CN102965630A - Sputtering target and manufacturing method therof, film, film piece and laminated piece obtained by target - Google Patents
Sputtering target and manufacturing method therof, film, film piece and laminated piece obtained by target Download PDFInfo
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- CN102965630A CN102965630A CN2012102701172A CN201210270117A CN102965630A CN 102965630 A CN102965630 A CN 102965630A CN 2012102701172 A CN2012102701172 A CN 2012102701172A CN 201210270117 A CN201210270117 A CN 201210270117A CN 102965630 A CN102965630 A CN 102965630A
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Abstract
The invention provides a sputtering target which is suit for forming good transparency and and gas interception film and manufacturing method therof, a film, a a film piece and Laminated piece obtained by target. The sputtering target of the invention is characterized in that, the sputtering target is formed by a sintering body fomed by the zinc oxide and silicon monoxide as as a main component. The relative density of the sintered compact is 95% or more. The molar ratio of zinc oxide and silicon monoxide is 40:60-95:5.
Description
Technical field
The present invention relates to a kind of be suitable for forming sputtering target and the manufacture method thereof of the film of the various characteristics excellences such as the transparency, gas barrier property, film, the diaphragm that possesses this film and the lamination sheets of utilizing this target to obtain.More specifically, relate to a kind of these various characteristicses excellences that is used to form, especially be suitable as sputtering target and the manufacture method thereof of the film of the gas barrier property materials such as liquid-crystal display, OLED display, Electronic Paper or solar module, film, the diaphragm that possesses this film and the lamination sheets of utilizing this target to obtain.
Background technology
The equipment such as liquid-crystal display, OLED display or solar cell are unable to undergo moisture usually, make its characteristic promptly deteriorated because of moisture absorption, so must be equipped with the assembly that has highly moistureproof, namely prevents the gas barrier property that block or water vapour etc. see through or enter.
For example, in the example of solar cell, be provided with backboard at the back side of the opposite side of the sensitive surface of solar module.About this backboard, representational have on base material a backboard that is made of the gas barrier property material with highly moistureproof and their parts of protection etc.
Backboard as this formation solar module; for example disclose by high-strength heat-resistant, weathering resistance resin sandwich moisture resistance tinsel, the back-protective that the solar module that glassiness evaporation epithelium forms is set in one side in addition is with sheet material (for example referring to Patent Document 1).In this sheet material, as tinsels such as gas barrier property materials'use aluminium foil, zinc-plated iron foil, zinc-plated iron foils.
In addition, disclose stacked high moisture barrier films and high Weather-proof film and make its integrated solar cell cover plate materials that forms use the overleaf solar cell of side guard block (for example referring to Patent Document 2).Use following film in the high moisture barrier films in this solar cell cover plate materials, namely by the CVD(chemical vapor deposition), the PVD(evaporation reaction) method etc. forms moisture barrier films as gas barrier property material at base material films such as PET films, described moisture barrier films is made of filming of the inorganic oxides such as silicon-dioxide, aluminum oxide.In addition, disclose and have base material film and blocking layer and blocking layer for by the inorganic nitride film of hollow cathode type ion plating film forming or the transparent blocking film (for example referring to Patent Document 3) of inorganic nitrogenize sull.In addition, disclose the solar module (for example referring to Patent Document 4) that is provided with the blocking layer that sees through more than a kind that stops water vapour, oxygen, resolvent or additive on the surface of solar cell device.In this solar module as blocking layer filming of using that the composition that is made of the vapor-deposited film by resin molding, barrier property resin molding, inorganic oxide, the polycondensate that obtained by the hydrolysis of silicon compound forms or by wherein the composite membrane that consists of more than 2 kinds.
In addition, disclose the photovoltaic module (for example referring to Patent Document 5) that possesses by the blocking layer that is inorganic oxide layer and is consisted of by plastic film or plastics composite.In this inorganic oxide layer, use aluminum oxide or silicon oxide as its coated material.In addition, disclose by the used for solar batteries backside protective sheet (for example referring to Patent Document 6) that the inorganic oxide film layer is set at heat-resisting, weathered plastics film and folded other duplexers heat-resisting, the weathered plastics film that are made of same resin consist of on this film aspect upper strata.Use any thin film layer that forms by silicon oxide or aluminum oxide as the inorganic oxide film layer in this used for solar batteries backside protective sheet.
In addition, disclose and stack gradually metal more than 3 valencys that mix or semi-conductor at the base material film with transparency and form and have a duplexer (for example referring to Patent Document 7) that the metal oxide layer of the zinc oxide film of ultraviolet screener characteristic and gas barrier property excellence forms.Metal oxide layer as this duplexer uses silicon oxide, aluminum oxide or magnesium oxide.
In addition, disclose at least one side of polymeric membrane base material and interdict layer by the vapour deposition process film forming by the gas that metal or metal oxide consist of, and form the transparent gas barrier property composite film material (for example referring to Patent Document 8) with ultraviolet protection of the resin layer that contains ultrafine particle at this gas blocking layer.Use the single layer structure that consisted of by aluminium or multilayered structure or by at least a single layer structure that consists of or the multilayered structure of aluminum oxide, Si oxide and magnesium oxide as the gas of this transparency gas barrier property composite film material blocking layer.
Patent documentation 1: Japanese Utility Model is announced flat 2-44995 communique (the 41st～44 row on utility model mandate claim and 5 hurdles)
Patent documentation 2: Japanese Patent Publication 2000-174296 communique (claim 1, claim 7 and [0019] section)
Patent documentation 3: Japanese Patent Publication 2000-15737 communique (claim 1)
Patent documentation 4: Japanese Patent Publication 2001-217441 communique (claim 1 and 3)
Patent documentation 5: the public table of Japanese Patent 2002-520820 communique (claim 1 and [0019] section)
Patent documentation 6: Japanese Patent Publication 2002-134771 communique (claim 1 and 2)
Patent documentation 7: Japanese Patent Publication 7-256813 communique (claim 1,3 reaches [0015]～[0016] section)
Patent documentation 8: Japanese Patent Publication 2000-6305 communique (claim 1,7,8 reaches [0020] section)
Yet the back-protective shown in the above-mentioned patent documentation 1 is used as gas barrier property material with sheet material with tinsels such as aluminium foils, if therefore this sheet material is applied to the backboard of solar module, might reduce and current leakage by proof voltage.And, with regard to the sheet material of using tinsel, if the thickness of tinsel becomes below the 20 μ m, then being increased in the pin hole that produces between thermotolerance weathering resistance resin and the tinsel, the gas barrier property obviously descends.On the other hand, if the thickness of thickening tinsel, then can produce the problem that manufacturing cost rises, and need to distinguish as waste, because not transmission of light, therefore can't use at the sensitive surface of solar cell, and, exist in power supply terminal danger of short circuit with the flash that produces tinsel around the punching hole.
In addition, when when using in the above-mentioned patent documentation 2,5～7 film that the single inorganic oxides such as the silicon-dioxide that uses, aluminum oxide obtain, if obtain higher gas barrier property, the thickness of film must be guaranteed more than 100nm that then the gas barrier property is very abundant even if this size also is far from being.And, when being the transparent blocking film of the inorganic nitride film that uses in as above-mentioned patent documentation 3 or inorganic nitrogenize sull, have pollution or the difficult problem of Composition Control of oxygen.In addition, when consist of for the composition as the polycondensate that obtains by the vapor-deposited film by resin molding, barrier property resin molding, inorganic oxide, by the hydrolysis of silicon compound of the barrier film of above-mentioned patent documentation 4 film the time, then preferably be made as composite membrane if obtain sufficient barrier property, have the elongated problem of film-forming process.In addition, when being the related invention of above-mentioned patent documentation 8, if will obtain sufficient barrier property, then preferably be made as multilayered structure, there is the elongated problem of film-forming process in the same manner in the invention related with above-mentioned patent documentation 4.
Summary of the invention
The object of the present invention is to provide a kind of sputtering target and manufacture method thereof that is suitable for forming the film of the transparency and gas barrier property excellence.
Another object of the present invention is to provide a kind of transparency and the film of gas barrier property excellence, the diaphragm that possesses this film and lamination sheets.
The 1st viewpoint of the present invention, be a kind of ZnO-SiO class sputtering target, wherein, by zinc oxide (ZnO) and silicon monoxide (SiO) sintered compact as main component is consisted of, the relative density of sintered compact is more than 95%, and zinc oxide (ZnO) is 40:60～95:5 with the mol ratio of silicon monoxide (SiO).
The 2nd viewpoint of the present invention, be a kind of manufacture method of ZnO-SiO class sputtering target, wherein, be that the mol ratio that the ZnO powder of 0.1～5.0 μ m and SiO powder are mixed into zinc oxide (ZnO) and silicon monoxide (SiO) is 40:60～95:5 with the median size of primary particle, dose tackiness agent and extrusion forming, carrying out sintering more than 1000 ℃, be sintered compact more than 95% thereby make relative density after the demoulding.
The 3rd viewpoint of the present invention is the invention based on the 2nd viewpoint, wherein, being further used as to remove organic solvent and moisture etc. is the predrying of purpose, with 50～150 ℃ of processing of carrying out 1～10 hour, as being the skimming treatment of purpose so that tackiness agent disappears, with 400～600 ℃ of processing of carrying out 3～15 hours, and as putting forward highdensity sintering circuit, with 1000～1500 ℃ of processing of carrying out 3～15 hours.
The 4th viewpoint of the present invention, be a kind of manufacture method of ZnO-SiO class film, wherein, form ZnO-SiO class film by utilizing the sputtering method based on the ZnO-SiO class sputtering target of the 1st viewpoint at substrate surface.
The 5th viewpoint of the present invention, be a kind of ZnO-SiO class film, wherein, form by the manufacture method based on the 4th viewpoint.
The 6th viewpoint of the present invention, be a kind of diaphragm, wherein, possess ZnO-SiO class film based on the 5th viewpoint at the 1st base material film, the water vapor transmission rate (WVTR) when placing 1 hour under the condition of 20 ℃ of temperature, relative humidity 50%RH is 0.3g/m
2Below it.
The 7th viewpoint of the present invention, be a kind of lamination sheets, this lamination sheets forms stacked the 2nd base material film of side by tack coat at the film based on the diaphragm of the 6th viewpoint and forms.
In the sputtering target of the 1st viewpoint of the present invention, by zinc oxide (ZnO) and silicon monoxide (SiO) sintered compact as main component is consisted of, the relative density of sintered compact is more than 95%, zinc oxide (ZnO) is 40:60～95:5 with the mol ratio of silicon monoxide (SiO), can form thus the film that significantly improves the gas barrier property than gas barrier property material in the past.And the barrier property of the single film layer that obtains is excellent, and therefore available less stacked number obtains higher barrier property, therefore can boost productivity, and can also reduce cost.And by being made as the blocking film of individual layer or less stacked number, the thickness attenuation of total can reduce breaking when making the blocking sheet, warpage etc.When but the blocking film that this thickness is thinner is used in the solar cell of bending, improves resistance to bending and improve the weather resistance of solar cell.
In the manufacture method of the sputtering target of the 2nd viewpoint of the present invention, be that the mol ratio that the ZnO powder of 0.1～5.0 μ m and SiO powder are mixed into zinc oxide (ZnO) and silicon monoxide (SiO) is 40:60～95:5 with the median size of primary particle, dose tackiness agent and extrusion forming, after the demoulding to carry out sintering more than 1000 ℃, thereby the manufacturing relative density is the sintered compact more than 95%, therefore can access and can form the target that significantly improves the film of gas barrier property than gas barrier property material in the past.
In the manufacture method of the sputtering target of the 3rd viewpoint of the present invention, as to remove predrying as purpose such as organic solvent and moisture, with 50～150 ℃ of processing of carrying out 1～10 hour, as being the skimming treatment of purpose so that tackiness agent disappears, with 400～600 ℃ of processing of carrying out 3～15 hours, and as putting forward highdensity sintering circuit, with 1000～1500 ℃ of processing of carrying out 3～15 hours, warpage in the time of can relaxing thus mixing raw material powder and moulding punching press, become sintering circuit when easily carrying out formal sintering, its fruit density improves.
In the diaphragm of the 5th viewpoint of the present invention, the water vapor transmission rate (WVTR) when placing 1 hour under the condition of 20 ℃ of temperature, relative humidity 50%RH is very high, up to 0.3g/m
2My god, and have because the deteriorated less gas barrier property that the process of time causes.
In the lamination sheets of the 6th viewpoint of the present invention, adopt by tack coat and form the further structure of stacked the 2nd base material film of side at the film of the diaphragm of the 5th viewpoint.Thus, the 2nd base material film can protective film, so can keep higher gas barrier property and make its stabilization.
Description of drawings
Fig. 1 is the sectional view that schematically represents the stepped construction of the diaphragm of embodiment of the present invention and lamination sheets.
Fig. 2 is the figure that schematically represents the cross section structure of diaphragm in the past.
Fig. 3 is the figure of cross section structure that schematically represents the diaphragm of embodiment of the present invention.
Fig. 4 is the synoptic diagram of sputter equipment.
Nomenclature
The 10-diaphragm, 11-the 1st base material film, 12-ZnO-SiO class film, 13-tack coat, 14-the 2nd base material film, 20-lamination sheets.
Embodiment
Then, describe being used for implementing mode of the present invention with reference to the accompanying drawings.
ZnO-SiO class sputtering target of the present invention can be applicable to the formation of film.The film that utilizes this sputtering target to form is the film that plays a role as the gas barrier property material that anti-block or water vapour etc. see through or enter.
This sputtering target forms by mixed oxidization zinc powder and silicon monoxide powder.The oxide compound purity of the Zinc oxide powder that uses in the making of sputtering target is more than 98%, is preferably more than 99.5%, and the oxide compound purity of silicon monoxide powder is more than 98%, to be preferably more than 99.8%.At this, with the oxide compound purity in the Zinc oxide powder be limited to more than 98% be because, if less than 98%, then crystallinity worsens because of impurity, the result is interdicted characteristic and is descended.In addition, with the oxide compound purity of silicon monoxide powder be limited to more than 98% be because, if less than 98%, then crystallinity worsens because of impurity, the result is interdicted characteristic and is descended.In addition, the purity of the powder in this specification sheets is according to spectrum analysis method (inductively coupled plasma emmission spectrometric analysis device: the purity of the Japanese Jarrell Ash ICAP-88 processed of company) measuring.And this sputtering target preferably is made of the polycrystalline that contains Zinc oxide particles and silicon monoxide particle, and its relative density is more than 95%, to be preferably more than 98%.It is because if less than 95%, then easy abnormal discharge during film forming is prone to defective in the film that obtains that relative density is made as more than 95%.Relative density in this specification sheets is according to volumetric method, by the density of calculating divided by the quality of measuring with mass spectrograph with the volume of vernier scale size up and calculating.In addition, in this embodiment, the tissue of sputtering target is made as polycrystalline, but also can be monocrystalline.
In addition, the median size of contained Zinc oxide particles is 0.1～5.0 μ m in this sputtering target, and the median size of silicon monoxide particle is 0.1～5.0 μ m, zinc oxide in the sputtering target and the mol ratio of silicon monoxide are 40:60～95:5, be preferably 60:40～90:10, especially be preferably 70:30.By Zinc oxide particles and the silicon monoxide particle that contains miniaturization like this with predetermined proportion, can make the film that utilizes this sputtering target to form manifest higher gas barrier property.
Its technology reason is as follows: normal operation (1) does not comprise the silicon monoxide particle and only comprises the sputtering target of Zinc oxide particles, (2) do not comprise Zinc oxide particles and only comprise the sputtering target of silicon monoxide particle, (3) comprise Zinc oxide particles and silicon monoxide particle both sides but Zinc oxide particles contain proportional less sputtering target, or (4) comprise Zinc oxide particles and silicon monoxide particle both sides but the silicon monoxide particle contain proportional less sputtering target the time, as shown in Figure 2, be formed at sull 32 on the 1st base material film 11 and become the structure that the crystallization phases of column crystal is gathered abreast to the infiltration direction of gas.Because the gas molecules such as water vapour advance along the interface of the crystal boundary of gathering abreast, so in the film 32 of the structure that the crystallization of above-mentioned column crystal is gathered abreast, barrier property is lower.On the other hand; when utilizing when containing the sputtering target of the Zinc oxide particles of miniaturization or silicon monoxide particle in the mode that becomes predetermined proportion; the part of formed column crystal is burst apart and near the microtexture of the densification of non-crystalline state when as shown in Figure 3, being formed at sull 12 on the 1st base material film 11 and becoming the sputtering target that utilizes single component.Because in the microtexture near the densification of non-crystalline state, the gas molecules such as water vapour need to be in labyrinth-like minister's distance moving, so in the film 12 of the microtexture of above-mentioned densification near non-crystalline state, barrier property improves.Like this, infer that the crystalline texture film forming is structure rather than the column crystal that is fit to prevent that moisture etc. from seeing through or entering, thereby the gas barrier property improves.At this, with Zinc oxide particles contained in the sputtering target and silicon monoxide particle both sides' median size be limited in the above-mentioned scope be because, if each median size is less than lower value, then in the manufacturing process of sputtering target, it is obvious that the cohesion of powder becomes, hinder uniformly and mix, if each median size surpasses higher limit, then can not fully obtain being formed with the effect of the virtual sosoloid that helps to improve the gas barrier property.Wherein, especially the median size of preferential oxidation zinc particle is in the scope of 0.1～5.0 μ m, and the median size of silicon monoxide particle is in the scope of 0.1～5.0 μ m.In addition, in this specification sheets, so-called median size refers to according to laser diffraction, scattering method (Microtrack method), utilizes day machine dress company's system (FRA type), use sodium hexametaphosphate as dispersion agent, 1 minute was made as 30 seconds and made the particle diameter of the value equalization of measuring 3 times.
And; with the mol ratio of zinc oxide contained in the sputtering target and silicon monoxide be limited in the above-mentioned scope be because; if the mol ratio of zinc oxide less than 40 or the mol ratio of silicon monoxide less than 5; then proportionally become very few containing of Zinc oxide particles or silicon monoxide particle; near single component; thereby the structure that the crystallization phases of getting easily column crystal of becoming is gathered abreast to the infiltration direction of gas, so can't form the film with fine and close microtexture.
Utilize the ZnO-SiO class film of sputtering target formation of the present invention because the barrier property of individual layer is excellent, therefore can obtain higher barrier property with less stacked number, therefore can boost productivity, can also reduce the cost.And by being made as the blocking film of individual layer or less stacked number, the thickness attenuation of total can alleviate breaking when making the blocking sheet, warpage etc.When but the blocking film that this thickness is thinner is used in the solar cell of bending, improves resistance to bending and improve the weather resistance of solar cell.And, owing to have higher gas barrier property, therefore except the purposes of the gas barrier property materials such as moisture barrier films of the backboard that consists of solar cell, can also be suitable as liquid-crystal display, OLED display, illumination with gas barrier property materials such as OLED display or Electronic Paper.And, it is about 85～95% the transparency that this ZnO-SiO class film has rate of permeation, so also be suitable as be used to the gas barrier property of having relatively high expectations and as require the parts of printing opacity, such as the gas barrier property material of the sensitive surface side of solar cell or the image vision side of indicating meter etc. etc.
Then, describe take the situation of making by sintering process as the manufacture method of representative to sputtering target of the present invention.At first, mix purity as Zinc oxide powder and be high purity powdered form 98% or more, be high purity powdered form, tackiness agent and organic solvent more than 98% as the purity of silicon monoxide powder that preparing concentration is the slurry of 30～75 quality %.The slurry of preferred preparation 40～65 quality %.In addition, Zinc oxide powder and the adjustment of silicon monoxide powder and be mixed into manufacturing after sputtering target in zinc oxide and the mol ratio of silicon monoxide satisfy above-mentioned scope.With the concentration limits of slurry fix on 30～75 quality % be because, if surpass 75 quality %, then because above-mentioned slurry is non-water system, therefore there is the problem points that is difficult to carry out stable mixing granulation, if less than 30 quality %, then can't obtain having the sintered compact of the densification of uniform tissue.And, the median size of the median size of relevant employed Zinc oxide powder, silicon monoxide powder, consider according to the median size of Zinc oxide powder contained in the sputtering target after will making, the reason that the median size of silicon monoxide powder is adjusted in the above-mentioned scope, preferably Zinc oxide powder is made as in the scope of 0.1～5.0 μ m, the silicon monoxide powder is made as in the scope of 0.1～5.0 μ m.
Preferably utilize polyoxyethylene glycol or polyvinyl butyral acetal etc. as tackiness agent, and preferably utilize ethanol or propyl alcohol etc. as organic solvent.Tackiness agent preferably adds 0.2～5.0 quality %.
In addition, the wet mixing of high purity powdered form, tackiness agent and organic solvent, especially high purity powdered form with as the wet mixing of the organic solvent of dispersion agent by wet ball-milling or stir mill and carry out.In wet ball-milling, when utilizing ZrO
2During ball processed, utilize a plurality of ZrO of diameter 5～10mm
2Ball wet mixing processed 8～24 hours, preferred wet mixing 20～24 hours.With ZrO
2It is because if less than 5mm, then mixing can become insufficient, if surpass 10mm, then has the unfavorable condition that impurity increases that the diameter of ball processed is limited to 5～10mm.And mixing time is long to be because also seldom produce impurity even long-time continuous is mixed by the longest 24 hours.
In stirring mill, utilize the ZrO of diameter 1～3mm
2Ball wet mixing processed 0.5～1 hour.With ZrO
2It is because if less than 1mm, then mixing can become insufficient, if surpass 3mm, then has the unfavorable condition that impurity increases that the diameter of ball processed is limited to 1～3mm.And it is because if above 1 hour, then be not only the mixing of raw material, ball itself also can wear and tear, and therefore becomes the reason that produces impurity, and as long as just can mix fully in 1 hour that mixing time is short to the longest 1 hour.
Then, to obtain median size be 50～250 μ m to the above-mentioned slurry of spraying drying, the mixing granulation powder that is preferably 50～200 μ m.This prilling powder is put into predetermined mold, and with predetermined pressure forming.Above-mentioned spraying drying preferably utilizes spray-dryer to carry out, and predetermined mold is utilized uniaxial pressing machine or isostatic cool pressing (CIP; Cold Isostatic Press) forming machine.In the uniaxial pressing machine, with 750～2000kg/cm
2(73.55～196.1MPa), preferably with 1000～1500kg/cm
2(98.1～147.1MPa) pressure carries out the single shaft extrusion forming to prilling powder, in the CIP forming machine, with 1000～3000kg/cm
2(98.1～294.2MPa), preferably with 1500～2000kg/cm
2(147.1～196.1MPa) pressure carries out the CIP moulding to prilling powder.It is in order to improve the density of formed body that pressure is limited in the above-mentioned scope, and prevents the distortion behind the sintering, and eliminates post-treatment.
In addition, after the demoulding, with the preset temperature sintered moulded body.Sintering in atmosphere, rare gas element, vacuum or reducing gas atmosphere with more than 1000 ℃, preferably with 1200～1400 ℃ temperature, carry out 1～10 hour, preferably carried out 2～5 hours.Can access thus relative density and be the sputtering target more than 95%.Although above-mentioned sintering under atmospheric pressure carries out, such as hot pressing (HP) sintering or hip moulding (HIP; When Hot Isostatic Press) sintering carries out pressure sintering like that, preferably in rare gas element, vacuum or reducing gas atmosphere, carried out 1～5 hour with the temperature more than 1000 ℃.
In addition, preferably before above-mentioned sintering, formed body is carried out predrying, skimming treatment.Can be used as to remove organic solvent and moisture etc. is the predrying of purpose, with 50～150 ℃ of processing of carrying out 1～10 hour, as being the skimming treatment of purpose so that tackiness agent disappears, with 400～600 ℃ of processing of carrying out 3～15 hours, and as putting forward highdensity sintering circuit, with 1000 ℃～1500 ℃ processing of carrying out 3～15 hours.By carrying out these predrying and skimming treatments, the warpage in the time of can relaxing mixing raw material powder and moulding punching press, the sintering circuit when easily carrying out formal sintering of becoming, its fruit density improves.
Then, diaphragm of the present invention and lamination sheets and its manufacture method are together described.As shown in Figure 1, the diaphragm 10 of the present invention ZnO-SiO class film 12 of the present invention that has the 1st base material film 11 and preferably utilize above-mentioned sputtering target to form.And lamination sheets 20 of the present invention has the diaphragm 10 of the invention described above and passes through the 2nd base material film 14 of tack coat 13 bondings in the film formation side of this diaphragm 10.
The 1st base material film 11 and the 2nd base material film 14 preferably have the physical strength of withstanding long hot and humid degree environmental testing or weathering resistance etc.For example, can enumerate the resin moldings such as polyethylene terephthalate (PET), polycarbonate, polymethylmethacrylate, polyacrylic ester, PEN (PEN), polyarylester, polyethersulfone, cellulosetri-acetate (TAC), cyclic olefin (being total to) polymers.These resin moldings also can be combined with fire retardant, antioxidant, UV light absorber and static inhibitor etc. as required.The thickness of the 1st base material film 11 and the 2nd base material film 14 is preferably 5～300 μ m, more preferably 10～150 μ m.
On the 1st base material film 11, preferably utilize the sputtering target of the invention described above, form the ZnO-SiO class film 12 as gas barrier property material.Wherein, the thickness of ZnO-SiO class film 12 especially is preferably in 20～100nm scope.
The manufacture method of ZnO-SiO class film 12 of the present invention is utilized above-mentioned resulting sputtering target, by sputtering method, such as form ZnO-SiO class film at substrate surfaces such as above-mentioned the 1st base material films.Spendable substrate can be known substrate in the past, especially restriction, but be preferably the resin substrate such as PET.
Sputtering method is physical vapor deposition (PVD method; Physical Vapor Deposition) a kind of, sputter refers to that the particle (or ion) that accelerates impacts when solid surface, obtains a momental part that its particle holds and near the solid surface atom is spilt the phenomenon to the space.Utilizing this sputtering phenomenon to carry out film forms.The dc sputtering of applying direct current electric field and the high-frequency sputtering of applying high frequency electric field are arranged in the sputtering method.And also be categorized as 2 utmost point formulas, 4 utmost point formula sputtering methods etc. according to number of electrodes.
Fig. 4 represents general sputter equipment 40.Vacuum vessel 41 has gas inlet 42 and vaccum exhaust outlet 43, and these container 41 inside arrange the electrode 44,46 of slab construction abreast.Electrode 44,46 links to each other with direct supply or high frequency electric source 47 at external container, and is grounded.Negative electrode 44 becomes can arrange target material 48, and anode 46 becomes the structure that also doubles as substrate holder, in order to substrate 49 can be set.
When utilizing the sputter equipment formation ZnO-SiO class film of this structure, at first at negative electrode 44 sputtering target 48 of the present invention is set, at anode 46 substrate 49 is set.Then, will be vented to 5 * 10 in the vacuum vessel 41 with vacuum pumping hardware
-4After Pa is following, becomes mode about 0.3～1.0Pa with the atmosphere of vacuum vessel 41 inside and 42 import Ar gas 51 or oxygen from the gas inlet.And substrate 49 does not heat, or is heated to the temperature below 150 ℃.Then, if to electrode 44,46 in addition direct current or high-frequency electric field, then produce among Ar ion 52(Fig. 4 in the Ar gas 51 interior generation glow discharges that import to vacuum vessel 41 inside be labeled as+).The negative voltage of Ar ion 52 negative electrodes 44 that produce by this glow discharge attracts and is accelerated, with target material 48 collisions that are arranged at negative electrode 44, and each metallic element and the Sauerstoffatom sputter vaporization of the target material that is ejected because of this impact.The atom of each metallic element 53 of sputter vaporization (being labeled as M among Fig. 4) all with the Sauerstoffatom of sputter vaporization or from the gas inlet 42 combination with oxygen that import, arrive and remain on the substrate 49 of anode 46, piled up by these and formed ZnO-SiO class film.
In addition, although do not illustrate among Fig. 1, but in order to improve the adhesion strength with ZnO-SiO class film 12, can be as required at the 1st base material film 11 prime coat that be made of acrylic polyol, isocyanic ester, silane coupling agent be set, or before the evaporation operation, implements to utilize the surface treatment of plasma body etc.
On the other hand, under the state that exposes on formed ZnO-SiO class film 12 surfaces, if when installation sheet, scratch or wearing and tearing film surface, then the gas barrier property is brought considerable influence.Therefore, the gas barrier property tunicle (not shown) etc. on protection ZnO-SiO class film 12 surfaces preferably is set at ZnO-SiO class film 12.This gas barrier property tunicle can form by heat drying after ZnO-SiO class film 12 surface coated are for example mixed the solution of silicon compound, titanium compound, zirconia compound, tin compound or its hydrolyzate with alkoxyl group and the water-soluble polymer with hydroxy.This gas barrier property tunicle not only plays a role as the protective layer of ZnO-SiO class film 12, also has the effect that improves the gas barrier property.
For example after placing 1 hour under the condition of 20 ℃ of temperature, relative humidity 50%RH, the water vapor transmission rate (WVTR) of measuring under the condition of 40 ℃ of temperature, relative humidity 90%RH is shown as 0.3g/m to the diaphragm of the present invention 10 that forms like this
2Below it.
In addition, in lamination sheets 20 of the present invention, film at the diaphragm 10 of the invention described above forms side, be on the ZnO-SiO class film 12 or above-mentioned gas barrier property tunicle forms tack coat 13, this tack coat 13 is formed with the 1st base material film 11 of ZnO-SiO class film 12 as being used for fitting and the binding agent of the 2nd base material film 14 plays a role.Therefore, need cohesive strength through can deteriorated, not producing delamination etc. for a long time and not, and can flavescence etc. condition, such as enumerating polyurethanes, polyester, polyester-polyurethane class, polycarbonate-based, poly-epoxy-amine class, hot melt class binding agent etc.The laminating method of tack coat 13 can be stacked with known methods such as dry laminate methods.
By at this tack coat 13 bonding the 2nd base material films 14 and fit complete layer lamination 20.In addition, as shown in Figure 1, ZnO-SiO class film 12 and tack coat 13 may not be defined in separately 1 layer of 1 layer of lamination sheets that ground is stacked, also can be made as alternately laminated ZnO-SiO class film 12 and tack coat 13 or 2～10 layers multilayer of the miscellaneous part such as stacked ZnO-SiO class film 12, above-mentioned gas barrier property tunicle and tack coat 13 alternately or brokenly.Thus, can further improve gas barrier property or weathering resistance.
The backboard, liquid-crystal display, OLED display, illumination that this lamination sheets 20 can be suitable as solar module is with purposes such as OLED display or Electronic Paper.
[embodiment]
Then, embodiments of the invention and comparative example together are elaborated.
＜embodiment 1 〉
Prepare at first, respectively median size and be 0.8 μ m and purity and be 99.8% high purity ZnO powder, pulverize median size that SiO piece (high-purity chemical company system) obtains be 5.0 μ m and purity be 99.9% high purity SiO powder, as the PVB resin of tackiness agent, as ethanol and the acetone of organic solvent.
Then, mix ZnO powder, SiO powder, tackiness agent and organic solvent by the wet mixing based on ball mill with predetermined proportion, preparation concentration is the slurry of 40 quality %.And it is that 40 % by mole, SiO are 60 % by mole that the combined amount of ZnO powder and SiO powder is adjusted in the sputtering target after the formation contained ZnO.
Then, the slurry that utilizes the spray-dryer spraying drying to prepare obtains median size and is this prilling powder being put into predetermined mould, by the impact briquetting of uniaxial pressing machine after the mixing granulation powder of 200 μ m.After the demoulding, in air atmosphere, with the resulting formed body of 1150 ℃ temperature sintering 5 hours, obtain sputtering target.
＜embodiment 2 〉
It is that 60 % by mole, SiO are 40 % by mole that the combined amount of ZnO powder and SiO powder is adjusted in the sputtering target after the formation contained ZnO, obtains in the same manner sputtering target with embodiment 1 in addition.
＜embodiment 3 〉
It is that 85 % by mole, SiO are 15 % by mole that the combined amount of ZnO powder and SiO powder is adjusted in the sputtering target after the formation contained ZnO, obtains in the same manner sputtering target with embodiment 1 in addition.
＜embodiment 4 〉
It is that 95 % by mole, SiO are 5 % by mole that the combined amount of ZnO powder and SiO powder is adjusted in the sputtering target after the formation contained ZnO, obtains in the same manner sputtering target with embodiment 1 in addition.
＜embodiment 5～9 〉
It is that 70 % by mole, SiO are 30 % by mole that the combined amount of ZnO powder and SiO powder is adjusted in the sputtering target after the formation contained ZnO, obtains in the same manner sputtering target with embodiment 1 in addition.
＜embodiment 10 〉
Using median size is that 0.1 μ m and purity are that 99.8% high purity ZnO powder and median size are that 0.1 μ m and purity are 99.9% high purity SiO powder, it is that 70 % by mole, SiO are 30 % by mole that the combined amount of ZnO powder and SiO powder is adjusted in the sputtering target after the formation contained ZnO, obtains in the same manner sputtering target with embodiment 1 in addition.
＜embodiment 11 〉
Using median size is that 5.0 μ m and purity are that 99.8% high purity ZnO powder and median size are that 5.0 μ m and purity are 99.9% high purity SiO powder, it is that 70 % by mole, SiO are 30 % by mole that the combined amount of ZnO powder and SiO powder is adjusted in the sputtering target after the formation contained ZnO, obtains in the same manner sputtering target with embodiment 1 in addition.
＜comparative example 1 〉
Do not mix the SiO powder and adjust, obtain in the same manner sputtering target with embodiment 1 in addition.
＜comparative example 2 〉
It is that 98 % by mole, SiO are 2 % by mole that the combined amount of ZnO powder and SiO powder is adjusted in the sputtering target after the formation contained ZnO, obtains in the same manner sputtering target with embodiment 1 in addition.
＜comparative example 3 〉
It is that 35 % by mole, SiO are 65 % by mole that the combined amount of ZnO powder and SiO powder is adjusted in the sputtering target after the formation contained ZnO, obtains in the same manner sputtering target with embodiment 1 in addition.
＜comparative example 4 〉
Do not mix ZnO powder and adjust, obtain in the same manner sputtering target with embodiment 1 in addition.
＜comparison test 〉
The sputtering target that utilization obtains in embodiment 1～11 and comparative example 1～4 is to carry out evaporation by the RF sputtering method on the PET film of 75 μ m and film forming thickness is the film of 100nm at thickness, forms diaphragm.Sputtering condition is, film forming speed is 1nm/sec, and substrate temperature, oxygen partial pressure are as shown in the following Table 1.These diaphragms are measured water vapor transmission rate (WVTR) estimate the gas barrier property.And, these diaphragms are measured transmittance estimate the transparency.These be the results are shown in following table 1.
(1) gas barrier property: diaphragm is placed in the clean room that is set as 20 ℃ of temperature, relative humidity 50%RH after 1 hour, utilize the water vapor transmission rate (WVTR) determinator (model name is PERMATRAN-W type 3/33) of MOCON company system, under the condition of 40 ℃ of temperature, relative humidity 90%RH, measure water vapor transmission rate (WVTR).
(2) transmittance: the spectrophotometer (model name is U-4000) that utilizes Hitachi Co., Ltd to make, measure the transmittance of diaphragm in 380～780nm wavelength.
[table 1]
As can be known clear and definite from table 1, if comparing embodiment 1～11 and comparative example 1～4, then in embodiment 1～11, transmittance is higher, and the water vapor transmission rate (WVTR) of at room temperature placing after 1 hour is 0.28g/m
2Below it, show excellent barrier property.And the mol ratio that confirms ZnO and SiO more more shows excellent water vapor transmission rate (WVTR) near 70:30.
On the other hand, at the comparative example 1 that utilizes the sputtering target consisted of by single component to form, 4 diaphragm or to utilize the containing ratio of ZnO be that the containing ratio of 35 % by mole or SiO is in the comparative example 2 that forms of 2 % by mole sputtering target, 3 the diaphragm, become the higher but very large result of water vapor transmission rate (WVTR) of transmittance.
And, if pay close attention to filming condition, can find that then the substrate for film deposition temperature more uprises the tendency that the blocking characteristic more improves and the larger transmittance of oxygen partial pressure more uprises.
Claims (7)
1. a ZnO-SiO class sputtering target is characterized in that,
By zinc oxide ZnO and silicon monoxide SiO are consisted of as the sintered compact of main component, the relative density of described sintered compact is more than 95%, and the mol ratio of described zinc oxide ZnO and described silicon monoxide SiO is 40:60～95:5.
2. the manufacture method of a ZnO-SiO class sputtering target is characterized in that,
Be that the ZnO powder of 0.1～5.0 μ m and mol ratio that the SiO powder is mixed into described zinc oxide ZnO and described silicon monoxide SiO are 40:60～95:5 with the median size of primary particle, dose tackiness agent and extrusion forming, carrying out sintering more than 1000 ℃, be sintered compact more than 95% thereby make relative density after the demoulding.
3. the manufacture method of ZnO-SiO class sputtering target as claimed in claim 2, wherein,
As to remove predrying as purpose such as organic solvent and moisture, with 50～150 ℃ of processing of carrying out 1～10 hour, as being the skimming treatment of purpose so that tackiness agent disappears, with 400～600 ℃ of processing of carrying out 3～15 hours, and as putting forward highdensity sintering circuit, with 1000～1500 ℃ of processing of carrying out 3～15 hours.
4. the manufacture method of a ZnO-SiO class film is characterized in that,
Form ZnO-SiO class film by the sputtering method that utilizes ZnO-SiO class sputtering target claimed in claim 1 at substrate surface.
5. a ZnO-SiO class film is characterized in that,
Form by manufacture method claimed in claim 4.
6. a diaphragm is characterized in that,
Possess ZnO-SiO class film claimed in claim 5 at the 1st base material film,
Water vapor transmission rate (WVTR) when placing 1 hour under the condition of 20 ℃ of temperature, relative humidity 50%RH is 0.3g/m
2Below it.
7. lamination sheets, this lamination sheets forms stacked the 2nd base material film of side by tack coat at the film of diaphragm claimed in claim 6 and forms.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
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| JP2011186043A JP5747738B2 (en) | 2011-08-29 | 2011-08-29 | Sputtering target, manufacturing method thereof, thin film using the target, thin film sheet including the thin film, and laminated sheet |
| JP2011-186043 | 2011-08-29 |
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| CN102965630A true CN102965630A (en) | 2013-03-13 |
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| CN105008306A (en) * | 2013-03-19 | 2015-10-28 | 住友金属矿山株式会社 | Zinc oxide-based sintered object, process for producing same, sputtering target, and transparent conductive film |
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| JP7124776B2 (en) | 2019-03-25 | 2022-08-24 | 株式会社豊田自動織機 | engine |
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| Publication number | Publication date |
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| JP5747738B2 (en) | 2015-07-15 |
| JP2013047364A (en) | 2013-03-07 |
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