3, TeO 2, Ti 2o 3, PbO, Bi 2o 3, MoO 3more than one oxide compounds in the group forming.
8) as above-mentioned 1)～7) in sintered compact as described in any one, it is characterized in that, relative density is more than 90%.
9) as above-mentioned 1)～8) in sintered compact as described in any one, it is characterized in that, body resistance value is below 10 Ω cm.
10), it is characterized in that, use above-mentioned 1)～9) in sintered compact described in any one.
11) material, is characterized in that, uses above-mentioned 5) described sintered compact.
12) a kind of film, it is characterized in that, zinc (Zn), trivalent metallic element, germanium (Ge) and/or silicon (Si), oxygen (O), consist of, the total content that the total content of establishing trivalent metallic element is scaled A % by mole, Ge and/or Si with oxide compound is with GeO 2and/or SiO 2while being scaled B % by mole, 15≤A+B≤70, and be amorphous film.
13), it is characterized in that, by the oxide compound formation of zinc (Zn), gallium (Ga), germanium (Ge), establish the content of Ga with Ga 2o 3be scaled A % by mole, the content of Ge with GeO 2when being scaled B % by mole and surplus and being ZnO, meet the condition of 15≤A+B≤50 and A>=3B/2, and be amorphous film.
14) as above-mentioned 12) or 13) as described in film, it is characterized in that, also contain with oxide weight be scaled 0.1～5 % by weight, form and to select free B 2o 3, P 2o 5, K 2o, V 2o 5, Sb 2o 3, TeO 2, Ti 2o 3, PbO, Bi 2o 3, MoO 3the metal of more than one oxide compounds in the group forming.
15) as above-mentioned 12)～14) in film as described in any one, it is characterized in that, the optical extinction coefficient under wavelength 450nm is below 0.01.
16) as above-mentioned 12)～15) in film as described in any one, it is characterized in that, the specific refractory power under wavelength 550nm is below 2.00.
17) as above-mentioned 12)～16) in film as described in any one, it is characterized in that, volume specific resistance is 1 * 10 -3～1 * 10 9Ω cm.
18) a kind of manufacture method of sintered compact, it is above-mentioned 1)～9) in the manufacture method of sintered compact described in any one, it is characterized in that, raw material powder is mixed, by resulting mixed powder under rare gas element or vacuum atmosphere, carry out pressure sintering at 1000 ℃～1500 ℃, or by after resulting mixed powder press molding, by this molding under rare gas element or vacuum atmosphere, at 1000 ℃～1500 ℃, carry out normal pressure-sintered.
Invention effect
The present invention has following excellent results: by the nesa coatings such as ITO are in the past replaced to material as implied above, at random regulating resistance rate and specific refractory power, can guarantee to utilize sputter or ion plating to carry out stable film forming with peer-level in the past or in higher than optical characteristics in the past, and then by forming amorphous film, can improve the characteristic of the optical device that possesses this film and boost productivity.
Embodiment
The sintered compact that zinc (Zn), trivalent metallic element, germanium (Ge) and/or silicon (Si), oxygen (O) is Constitution Elements is take in the present invention, it is characterized in that, the total content that the total content of establishing trivalent metallic element is scaled A % by mole, Ge and/or Si with oxide compound is with GeO 2and/or SiO 2while being scaled B % by mole, meet 15≤A+B≤70.
When prepared by raw material, so that form, to reach surplus be that the ratio of ZnO and each oxide compound is counted the mode of 100 % by mole with its total amount and is prepared, and therefore, the content of Zn can be converted and be obtained by such surplus ZnO.By adopting this composition, can form the amorphous film of low-refraction, thereby obtain above-mentioned effect of the present invention.
In addition, in the present invention, with oxide compound, convert the content of each metal in regulation sintered compact, but part or all form with composite oxides of each metal in sintered compact exists.In addition, in the composition analysis of normally used sintered compact, with the form of metal, the form of non-oxidized substance is measured content separately.
Germanium oxide (the GeO containing in sintered compact of the present invention 2) and silicon-dioxide (SiO 2) be vitrifying composition (network former), be for making the effective constituent of film decrystallized (vitrifying).On the other hand, this vitrifying composition sometimes reacts with zinc oxide (ZnO) and forms ZnGe 2o 4such material and become crystalline film, the membrane stress of this crystalline film increases and causes that film is peeled off or film rupture.Therefore, can expect to form mullite composition (3M by introducing trivalent metallic element (being denoted as M) 2o 3-2GeO 2, 3M 2o 3-2SiO 2) and suppress the generation of this material.
In addition, germanium oxide (GeO 2), silicon oxide (SiO 2) such network former and the oxide compound of trivalent metallic element be the low material of refractive index ratio zinc oxide (ZnO), therefore, by adding these oxide compounds, can reduce the specific refractory power of film.On the other hand, while regulating composition to reduce the mode of specific refractory power (while reducing ZnO), resistance value has the tendency of rising.
Therefore,, when the total addition level that the total addition level of establishing the oxide compound of trivalent metallic element is (A), germanium oxide and/or silicon-dioxide is (B), make 15≤A+B≤70.During A+B < 15, be difficult to form amorphous, therefore not preferred, while making A+B > 70, the content of ZnO reduces and the film of formation insulativity, therefore not preferred.
In the present invention, with oxide compound, convert the content of regulation trivalent metallic element, when this said oxide compound represents to establish trivalent metallic element and is M by M 2o 3the oxide compound forming.
For example, in the situation that trivalent metallic element is aluminium (Al), represent by Al 2o 3the oxide compound forming.As trivalent metallic element, be particularly preferably more than one elements in the group of selecting free aluminium (Al), gallium (Ga), boron (B), yttrium (Y) and indium (In) composition.
Trivalent metallic element contributes to electroconductibility as the doping agent of zinc oxide (ZnO), wherein the specific refractory power of Al, Ga, B, Y, In is low, by can easily regulating specific refractory power and resistance value with above-mentioned network former combination, it is therefore effective especially material.The oxide compound consisting of these metallic elements can add separately or compound interpolation separately, can realize the object of the present application.
In the present invention, form the Ge of network former and/or the total content of Si with GeO 2and/or SiO 2more than conversion is preferably set to 5 % by mole and below 30 % by mole, more than being more preferably set as 5 % by mole and below 20 % by mole.This is because while being less than 5 % by mole, the effect that reduces specific refractory power reduces and can not get sufficient decrystallized effect.On the other hand, while surpassing 30 % by mole (20 % by mole), the body resistance value of sintered compact easily rises, and is difficult to carry out stable DC sputter.
In addition, in the present invention, the total content of above-mentioned trivalent metallic element is more preferably set as more than 0.15 than being preferably set to more than 0.1 in the atomicity of trivalent metallic element/(Zn+ trivalent metallic element).In this case, to low-refraction and decrystallized effective.In order to bring into play this effect, in atomicity ratio, be set as more than 0.1, being more preferably set as more than 0.15.
In addition, the invention provides a kind of sintered compact, by the oxide compound formation of zinc (Zn), gallium (Ga), germanium (Ge), establish the content of Ga with Ga 2o 3be scaled A % by mole, the content of Ge with GeO 2when being scaled B % by mole and surplus and being ZnO, meet the condition of 15≤A+B≤50 and A>=3B/2.By this one-tenth, be grouped into the material that the sintered compact that forms uses as ion plating particularly useful.
Ion plating method is to utilize in a vacuum electron beam etc. to make evaporation of metal, utilize high frequency plasma etc. to make its ionization (positively charged ion), by apply negative potential to substrate, make this positively charged ion accelerate the technology that postadhesion forms film.Compare with sputter, ion plating has advantages of that the service efficiency of material is high, estimates that productivity improves.
Sintered compact of the present invention, can be as ion plating materials'use when adopting a part as above to form.This is because by Ga, Ge element and ratio of components are selected, make the reductions such as vapour pressure, thereby can carry out ion plating.
As ion plating materials'use in the situation that, except can using the board-like material that sintered compact precision work is obtained, can also use this sintered compact is further made to powder or material granular and that obtain after pulverizing.After pulverizing, make powder or material granular and that obtain more easily evaporates than tabular material, therefore from the viewpoint of production efficiency more preferably.
Sintered compact of the present invention can also contain take oxide weight be scaled 0.1～5 % by weight, form the metal that fusing point is the oxide compound below 1000 ℃ (low melting point oxide).Due to easily reduction of zinc oxide (ZnO), evaporation, the sintering temperature that therefore cannot excessively raise, is difficult to make the density of sintered compact to improve sometimes.But, by adding this low melting point oxide, have and can in the situation that excessively not raising sintering temperature, realize the effect of densification.
While being less than 0.1 % by weight, can not bring into play this effect, in addition, while surpassing 5 % by weight, may make characteristic change thereby not preferred, therefore be set as above-mentioned numerical range.
As above-mentioned low melting point oxide, can enumerate for example B 2o 3, P 2o 5, K 2o, V 2o 5, Sb 2o 3, TeO 2, Ti 2o 3, PbO, Bi 2o 3, MoO 3.These oxide compounds can add separately or compound interpolation separately, can realize the object of the present application.Sintered compact of the present invention can be used as sputtering target and uses, and in this case, it is more than 90% preferably making relative density.The increase of density can improve the homogeneity of sputtered film, and has the effect that produces powder in the time of can suppressing sputter.
It is below 10 Ω cm that sintered compact of the present invention can be realized its body resistance.By reducing body resistance value, can utilize direct current (DC) sputter to carry out high speed film forming.According to the selection of material, high frequency (RF) sputter or magnetron sputtering need to be carried out, also film forming speed can be improved in this case.By improving film forming speed, can improve throughput, thereby can go far towards cutting down cost.
In the present invention, importantly by sintered compact is carried out to the film that spatter film forming obtains or the film forming by above-mentioned ion plating is amorphous film through the target that obtains of processing.Whether resulting film is that amorphous film can be by for example being used X-ray diffraction method to observe to judge to there is near the diffracted intensity 2 θ=34.4 ° at peak of (002) face of ZnO.The membrane stress of the film that the ZnO of take is main component is large, therefore, when for crystalline film, can crack or break, and then produce film and the problem such as peel off, but by making this film, be amorphous film, there is the excellent results of the problems such as breaking of can avoiding being caused by membrane stress or crackle.
By the machined target obtaining of sintered compact of the present invention being carried out to the optical extinction coefficient that the film that sputter forms or the film forming by above-mentioned ion plating can realize under wavelength 450nm, be below 0.01.The film that indicating meter is used need to be transparent in whole visible-range, but the oxide compound mesenterys such as IZO film generally have absorption in short wavelength range, is therefore difficult to send distinct blueness.According to the present invention, the optical extinction coefficient under wavelength 450nm is 0.01 when following, in short wavelength range, does not almost absorb, and therefore can say that as transparent material be the material being extremely applicable to.
In addition, by the machined target obtaining of sintered compact of the present invention being carried out to the specific refractory power that the film that sputter forms or the film forming by above-mentioned ion plating can realize under wavelength 550nm, be (preferably below 1.90) below 2.00.And the volume specific resistance of above-mentioned film can realize 1 * 10 -3～1 * 10 9Ω cm.
By germanium oxide (GeO 2), silicon-dioxide (SiO 2), the oxide compound that forms of trivalent metallic element (preferred Al wherein 2o 3, Ga 2o 3, B 2o 3, Y 3o 2, In 2o 3) be specific refractory power lower than the material of zinc oxide (ZnO), therefore, by adding these oxide compounds, can access refractive index ratio low film in the past.
In addition, by the machined target obtaining of sintered compact of the present invention being carried out to the film that sputter forms or the film forming by above-mentioned ion plating, can or form the optical thin film of the protective layer of optical information recording medium for the nesa coating in the various indicating meters such as organic EL televisor.In the situation that the protective layer of optical information recording medium, particularly owing to not using ZnS, therefore, there is the pollution that do not exist S to cause, can not make thus the deteriorated unusual effect of recording layer.
Embodiment
Below, based on embodiment and comparative example, describe.In addition, the present embodiment is an example at most, and the present invention is without any restriction by this example.That is, the present invention is only defined by the claims, and comprises embodiment contained in the present invention various distortion in addition.
(embodiment 1)
Prepare ZnO powder, Al 2o 3powder, SiO 2powder and as the B of low melting point oxide 2o 3powder.Then, these powder are deployed in table 1 to the proportioning of recording, after being mixed, by powdered material in a vacuum, 1100 ℃ of temperature, pressure 250kgf/cm 2condition under carry out hot pressed sintering.
Then, by mechanical workout, this sintered compact is finish-machined to sputtering target shape.Body resistance and the relative density of measuring resulting target, result is as shown in table 1, and relative density reaches 99.3%, and body resistance is 2.1m Ω cm, can carry out stable DC sputter.
In addition, use the target after above-mentioned precision work to carry out sputter.At the O that is set as DC sputter, sputtering power 500W, contains 2 volume % 2the sputtering condition of Ar air pressure 0.5Pa under, film forming is thickness.Measure into amorphism, specific refractory power (wavelength 550nm), volume specific resistance, the optical extinction coefficient (wavelength 450nm) of membrane sample.As shown in table 1, the film forming by sputter is amorphous film, and its specific refractory power is 1.80 (wavelength 550nm), and volume specific resistance is 2 * 10 8Ω cm, optical extinction coefficient is less than 0.01 (wavelength 450nm), has obtained the amorphous film of low-refraction.
Figure BDA00003457943900111
(embodiment 2)
Prepare ZnO powder, Ga 2o 3powder, SiO 2powder and as the B of low melting point oxide 2o 3powder.Then, these powder are deployed in table 1 to the proportioning of recording, after being mixed, by powdered material in argon gas atmosphere, 1100 ℃ of temperature, pressure 250kgf/cm 2condition under carry out hot pressed sintering.Then, by mechanical workout, this sintered compact is finish-machined to sputtering target shape.Body resistance and the relative density of measuring resulting target, result is as shown in table 1, and relative density reaches 98.5%, and body resistance is 1.6m Ω cm, can carry out stable DC sputter.
In addition, use the target after above-mentioned precision work, under condition similarly to Example 1, carry out sputter, measure into amorphism, specific refractory power (wavelength 550nm), volume specific resistance, the optical extinction coefficient (wavelength 450nm) of membrane sample.As shown in table 1, the film forming by sputter is amorphous film, and its specific refractory power is 1.89 (wavelength 550nm), and volume specific resistance is 2 * 10 -1Ω cm, optical extinction coefficient is less than 0.01 (wavelength 450nm), has obtained the amorphous film of low-refraction.
(embodiment 3)
Prepare ZnO powder, Al 2o 3powder, GeO 2powder and as the B of low melting point oxide 2o 3powder.Then, these powder are deployed in table 1 to the proportioning of recording, after being mixed, by powdered material in argon gas atmosphere, 1100 ℃ of temperature, pressure 250kgf/cm 2condition under carry out hot pressed sintering.Then, by mechanical workout, this sintered compact is finish-machined to sputtering target shape.Body resistance and the relative density of measuring resulting target, result is as shown in table 1, and relative density reaches 98.6%, and body resistance is 3.6m Ω cm, can carry out stable DC sputter.
In addition, use the target after above-mentioned precision work, under condition similarly to Example 1, carry out sputter, measure into amorphism, specific refractory power (wavelength 550nm), volume specific resistance, the optical extinction coefficient (wavelength 450nm) of membrane sample.As shown in table 1, the film forming by sputter is amorphous film, and its specific refractory power is 1.79 (wavelength 550nm), and volume specific resistance is 5 * 10 6Ω cm, optical extinction coefficient is less than 0.01 (wavelength 450nm), has obtained the amorphous film of low-refraction.
(embodiment 4)
Prepare ZnO powder, Y 2o 3powder, GeO 2powder and as the B of low melting point oxide 2o 3powder.Then, these powder are deployed in table 1 to the proportioning of recording, after being mixed, by powdered material in argon gas atmosphere, 1000 ℃ of temperature, pressure 250kgf/cm 2condition under carry out hot pressed sintering.Then, by mechanical workout, this sintered compact is finish-machined to sputtering target shape.Body resistance and the relative density of measuring resulting target, result is as shown in table 1, and relative density reaches 98.3%, and body resistance is 7.6m Ω cm, can carry out stable DC sputter.
In addition, use the target after above-mentioned precision work, under condition similarly to Example 1, carry out sputter, measure into amorphism, specific refractory power (wavelength 550nm), volume specific resistance, the optical extinction coefficient (wavelength 450nm) of membrane sample.As shown in table 1, the film forming by sputter is amorphous film, and its specific refractory power is 1.88 (wavelength 550nm), and volume specific resistance is 7 * 10 4Ω cm, optical extinction coefficient is less than 0.01 (wavelength 450nm), has obtained the amorphous film of low-refraction.
(embodiment 5)
Prepare ZnO powder, In 2o 3powder, GeO 2powder.Then, these powder are deployed in table 1 to the proportioning of recording, after being mixed, by powdered material in argon gas atmosphere, 1050 ℃ of temperature, pressure 250kgf/cm 2condition under carry out hot pressed sintering.Then, by mechanical workout, this sintered compact is finish-machined to sputtering target shape.
Body resistance and the relative density of measuring resulting target, result is as shown in table 1, and relative density reaches 98.7%, and body resistance is 1.3m Ω cm, can carry out stable DC sputter.
In addition, use the target after above-mentioned precision work, under condition similarly to Example 1, carry out sputter, measure into amorphism, specific refractory power (wavelength 550nm), volume specific resistance, the optical extinction coefficient (wavelength 450nm) of membrane sample.
As shown in table 1, the film forming by sputter is amorphous film, and its specific refractory power is 1.88 (wavelength 550nm), and volume specific resistance is 2 * 10 -3Ω cm, optical extinction coefficient is less than 0.01 (wavelength 450nm), has obtained the amorphous film of low-refraction.
(embodiment 6)
Prepare ZnO powder, B 2o 3powder, SiO 2powder and as the Bi of low melting point oxide 2o 3powder.Then, these powder are deployed in table 1 to the proportioning of recording, after being mixed, by powdered material at 500kgf/cm 2pressure under press molding, by this molding in a vacuum, carry out under the condition of 1300 ℃ of temperature normal pressure-sintered.Then, by mechanical workout, this sintered compact is finish-machined to sputtering target shape.Body resistance and the relative density of measuring resulting target, result is as shown in table 1, and relative density reaches 96.5%, and body resistance is 2.3 Ω cm, can carry out stable DC sputter.
In addition, use the target after above-mentioned precision work, under condition similarly to Example 1, carry out sputter, measure into amorphism, specific refractory power (wavelength 550nm), volume specific resistance, the optical extinction coefficient (wavelength 450nm) of membrane sample.As shown in table 1, the film forming by sputter is amorphous film, and its specific refractory power is 1.73 (wavelength 550nm), and volume specific resistance is 3 * 10 Ω cm, and optical extinction coefficient is less than 0.01 (wavelength 450nm), has obtained the amorphous film of low-refraction.
(embodiment 7)
Prepare ZnO powder, Ga 2o 3powder, GeO 2powder and as the B of low melting point oxide 2o 3powder.Then, these powder are deployed in table 1 to the proportioning of recording, after being mixed, by powdered material at 500kgf/cm 2pressure under press molding, by this molding in argon gas atmosphere, carry out under the condition of 1100 ℃ of temperature normal pressure-sintered.Then, by mechanical workout, this sintered compact is finish-machined to sputtering target shape.Body resistance and the relative density of measuring resulting target, result is as shown in table 1, and relative density reaches 99.8%, and body resistance is 0.9m Ω cm, can carry out stable DC sputter.
In addition, use the target after above-mentioned precision work, under condition similarly to Example 1, carry out sputter, measure into amorphism, specific refractory power (wavelength 550nm), volume specific resistance, the optical extinction coefficient (wavelength 450nm) of membrane sample.As shown in table 1, the film forming by sputter is amorphous film, and its specific refractory power is 1.89 (wavelength 550nm), and volume specific resistance is 2 * 10 -3Ω cm, optical extinction coefficient is less than 0.01 (wavelength 450nm), has obtained the amorphous film of low-refraction.
(comparative example 1)
Prepare ZnO powder, Ga<sub TranNum="303">2</sub>o<sub TranNum="304">3</sub>powder, GeO<sub TranNum="305">2</sub>powder and as the B of low melting point oxide<sub TranNum="306">2</sub>o<sub TranNum="307">3</sub>powder.Then, these powder are deployed into as described in Table 1 to the proportioning of A+B<15, after being mixed, by powdered material in argon gas atmosphere, 1050 ℃ of temperature, pressure 250kgf/cm<sup TranNum="308">2</sup>condition under carry out hot pressed sintering.Then, by mechanical workout, this sintered compact is finish-machined to sputtering target shape.
Body resistance and the relative density of measuring resulting target, result is as shown in table 1, and relative density is 95.8%, and body resistance is 1.2m Ω cm, can carry out DC sputter.
But, use the target after above-mentioned precision work, under condition similarly to Example 1, carry out sputter, measure into amorphism, specific refractory power (wavelength 550nm), volume specific resistance, the optical extinction coefficient (wavelength 450nm) of membrane sample, result is as shown in table 1, and the film forming by sputter does not form amorphous film.In addition, specific refractory power is 1.98 (wavelength 550nm), and volume specific resistance is 3 * 10 -3Ω cm, optical extinction coefficient is less than 0.01 (wavelength 450nm).
(comparative example 2)
Prepare ZnO powder, Al 2o 3powder, SiO 2powder and as the B of low melting point oxide 2o 3powder.Then, these powder are deployed into A+B as described in Table 1 like that>70 proportioning, after being mixed, by powdered material in argon gas atmosphere, 1100 ℃ of temperature, pressure 250kgf/cm 2condition under carry out hot pressed sintering.Then, by mechanical workout, this sintered compact is finish-machined to sputtering target shape.
Body resistance and the relative density of measuring resulting target, result is as shown in table 1, and relative density is 96.4%, and body resistance is 40m Ω cm, can carry out DC sputter.But, use the target after above-mentioned precision work, under condition similarly to Example 1, carry out sputter, measure into amorphism, specific refractory power (wavelength 550nm), volume specific resistance, the optical extinction coefficient (wavelength 450nm) of membrane sample, result is as shown in table 1, and the volume specific resistance of the film forming by sputter surpasses 1 * 10 9Ω cm and demonstrate insulativity.In addition, its for specific refractory power be that 1.66 (wavelength 550nm), optical extinction coefficient are less than the amorphous film of 0.01 (wavelength 450nm).
(embodiment 8)
Preparation is equivalent to ZnO powder below the 5 μ m of 3N, be equivalent to the Ga below the median size 5 μ m of 3N 2o 3powder, be equivalent to the GeO below the median size 5 μ m of 3N 2powder.Then, by ZnO powder, Ga 2o 3powder and GeO 2powder is deployed into ZnO:Ga 2o 3: GeO 2the proportioning of=80.0:13.0:7.0 % by mole, after being mixed, by powdered material in argon gas atmosphere, 850 ℃, 250kgf/cm 2pressure under carry out hot pressed sintering and make ion plating sintered compact.
Use this sintered compact to implement ion plating, result is as shown in table 2, can carry out stable ion plating, and the specific refractory power of the film of made reaches 1.87 (wavelength 550nm).In addition, optical extinction coefficient is less than 0.01 (wavelength 450nm), and the volume specific resistance of film is 1 * 10 -2Ω cm and demonstrate electroconductibility.In addition, confirm as amorphous film.
(embodiment 9)
Preparation is equivalent to ZnO powder below the 5 μ m of 3N, be equivalent to the Ga below the median size 5 μ m of 3N 2o 3powder, be equivalent to the GeO below the median size 5 μ m of 3N 2powder.Then, by ZnO powder, Ga 2o 3powder and GeO 2powder is deployed into ZnO:Ga 2o 3: GeO 2the proportioning of=52.7:29.4:17.9 % by mole, after being mixed, by powdered material in argon gas atmosphere, 850 ℃, 250kgf/cm 2pressure under carry out hot pressed sintering and make ion plating sintered compact.
Use this sintered compact to implement ion plating, result can be carried out stable ion plating, and the specific refractory power of the film of made reaches 1.71 (wavelength 550nm).
In addition, optical extinction coefficient is less than 0.01 (wavelength 450nm), and the volume specific resistance of film is 3 * 10 6Ω cm and demonstrate electroconductibility.In addition, confirm as amorphous film.
(embodiment 10)
Preparation is equivalent to ZnO powder below the 5 μ m of 3N, be equivalent to the Ga below the median size 5 μ m of 3N 2o 3powder, be equivalent to the GeO below the median size 5 μ m of 3N 2powder.Then, by ZnO powder, Ga 2o 3powder and GeO 2powder is deployed into ZnO:Ga 2o 3: GeO 2the proportioning of=66.3:20.6:13.1 % by mole, after being mixed, by powdered material in argon gas atmosphere, 850 ℃, 250kgf/cm 2pressure under carry out hot pressed sintering and make ion plating sintered compact.
Use this sintered compact to implement ion plating, result can be carried out stable ion plating, and the film of having confirmed made is amorphous film.In addition, the specific refractory power of this film reaches 1.75 (wavelength 550nm).In addition, optical extinction coefficient is less than 0.01 (wavelength 450nm), and the volume specific resistance of film is 6 * 10 4Ω cm and demonstrate electroconductibility.
(embodiment 11)
Preparation is equivalent to ZnO powder below the 5 μ m of 3N, be equivalent to the Ga below the median size 5 μ m of 3N 2o 3powder, be equivalent to the GeO below the median size 5 μ m of 3N 2powder.Then, by ZnO powder, Ga 2o 3powder and GeO 2powder is deployed into ZnO:Ga 2o 3: GeO 2the proportioning of=74.5:16.9:8.6 % by mole, after being mixed, by powdered material in argon gas atmosphere, 850 ℃, 250kgf/cm 2pressure under carry out hot pressed sintering and make ion plating sintered compact.
Use this sintered compact to implement ion plating, result can be carried out stable ion plating, and the film of having confirmed made is amorphous film.In addition, specific refractory power reaches 1.82 (wavelength 550nm).In addition, optical extinction coefficient is less than 0.01 (wavelength 450nm), and the volume specific resistance of film is 8 * 10 -2Ω cm and demonstrate electroconductibility.
(embodiment 12)
Preparation is equivalent to ZnO powder below the 5 μ m of 3N, be equivalent to the Ga below the median size 5 μ m of 3N 2o 3powder, be equivalent to the GeO below the median size 5 μ m of 3N 2powder.Then, by ZnO powder, Ga 2o 3powder and GeO 2powder is deployed into ZnO:Ga 2o 3: GeO 2the proportioning of=67.7:23.4:8.9 % by mole, after being mixed, by powdered material in argon gas atmosphere, 850 ℃, 250kgf/cm 2pressure under carry out hot pressed sintering and make ion plating sintered compact.
Use this sintered compact to implement ion plating, result can be carried out stable ion plating, and the film of having confirmed made is amorphous film.In addition, the specific refractory power of this film reaches 1.77 (wavelength 550nm).In addition, optical extinction coefficient is less than 0.01 (wavelength 450nm), and the volume specific resistance of film is 3 * 10 -1Ω cm and demonstrate electroconductibility.
(embodiment 13)
Preparation is equivalent to ZnO powder below the 5 μ m of 3N, be equivalent to the Ga below the median size 5 μ m of 3N 2o 3powder, be equivalent to the GeO below the median size 5 μ m of 3N 2powder.Then, by ZnO powder, Ga 2o 3powder and GeO 2powder is deployed into ZnO:Ga 2o 3: GeO 2the proportioning of=50.2:41.9:7.9 % by mole, after being mixed, by powdered material in argon gas atmosphere, 850 ℃, 250kgf/cm 2pressure under carry out hot pressed sintering and make ion plating sintered compact.
Use this sintered compact to implement ion plating, result can be carried out stable ion plating, and the film of having confirmed made is amorphous film.In addition, the specific refractory power of this film reaches 1.66 (wavelength 550nm).In addition, optical extinction coefficient is less than 0.01 (wavelength 450nm), and the volume specific resistance of film is 3 * 10 3Ω cm and demonstrate electroconductibility.
(comparative example 3)
Preparation is equivalent to ZnO powder below the 5 μ m of 3N, be equivalent to the Ga below the median size 5 μ m of 3N 2o 3powder, be equivalent to the GeO below the median size 5 μ m of 3N 2powder.Then, by ZnO powder, Ga 2o 3powder and GeO 2powder is deployed into ZnO:Ga 2o 3: GeO 2the proportioning of=85.0:2.2:12.8 % by mole, after being mixed, by powdered material in argon gas atmosphere, 850 ℃, 250kgf/cm 2pressure under carry out hot pressed sintering and make ion plating sintered compact.
Use this sintered compact to implement ion plating, result can be carried out stable ion plating, and the specific refractory power of the film of made is 1.94 (wavelength 550nm).In addition, optical extinction coefficient is less than 0.01 (wavelength 450nm), and the volume specific resistance of film is 4 * 10 -3Ω cm and demonstrate electroconductibility.But, confirm that crystallization has occurred film.
(comparative example 4)
Preparation is equivalent to ZnO powder below the 5 μ m of 3N, be equivalent to the Ga below the median size 5 μ m of 3N 2o 3powder, be equivalent to the GeO below the median size 5 μ m of 3N 2powder.Then, by ZnO powder, Ga 2o 3powder and GeO 2powder is deployed into ZnO:Ga 2o 3: GeO 2the proportioning of=44.0:34.0:22.0 % by mole, after being mixed, by powdered material in argon gas atmosphere, 850 ℃, 250kgf/cm 2pressure under carry out hot pressed sintering and make ion plating sintered compact.
Use this sintered compact to implement ion plating, result, although the film of made is amorphous film, the specific refractory power of film is 1.68 (wavelength 550nm), optical extinction coefficient is less than 0.01 (wavelength 450nm), the volume specific resistance of film>1 * 10 9Ω cm, electroconductibility significantly reduces.
(comparative example 5)
Preparation is equivalent to ZnO powder below the 5 μ m of 3N, be equivalent to the Ga below the median size 5 μ m of 3N 2o 3powder, be equivalent to the GeO below the median size 5 μ m of 3N 2powder.Then, by ZnO powder, Ga 2o 3powder and GeO 2powder is deployed into ZnO:Ga 2o 3: GeO 2the proportioning of=90.0:7.0:3.0 % by mole, after being mixed, by powdered material in argon gas atmosphere, 850 ℃, 250kgf/cm 2pressure under carry out hot pressed sintering and make ion plating sintered compact.
Use this sintered compact to implement ion plating, result, the specific refractory power of film is 1.93 (wavelength 550nm), and optical extinction coefficient is less than 0.01 (wavelength 450nm), and the volume specific resistance of film is 1 * 10 -3Ω cm and demonstrate electroconductibility, but there is crystallization in the film of making.
Utilizability in industry
Sintered compact of the present invention can be made sputtering target or ion plating material; the film that uses these sputtering targets or ion plating material to form has following effect: by forming nesa coating in various indicating meters or the protective membrane of optical device, have extremely good characteristic aspect transmissivity, specific refractory power, electroconductibility.In addition, of the present invention one be characterised in that greatly the excellent results by forming amorphous film with crackle and the etching performance that can significantly improve film.
In addition, use sintered compact of the present invention and the body resistance value of the sputtering target that obtains is low and relative density up to more than 90%, therefore, can carry out stable DC sputter.And, thereby have the feature that can easily bring into play this DC sputter be sputter controlled, improve the unusual effect that film forming speed improves sputtering yield.In the situation that implementing as required RF sputter, also can be observed the raising of film forming speed.In addition, the powder producing when sputter in the time of can reducing film forming, dross, reduce quality fluctuation and improve mass productivity.
In addition, use sintered compact of the present invention and the ion plating material that obtains can form the amorphous film of low-refraction, therefore, have and can suppress the crackle that membrane stress causes or break and the effect of the generation that film is peeled off.This amorphous film uses film particularly useful as the optical thin film of the protective layer of formation optical information recording medium, organic EL used as television film, transparency electrode.

Claims (18)

1. a sintered compact, it is characterized in that, zinc (Zn), trivalent metallic element, germanium (Ge) and/or silicon (Si), oxygen (O), consist of, the total content that the total content of establishing trivalent metallic element is scaled A % by mole, Ge and/or Si with oxide compound is with GeO 2and/or SiO 2while being scaled B % by mole, 15≤A+B≤70.
2. sintered compact as claimed in claim 1, is characterized in that, the total content of described Ge and/or Si is 5≤B≤30.
3. sintered compact as claimed in claim 1 or 2, is characterized in that, the total content of described trivalent metallic element is counted more than 0.1 with the atomicity ratio of trivalent metallic element/(Zn+ trivalent metallic element).
4. the sintered compact as described in any one in claim 1～3, is characterized in that, described trivalent metallic element is for selecting more than one elements in the group of free aluminium (Al), gallium (Ga), boron (B), yttrium (Y) and indium (In) composition.
5. a sintered compact, is characterized in that, by the oxide compound formation of zinc (Zn), gallium (Ga), germanium (Ge), establishes the content of Ga with Ga 2o 3be scaled A % by mole, the content of Ge with GeO 2when being scaled B % by mole and surplus and being ZnO, meet the condition of 15≤A+B≤50 and A>=3B/2.
6. the sintered compact as described in any one in claim 1～5, is characterized in that, also contain take oxide weight be scaled 0.1～5 % by weight, form the metal that fusing point is the oxide compound below 1000 ℃.
7. sintered compact as claimed in claim 6, is characterized in that, described fusing point is that 1000 ℃ of following oxide compounds are for selecting free B 2o 3, P 2o 5, K 2o, V 2o 5, Sb 2o 3, TeO 2, Ti 2o 3, PbO, Bi 2o 3, MoO 3more than one oxide compounds in the group forming.
8. the sintered compact as described in any one in claim 1～7, is characterized in that, relative density is more than 90%.
9. the sintered compact as described in any one in claim 1～8, is characterized in that, body resistance value is below 10 Ω cm.
10. a sputtering target, is characterized in that, right to use requires the sintered compact described in any one in 1～9.
11. 1 kinds of ion plating materials, is characterized in that, right to use requires the sintered compact described in 5.
12. 1 kinds of films, it is characterized in that, zinc (Zn), trivalent metallic element, germanium (Ge) and/or silicon (Si), oxygen (O), consist of, the total content that the total content of establishing trivalent metallic element is scaled A % by mole, Ge and/or Si with oxide compound is with GeO 2and/or SiO 2while being scaled B % by mole, 15≤A+B≤70, and be amorphous film.
13. 1 kinds of films, is characterized in that, by the oxide compound formation of zinc (Zn), gallium (Ga), germanium (Ge), establish the content of Ga with Ga 2o 3be scaled A % by mole, the content of Ge with GeO 2when being scaled B % by mole and surplus and being ZnO, meet the condition of 15≤A+B≤50 and A>=3B/2, and be amorphous film.
14. films as described in claim 12 or 13, is characterized in that, also contain with oxide weight be scaled 0.1～5 % by weight, form and select free B 2o 3, P 2o 5, K 2o, V 2o 5, Sb 2o 3, TeO 2, Ti 2o 3, PbO, Bi 2o 3, MoO 3the metal of more than one oxide compounds in the group forming.
15. films as described in any one in claim 12～14, is characterized in that, the optical extinction coefficient under wavelength 450nm is below 0.01.
16. films as described in any one in claim 12～15, is characterized in that, the specific refractory power under wavelength 550nm is below 2.00.
17. films as described in any one in claim 12～16, is characterized in that, volume specific resistance is 1 * 10 -3～1 * 10 9Ω cm.
The manufacture method of 18. 1 kinds of sintered compacies, it is the manufacture method of the sintered compact described in any one in claim 1～9, it is characterized in that, raw material powder is mixed, by resulting mixed powder under rare gas element or vacuum atmosphere, carry out pressure sintering at 1000 ℃～1500 ℃, or by after resulting mixed powder press molding, by this molding under rare gas element or vacuum atmosphere, at 1000 ℃～1500 ℃, carry out normal pressure-sintered.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105807986A (en) * 2015-01-21 2016-07-27 Tdk株式会社 Transparent electric conductor and touch screen
CN107207356A (en) * 2015-02-27 2017-09-26 捷客斯金属株式会社 Oxidate sintered body, oxide sputtering target and sull
CN105986230B (en) * 2014-09-10 2018-11-02 吉坤日矿日石金属株式会社 The manufacturing method of oxidate sintered body, sputtering target and film and oxidate sintered body

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015118724A1 (en) * 2014-02-07 2015-08-13 リンテック株式会社 Transparent conductive laminate, method for producing transparent conductive laminate, and electronic device formed using transparent conductive laminate

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009228034A (en) * 2008-03-19 2009-10-08 Iwate Univ ZnO-BASED TARGET, MANUFACTURING METHOD THEREFOR, METHOD FOR MANUFACTURING ELECTROCONDUCTIVE THIN FILM, AND ELECTROCONDUCTIVE THIN FILM
CN102245532A (en) * 2008-12-15 2011-11-16 出光兴产株式会社 Composite oxide sintered body and sputtering target comprising same
TW201202452A (en) * 2010-04-07 2012-01-16 Kobe Steel Ltd Oxide for semiconductor layer of thin film transistor, sputtering target, and thin film transistor
CN102482156A (en) * 2009-09-30 2012-05-30 出光兴产株式会社 In-Ga-Zn-O oxide sintered body

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3947575B2 (en) * 1994-06-10 2007-07-25 Ｈｏｙａ株式会社 Conductive oxide and electrode using the same
JPH0845352A (en) * 1994-08-02 1996-02-16 Sekisui Chem Co Ltd Transparent conductor
US8461583B2 (en) * 2007-12-25 2013-06-11 Idemitsu Kosan Co., Ltd. Oxide semiconductor field effect transistor and method for manufacturing the same
WO2009145152A1 (en) * 2008-05-27 2009-12-03 株式会社カネカ Transparent conductive film and method for producing the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009228034A (en) * 2008-03-19 2009-10-08 Iwate Univ ZnO-BASED TARGET, MANUFACTURING METHOD THEREFOR, METHOD FOR MANUFACTURING ELECTROCONDUCTIVE THIN FILM, AND ELECTROCONDUCTIVE THIN FILM
CN102245532A (en) * 2008-12-15 2011-11-16 出光兴产株式会社 Composite oxide sintered body and sputtering target comprising same
CN102482156A (en) * 2009-09-30 2012-05-30 出光兴产株式会社 In-Ga-Zn-O oxide sintered body
TW201202452A (en) * 2010-04-07 2012-01-16 Kobe Steel Ltd Oxide for semiconductor layer of thin film transistor, sputtering target, and thin film transistor

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105986230B (en) * 2014-09-10 2018-11-02 吉坤日矿日石金属株式会社 The manufacturing method of oxidate sintered body, sputtering target and film and oxidate sintered body
CN105807986A (en) * 2015-01-21 2016-07-27 Tdk株式会社 Transparent electric conductor and touch screen
CN105807986B (en) * 2015-01-21 2019-03-08 Tdk株式会社 Transparent conductive body and touch screen
CN107207356A (en) * 2015-02-27 2017-09-26 捷客斯金属株式会社 Oxidate sintered body, oxide sputtering target and sull

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TWI631579B (en) 2018-08-01
KR101841791B1 (en) 2018-03-23
CN106380188A (en) 2017-02-08
TW201405580A (en) 2014-02-01
KR20140004586A (en) 2014-01-13

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Application publication date: 20140122