CN103380229A - Transparent oxide film and process for producing same - Google Patents

Transparent oxide film and process for producing same Download PDF

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CN103380229A
CN103380229A CN2012800075651A CN201280007565A CN103380229A CN 103380229 A CN103380229 A CN 103380229A CN 2012800075651 A CN2012800075651 A CN 2012800075651A CN 201280007565 A CN201280007565 A CN 201280007565A CN 103380229 A CN103380229 A CN 103380229A
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oxide film
transparent oxide
film
sputter
sio
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CN103380229B (en
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山口刚
张守斌
近藤佑一
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Mitsubishi Materials Corp
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Abstract

Provided are: a zinc oxide-based transparent oxide film which has a low refractive index and good gas barrier properties; and a process for producing the same. This transparent oxide film is amorphous, and has a composition which contains, relative to the total amount of all the metal components, 0.9 to 20.0at% of Al and 25.5 to 68.0at% of Si with the balance consisting of Zn and unavoidable impurities. In this process, DC sputtering is conducted in an inert gas atmosphere that contains oxygen and/or under such conditions that the substrate is in a heated state, using a sputtering target consisting of a sintered oxide which has a composition that contains, relative to the total amount of all the metal components, 0.3 to 4.0wt% of Al and 6.0 to 14.5wt% of Si with the balance consisting of Zn and unavoidable impurities and in which both a composite oxide, Zn2SiO4, and ZnO are present in the structure.

Description

Transparent oxide film and manufacture method thereof
Technical field
The present invention relates to a kind of transparent oxide film and manufacture method thereof of gas barrier property excellence of Zinc oxide, this transparent oxide film be used as being included in for the mineral membrane of the gas barrier layer of the Electronic Paper such as organic illuminated display element, liquid crystal display device, electro-luminescent display unit, electrophoresis type display element, toning agent display element or thin film solar cell etc. or thin film encapsulation layers, and the transparent electrode layer of the thin-film solar cells of based compound semiconductor on gas barrier layer.
Background technology
In the past, known have by sputtering method make the technology that the transparent oxide film is used as following gas barrier layer, namely be used for the gas barrier layer of the Electronic Paper such as liquid crystal display device or electro-luminescent display unit, electrophoresis type display element, toning agent display element or thin film solar cell etc. and thin-film solar cells (for example CIGS(Cu-In-Ga-Se) the class solar cell of based compound semiconductor) transparent electrode layer on gas barrier layer.
For example, in patent documentation 1, propose to have following method: oxidate sintered body is used as sputtering target, and by having utilized the sputtering method of dc-pulse method, surface at the resin film base material forms the transparent oxide film, wherein, oxidate sintered body is: contain stannic oxide and be selected from Si, Ge, at least a interpolation element among the Al, and this interpolation element that contains 15 atom %～63 atom % ratios with respect to the summation of adding element and Sn content, with regard to the formation of crystallization phases, comprise the metallographic phase that adds element, this adds the oxidation phase of element, in this additive and the Sn combined oxidation phase more than one, the combined oxidation phase of the oxidation phase of this interpolation element and this interpolation element and Sn is take median size as the size dispersion below the 50 μ m.
The transparent oxide film that obtains by the method is the transparent oxide film that contains stannic oxide and be selected from least a interpolation element among Si, Ge, the Al, this interpolation element that contains 15 atom %～63 atom % ratios with respect to the summation of adding element and Sn, and be amorphous film, and wavelength when being 633nm specific refractory power be below 1.90.
And proposition forms the method for following light transmissive films in patent documentation 2: as being used for the light transmissive films of phase change disc with protective membrane, although purposes is different, all utilize the Nb that is selected from that contains 0.01～20 % by weight 2O 5, V 2O 5, B 2O 3, SiO 2, P 2O 5In more than one network former and the Al of 0.01～20 % by weight 2O 3Or Ga 2O 3, remainder is selected from In 2O 3, SnO 2, more than one oxide compounds among the ZnO sputtering target, and contain the Nb that is selected from of 0.01～20 % by weight by sputtering film-forming 2O 5, V 2O 5, B 2O 3, SiO 2, P 2O 5In more than one network former and the Al of 0.01～20 % by weight 2O 3Or Ga 2O 3, remainder is selected from In 2O 3, SnO 2, more than one oxide compounds among the ZnO.
Patent documentation 1: Japanese Patent Publication: 2007-290916 communique
Patent documentation 2: Japanese Patent Publication: 2000-119062 communique
In above-mentioned prior art, leave following problem.In the target of namely putting down in writing in the technology of above-mentioned patent documentation 1, expend time in when cleaning plant etc. owing to produce a lot of agglomerates when sputter, therefore requiring is that non-for Sn system other form the transparent oxide film of the gas barrier property excellence of system.Yet, the transparent oxide film of the fabrication techniques by above-mentioned patent documentation 2 is the CD film, therefore specific refractory power is higher, when using for the gas barrier layer on the resin film base material of above-mentioned Electronic Paper or solar cell, then need to reduce specific refractory power, so that near the specific refractory power of resin film base material (when for example wavelength is 633nm, refractive index n: 1.5～1.7).Therefore, considered by making the zinc oxide transparent oxide film contain more SiO 2Reduce the method for specific refractory power, but such as record in the patent documentation 2, if SiO 2Surpass 20wt%, then existing and causing separating out the composition that adds is SiO 2The unfavorable condition of crystallization phases.Therefore crystallization phases can't be adopted as protective membrane once separating out the function reduction that causes as gas barrier property (for example water-vapor barrier).
Summary of the invention
The present invention finishes in view of above-mentioned problem, its purpose be to utilize film forming speed faster sputtering method provide a kind of specific refractory power low and have zinc oxide transparent oxide film and a manufacture method thereof of good gas barrier property.
The inventor etc. are from making AZO(Al-Zn-O:Aluminium doped Zinc Oxide: Al-Doped ZnO) film contains SiO 2Reduce the specific refractory power this point and set out, in order to form the ZnO-SiO as the transparent oxide film by sputter 2-Al 2O 3Film and being studied.In this research, study carefully the bright sputtering target that has particular organization to consist of by utilization, and the atmosphere during with spatter film forming or the Temperature Setting of substrate become specified conditions, obtain transparent and specific refractory power is low and have the ZnO-SiO of high-gas resistance 2-Al 2O 3Film.
Thereby the present invention has adopted following formation for what obtain based on above-mentioned opinion in order to solve described problem.Be that transparent oxide film of the present invention is characterised in that, have following one-tenth and be grouped into, namely contain the Al of 0.9～20.0at% and the Si of 25.5～68.0at% with respect to total metal ingredient amount, and remainder is made of Zn and inevitable impurity, and be amorphousness.Namely in this transparent oxide film, having following one-tenth is grouped into, namely contain the Al of 0.9～20.0at% and the Si of 25.5～68.0at% with respect to total metal ingredient amount, remainder is made of Zn and inevitable impurity, and be amorphousness, therefore can in the visible region, obtain than in the past lower specific refractory power, and have higher gas barrier property (for example water-vapor barrier).In addition, can obtain the high-transmission rate more than 95% in the visible region, and have the good transparency.
In addition, the reason that the content of above-mentioned Al is made as 0.9～20.0at% is, produce paradoxical discharge at the sputtering target that is set as for obtaining less than the composition of the film of 0.9at%, and can't carry out stable DC sputter, and also produce paradoxical discharge at the sputtering target that is set as for the composition of the film that to surpass 20.0at%, and can't carry out stable DC sputter.In addition, the content of Al is more preferably below the 12at%.Be that reason is, if the content of Al is below the 12at%, it is high Si content can be kept ground comparatively speaking, therefore can obtain lower specific refractory power and higher gas barrier property.And, the reason that the content of above-mentioned Si is made as 25.5～68.0at% is, if less than 25.5at%, then can't obtain desirable low-refraction and gas barrier property, be set as for the sputtering target Si amount increase of acquisition above the composition of the film of 68.0at%, and can't carrying out the DC sputter.
And transparent oxide film of the present invention is characterised in that wavelength is that the optical transmittance of 750nm is more than 93%.Namely, be different from the oxide compound that can come with general DC sputter film forming, absorption at the long wavelength side that is present in the electronics in the electroconductive oxide based on picture is less, therefore pass through the DC spatter film forming, and become the film that has the higher transparency in the whole visible region of the light that does not lose the visible light long wavelength.
And transparent oxide of the present invention is characterised in that the specific refractory power mean value in the visible region is 1.59～1.80, thickness be 50nm when above water vapor transmission rate (WVTR) be 0.01g/ (m 2My god) below.Namely in this transparent oxide film, the specific refractory power mean value in the visible region is 1.59～1.80, thickness be 50nm when above water vapor transmission rate (WVTR) be 0.01g/ (m 2My god) below, therefore be suitable as the gas barrier layer of film forming on the resin film base material that in Electronic Paper or solar cell, adopts.In addition, at this visible region is made as the scope that wavelength is 380nm～750nm.
The manufacture method of transparent oxide film of the present invention is the method for the transparent oxide film of manufacturing foregoing invention, it is characterized in that, in oxygen containing inert gas atmosphere and under at least a environment of the state of heated substrates, utilize sputtering target, the input direct-current electric current carries out sputter, wherein, this sputtering target is made of oxidate sintered body, and has composite oxides Zn in this tissue of sintered body 2SiO 4And ZnO, this oxidate sintered body has following one-tenth and is grouped into: contain the Al of 0.3～4.0wt% and the Si of 6.0～14.5wt% with respect to total metal ingredient amount, and remainder is made of Zn and inevitable impurity.Namely in the manufacture method of this transparent oxide film, utilized in the tissue of above-mentioned oxidate sintered body, to have composite oxides Zn 2SiO 4Sputtering target with ZnO, therefore be achieved the DC sputter, and then the input direct-current electric current carries out sputter (DC sputter) in oxygen containing inert gas atmosphere and under at least a environment of the state of heated substrates, thereby can form the amorphousness transparent oxide film (ZnO-SiO that is rich in Si 2-Al 2O 3Film).Therefore according to method for making of the present invention, can add than in the past more SiO 2, and when reducing specific refractory power, can form with the DC sputter transparent oxide film of amorphousness and high-gas resistance.
In addition, the reason that the content of above-mentioned Al is made as 0.3～4.0wt% is, if less than 0.3wt%, then can't carry out the DC sputter because producing paradoxical discharge, if surpass 4.0wt%, the Al that then produces 2O 3Composite oxides ZnAl with ZnO 2O 4Cause producing paradoxical discharge and can't carry out the DC sputter.And the reason that the content of above-mentioned Si is made as 6.0～14.5wt% is, if less than 6.0wt%, then can't obtain fully to reduce the effect of specific refractory power, if surpass 14.5wt%, then can't obtain sufficient electroconductibility, and produces paradoxical discharge and can't carry out the DC sputter.
And the film of transparent oxide film of the present invention is characterised in that described substrate is the resin film base material, and the Heating temperature of described substrate is set in 100～200 ℃ of scopes.Namely in the manufacture method of this transparent oxide film, the Heating temperature of substrate is set in 100～200 ℃ of scopes, therefore in the heat affecting that suppresses the resin film base material that carries out film forming, obtain to have as the gas barrier layer that in Electronic Paper or solar cell, adopts the transparent oxide film of the sufficient transparency and low-refraction.In addition, the reason that the Heating temperature of aforesaid substrate is set in 100～200 ℃ of scopes is, if be lower than 100 ℃, Si content in the film reduced and the transparency descends, and cause specific refractory power to change, if surpass 200 ℃, then the resin film base material is with impaired.
And the film of transparent oxide film of the present invention is characterised in that, will be set as more than 0.05 with respect to the dividing potential drop of the oxygen of the whole atmosphere gas of described oxygen and rare gas element.Namely in the manufacture method of this transparent oxide film, owing to will be set as more than 0.05 with respect to the dividing potential drop of the oxygen of the whole atmosphere gas of oxygen and rare gas element, thereby can obtain the gas barrier layer that conduct adopts and have the transparent oxide film of the sufficient transparency and low-refraction in Electronic Paper or solar cell.Its reason is, if the dividing potential drop of oxygen less than 0.05, then can cause the Si content in the film to reduce and transparency decline, and causes specific refractory power to change.In addition, if the dividing potential drop of oxygen surpasses 0.2, then cause productivity to descend because the film forming speed of sputter slows down, therefore preferably be made as below 0.2.So, can carry out the DC sputter by at least a in the dividing potential drop of adjusting aforesaid substrate Heating temperature and above-mentioned oxygen in the present invention, adjust the content of Si in the film.
Bring into play following effect according to the present invention.Namely according to transparent oxide film involved in the present invention, having following one-tenth is grouped into, namely contain the Al of 0.9～28.5at% and the Si of 25.5～68.0at% with respect to total metal ingredient amount, and remainder is made of Zn and inevitable impurity, and be amorphousness, therefore can obtain than in the past lower specific refractory power in the visible region, and have high-gas resistance.And, according to the manufacture method of transparent oxide film involved in the present invention, utilize in above-mentioned oxidesintering body tissue to have composite oxides Zn 2SiO 4Sputtering target with ZnO, therefore can carry out the DC sputter, and the input direct-current electric current carries out sputter in oxygen containing inert gas atmosphere and under at least a environment of the state of heated substrates, therefore can form the transparent oxide film (ZnO-SiO of amorphous above-mentioned composition 2-Al 2O 3Film).Therefore, in the gas barrier layer of Electronic Paper or solar cell etc., adopt transparent oxide film of the present invention, thereby obtain desired high transparent, low-refraction and high-gas resistance, and can make good solar cell of visibility is higher when having high reliability Electronic Paper or efficiency of conversion etc.
Description of drawings
Fig. 1 is illustrated in the embodiment of transparent oxide film involved in the present invention and manufacture method thereof the schema of the manufacturing process of employed sputtering target.
Fig. 2 is illustrated among the embodiment of transparent oxide film involved in the present invention and manufacture method thereof, the graphic representation of the analytical results of the X-ray diffraction (XRD) of transparent oxide film (embodiment 3).
Fig. 3 is illustrated among the embodiment of transparent oxide film involved in the present invention and manufacture method thereof, the graphic representation of the analytical results of the X-ray diffraction of transparent oxide film (embodiment 5).
Fig. 4 is illustrated among the embodiment of transparent oxide film involved in the present invention and manufacture method thereof, the graphic representation of the analytical results of the X-ray diffraction of transparent oxide film (embodiment 6).
Fig. 5 is illustrated among the embodiment of transparent oxide film involved in the present invention and manufacture method thereof, the graphic representation of the analytical results of the X-ray diffraction of transparent oxide film (embodiment 11).
Fig. 6 is the graphic representation that is illustrated in the analytical results of the X-ray diffraction of transparent oxide film (comparative example 4) in the comparative example of transparent oxide film involved in the present invention and manufacture method thereof.
Fig. 7 is illustrated in the embodiment of transparent oxide film involved in the present invention and manufacture method thereof and the comparative example transmissivity with respect to the graphic representation of wavelength.
Fig. 8 is illustrated in the embodiment of transparent oxide film involved in the present invention and manufacture method thereof and the comparative example specific refractory power with respect to the graphic representation of wavelength.
Fig. 9 is the graphic representation of the analytical results of the X-ray diffraction (XRD) that is illustrated in sputtering target in the reference example.
Figure 10 is the graphic representation of the analytical results of the X-ray diffraction (XRD) that is illustrated in sputtering target in the comparison reference example.
Embodiment
Below with reference to Fig. 1 one embodiment of transparent oxide film involved in the present invention and manufacture method thereof is described.
The transparent oxide film of present embodiment is the film as the gas barrier layer of such use, having following one-tenth is grouped into, namely contain the Al of 0.9～20.0at% and the Si of 25.5～68.0at% with respect to total metal ingredient amount, and remainder is made of Zn and inevitable impurity, and is amorphousness.And this transparent oxide film square resistance when thickness is 100nm is 1.0 * 10 14More than Ω/sq.In addition, the specific refractory power mean value of this transparent oxide film in the visible region is 1.59～1.80, thickness be 50nm when above water vapor transmission rate (WVTR) be 0.01g/ (m 2My god) below.In addition, water vapor transmission rate (WVTR) is measured based on film health (mocon) method (モ コ Application method) according to the K7129 method of JIS standard.
And, the manufacture method of the transparent oxide film of present embodiment is as follows: in oxygen containing inert gas atmosphere or under at least a environment of the state of heated substrates, utilize sputtering target, the input direct-current electric current carries out sputter (DC sputter), wherein, this sputtering target is made of oxidate sintered body, and has composite oxides Zn in this tissue of sintered body 2SiO 4And ZnO, this oxidate sintered body has following one-tenth and is grouped into: contain the Al of 0.3～4.0wt% and the Si of 6.0～14.5wt% with respect to total metal ingredient amount, and remainder is made of Zn and inevitable impurity.
At this moment, the resin film base material is used as substrate, and the Heating temperature of substrate is set in 100～200 ℃ of scopes.And will be made as more than 0.05 with respect to the dividing potential drop of the oxygen of the whole atmosphere gas of oxygen and rare gas element.Can the synthetic transparency carrier of acrylic resin, polyamide resin, polyimide resin, vibrin Mierocrystalline cellulose and their copolymer resins be shown example as above-mentioned transparent film base material.Can enumerate polyester, polyethylene terephthalate (PET), polybutylene terephthalate, polymethylmethacrylate (PMMA), vinylformic acid, polycarbonate (PC), polystyrene, polyvinyl alcohol, polyethylene etc. as detailed example, but be not limited to this.In addition, the density of sintered compact is 100～108% of theoretical density in the above-mentioned sputtering target.In addition, the body resistance value of this sputtering target is below the 1 Ω cm.
The density of above-mentioned sintered compact is than the reason that is made as 100～108% in theoretical density if less than 100%, then can produce and cause the problems such as target is isolated, if surpass 108%, then major part becomes composite oxides Zn 2SiO 4Tissue, can't carry out discharge based on the DC sputter and become.Wherein, in the calculating of theoretical density ratio, use 5.61g/cm for ZnO 3, for SiO 2Use 2.20g/cm 3, for Al 2O 3Use 3.99g/cm 3Value calculate.And, because the body resistance value of sputtering target is below the 1 Ω cm, therefore can stablize and good DC sputter.
The method of making this sputtering target has following operation: the mixed powder operation, in this operation with Al 2O 3Powder, SiO 2Powder and ZnO powder are mixed into Al 2O 3: 0.5～5.0wt%, SiO 2: 10～22wt%, and remainder: by ZnO and inevitably impurity consist of; And sintering circuit, in this operation, in a vacuum this mixed powder is carried out sintering with hot pressing.
Example for above-mentioned method for making describes in detail, for example as shown in Figure 1, is Al more than 99.9% to purity at first 2O 3Powder, SiO 2Powder and ZnO powder carry out weighing, reaching above-mentioned content range, and pulverize, mix to make mixed powder by wet-type ball mill.For example, each powder and zirconia ball that weighing obtains are put into plastic containers (polyethylene kettle processed), and be used as mixed powder with the ball mill device wet mixing specified time.In addition, for example use alcohol as solvent.
Then, the mixed powder that obtains being carried out after the drying, is that the sieve of 250 μ m carries out granulation with mesh for example, further after the vacuum-drying, for example with 1200 ℃, 200kgf/cm 2Pressure, hot pressing was used as sintered compact in 5 hours in a vacuum.In addition, the scope that hot pressing temperature is preferred 1100～1250 ℃, the preferred 150～350kgf/cm of pressure 2Scope.So carry out the sintered compact of hot pressing, general using electrodischarge machining(E.D.M.), cutting or filing are machined into the target of designated shape, and the target that will process take In as scolder joins to by Cu, SUS(stainless steel) or the backing plate (バ ッ キ Application グ プ レ ー ト) that consists of of other metals (for example Mo) upper for sputter.
In addition, also can be following method as other manufacture method: carry out pulverizing, mixing based on the wet-type ball mill of above-mentioned manufacture method take pure water as solvent and with internal volume as the ball mill device of 300L, afterwards, the product that carries out drying-granulating by spraying drying is further pulverized with dry ball, and with this pulverized powder and above-mentionedly similarly carry out hot pressing.And, also can be the method for omitting based on the pulverizing process of above-mentioned dry ball.
When utilizing this sputtering target to come transparent oxide film to present embodiment to carry out the DC sputter, above-mentioned sputtering target is installed in the magnetic control sputtering device, with regulation power input, final vacuum and sputtering pressure the sputter gas dividing potential drop is being made as O 2/ (Ar+O 2) in 0.05～0.2 scope, base plate heating is made as under 100 ℃～200 ℃ the condition, carries out film forming at the resin film base material.
So in the transparent oxide film of present embodiment, having following one-tenth is grouped into, namely contain the Al of 0.9～20.0at% and the Si of 25.5～68.0at% with respect to total metal ingredient amount, and remainder is made of Zn and inevitable impurity, therefore and be amorphousness, can obtain than in the past lower specific refractory power in the visible region and have higher gas barrier property (for example water-vapor barrier).Especially, the specific refractory power mean value in the visible region is 1.59～1.80, thickness be 50nm when above water vapor transmission rate (WVTR) be 0.01g/ (m 2My god) below, be suitable as thus the gas barrier layer of film forming on the resin film base material that uses Electronic Paper or solar cell.
And, in the manufacture method of this transparent oxide film, utilize the composite oxides Zn that in the tissue of above-mentioned oxidate sintered body, exists 2SiO 4Therefore with the sputtering target of ZnO, can carry out the DC sputter, and then the input direct-current electric current carries out sputter under at least a environment of the state of oxygen containing inert gas atmosphere and heated substrates, therefore can form the amorphousness transparent oxide film (ZnO-SiO that is rich in Si 2-Al 2O 3Film).Therefore, can add more than ever before SiO according to method for making of the present invention 2, when reducing specific refractory power, can form the higher transparent oxide film of amorphous gas barrier property with the DC sputter.In addition, can obtain the high-transmission rate more than 95% in the visible region, and the film that can obtain to have the good transparency.
And, because the Heating temperature of substrate is set in 100～200 ℃ of scopes, therefore in the heat affecting of inhibition to the resin film base material of formation, can obtain to have as the gas barrier layer that uses Electronic Paper or solar cell the transparent oxide film of the sufficient transparency and low-refraction.In addition, owing to will be set as more than 0.05 with respect to the dividing potential drop of the oxygen of the whole atmosphere gas of oxygen and rare gas element, therefore can obtain to have as the gas barrier layer that uses Electronic Paper or solar cell the transparent oxide film of the sufficient transparency and low-refraction.
Embodiment
Below, with reference to figure 2～Fig. 8 the evaluation result of the embodiment of the relevant transparent oxide film of making based on above-mentioned present embodiment is described.
Carry out the manufacturing of embodiments of the invention with following condition.At first to Al 2O 3Powder, SiO 2Powder and ZnO powder carry out weighing, to reach the proportion of composing shown in the table 1, and the powder that obtains and the zirconia ball (ball of the ball of diameter 5mm and diameter 10mm respectively accounts for half) that is equivalent to 4 times of amounts (weight ratio) of its powder put into 10L plastic containers (polyethylene kettle processed), be used as mixed powder in 48 hours with the ball mill device wet mixing.In addition, for example use alcohol as solvent.
Then, the mixed powder that obtains being carried out after the drying, is that the sieve of 250 μ m carries out granulation with mesh for example, after the further vacuum-drying, with 1200 ℃ and 200kgf/cm 2Pressure, hot pressing was used as sintered compact in 5 hours in a vacuum.The sintered compact that so carries out hot pressing is machined into the target (diameter is 125mm, and thickness is 10mm) of designated shape, the product of processing and the backing plate that is made of oxygen free copper is engaged to make the sputtering target of present embodiment 1～16.
In addition, carried out following trial, be about to these sputtering targets and be installed in the magnetic control sputtering device, in power supply: DC, power input: 500W, final vacuum: 1 * 10 -4Pa, sputter dividing potential drop are (with respect to the dividing potential drop O of the oxygen of the whole atmosphere gas of oxygen and rare gas element 2/ (Ar+O 2)): more than 0.05, sputtering pressure: 0.67Pa, base plate heating be under 100 ℃～200 ℃ the condition, measure purposes as specific refractory power and transmissivity, at the glass substrate (1737# of Corning Incorporated, long: 20 * wide: 20, thickness: 0.7mm) the upper transparent film with 150nm thickness that forms, and, see through the mensuration purposes as water vapour, the PET film (long: 100mm * wide: 100, thickness: 120 μ m) the upper transparent film with 50nm that forms.And, with the adhesiveness test purposes, carried out at Kapton (long: 100mm * wide: 100mm, thickness: 120 μ m) the upper trial that forms the transparent film with 50nm.
In addition, transparent oxide film as a comparative example, under the conditions shown in Table 1, making Heating temperature with substrate as above-described embodiment is set as the transparent oxide film (comparative example 1,2) that exceeds 100～200 ℃ of scopes and the Si content of sputtering target is made as transparent oxide film (comparative example 3,4) less than 6.08wt%.In addition, as past case, be made as less than 6.08wt% as the content of above-described embodiment making with the Si of sputtering target, and pass through the transparent oxide film that the RF sputter forms.
Figure BDA00003613235600091
For the transparent oxide film of embodiments of the invention, comparative example and the past case of making like this, measure the result that film forms with the ICP emission spectrometry method, with respect to each metal ingredient of total metal ingredient as shown in Table 1.And, carrying out that X-ray diffraction (XRD) is analyzed and the investigation result that has or not of the relevant peak crystallization that draws for the transparent oxide film of embodiments of the invention and comparative example shown in the table 1.In addition, for exemplary embodiments 3,5,6,11 and graphic representation comparative example 4, XRD analysis result be shown in Fig. 2～Fig. 6.
And, measure the specific refractory power of each the transparent oxide film that obtains according to light splitting ellipsometer (the UVISEL NIA processed AGMS of HORIBA Jobin Yvon company), and measure transmissivity by spectrophotometer (the Japanese light splitting V-550 processed of company).Each measurement result is shown in table 1.In addition, for typical embodiment 3,5,6,11 and comparative example 4, expression is shown in Fig. 7 with respect to the graphic representation of the transmission characteristics of wavelength.And the transmissivity of wavelength the results are shown in table 2 under the 750nm the when thickness of transparent oxide film is 50nm, 100nm, 300nm.
[table 2]
Figure BDA00003613235600111
In addition, the PERMATRAN-WMODEL3/33 that utilizes film health (mocon) method and use mocon company to make measures water vapor transmission rate (WVTR) (water-vapor barrier) according to the K7129 method of JIS standard.Each result who is being measured to shown in the table 1.In addition, for exemplary embodiments 3,5,6,11 and comparative example 4, expression is shown in Fig. 8 with respect to the graphic representation of the refractive index characteristic of wavelength.
The result of these evaluations, in comparative example 1,3,4, in XRD analysis, confirm peak crystallization and in film crystallization, water vapor transmission rate (WVTR) also surpasses 0.01g/ (m 2My god).And transmissivity is also lower less than 95% when the specific refractory power of visible region surpasses 1.80.In addition, in the comparative example 2, because base plate heating temperature higher is 210 ℃, therefore causes the thermal distortion of resin film base material and can't make evaluation.In addition, in the past case with the RF spatter film forming, the content of Si specific refractory power lower and in the visible region is higher to be 2.05, and transmissivity also low be 90.6%.
Comparatively speaking, unconfirmed to peak crystallization in the XRD analysis of all embodiment of the present invention, and be amorphous film, and with regard to water vapor transmission rate (WVTR), be 0.01g/ (m 2My god) below, have higher water-vapor barrier.And, among all embodiment, the specific refractory power in the visible region also be below 1.80 and transmissivity also higher be more than 95%, and can obtain the film of low-refraction and high transparent.So, as the gas barrier layer that uses Electronic Paper or solar cell, all possesses suitable membrane property in the transparent oxide film of embodiments of the invention.But, although the characteristic of the film under the condition of record is excellent among the embodiment 16, the O when carrying out sputter in the atmosphere 2Amount is too much, and film forming speed is slowed down.
＜adhering mensuration＞measure as adhesivity, at first with double sticky tape the transparent oxide film on the film that obtains (embodiment 1～17, comparative example 1～7 and past case) is pasted on the glass substrate, and utilize cutting knife from the top of transparent oxide film, to engrave 100 otch with chessboard grid shape.Then, paste securely scotch tape, afterwards with 90 ° of rapid strip ofves of direction, and check whether produce peeling off of transparent oxide film.To the results are shown in table 3.In 100 grid, represent unstripped grid number with X.Namely when the position is peeled off in existence, be expressed as X/100, be expressed as 100/100 when not peeling off the position.
[table 3]
Figure BDA00003613235600131
As can be known from these results, with respect to the comparative example of peeling off or past case, all do not peel off in the embodiments of the invention, obtain higher adhesivity.
In addition, technical scope of the present invention is not limited to above-mentioned embodiment and above-described embodiment, in addition various changes in the scope that does not break away from aim of the present invention.For example not only can be on resin film film forming, also can constitute on the contrary, at formation transparent oxide film on glass, and on it, paste resin molding, and then from glass simultaneously strip off resin molding and transparent oxide film.
Among (reference example of relevant sputtering target) the present invention, require by the DC spatter film forming, the relevant result of study that can carry out the sputtering target of DC sputter below is shown.The manufacturing of the sputtering target that this reference example is related is carried out under the following conditions.At first, to Al 2O 3Powder, SiO 2Powder and ZnO powder carry out weighing, to reach each ratio shown in the table 1, and the powder that obtains and the zirconia ball (ball of the ball of diameter 5mm and diameter 10mm respectively accounts for half) that is equivalent to 4 times of amounts (weight ratio) of its powder put into 10L plastic containers (polyethylene kettle processed), be used as mixed powder in 48 hours with the ball mill device wet mixing.In addition, for example use alcohol as solvent.
Then, the mixed powder that obtains being carried out after the drying, is that the sieve of 250 μ m carries out granulation with mesh for example, further after the vacuum-drying, with 1200 ℃, 200kgf/cm 2Pressure, hot pressing was used as sintered compact in 5 hours in a vacuum.The sintered compact that so carries out hot pressing is machined into the target (diameter is 125mm, and thickness is 10mm) of designated shape, the product of processing is engaged the sputtering target of this reference example made from the backing plate that is made of oxygen free copper.
In addition, reference example 1～11 as a comparison, with each ratio shown in the table 2 to Al 2O 3Powder, SiO 2Powder and ZnO powder carry out weighing, and mix each powder that obtains, with 0.6t/cm 2Carry out punching press, use again the CIP(cold isostatic press) with the 175MPa moulding, and it is carried out atmosphere with 1400 ℃ burn till to produce sputtering target.And reference example 12～14 as a comparison, carry out weighing with extraneous each ratio that is shown in table 2 that one-tenth of the present invention is grouped into, and carry out vacuum hotpressing with the condition identical with this reference example and make sputtering target.
And, carried out following trial: be about to these sputtering targets and be installed in the magnetic control sputtering device, with power supply: DC, power input: 200W, final vacuum: 1 * 10 -4The condition of Pa, sputter gas: Ar and sputtering pressure: 0.67Pa, be heated to 200 ℃ glass substrate (1737# of Corning Incorporated, long: 20 * wide: 20, thickness: 0.7mm) the upper transparent film with 300nm thickness that forms.
In the reference example of the present invention and comparison reference example of so making, respectively to the density (theoretical density ratio) of sintered compact, have or not the ZnO(101 based on X-ray diffraction method (XRD)) and Zn 2SiO 4(410) diffraction peak, could carry out DC sputter, body resistance value, the paradoxical discharge number of times when carrying out DC sputter in 60 minutes, and the specific refractory power (with respect to the light of 380nm, 550nm, 750nm wavelength) of the transparent film of DC sputter measure, estimate.The results are shown in table 4.
Figure BDA00003613235600151
From this result as can be known, utilize Al in the comparison reference example that atmosphere burns till 2O 3Content is less and do not contain SiO 2Comparison reference example 1,2 in, the paradoxical discharge number of times is more and can't carry out stable DC sputter, is containing a certain amount of Al 2O 3But do not contain SiO 2Comparison reference example 3～5 in can't obtain low-refraction.And, utilize the Al in the comparison reference example that atmosphere burns till 2O 3Content is more and do not contain SiO 2Comparison reference example 6,7 in, the paradoxical discharge number of times is more and can't carry out stable DC sputter, is containing Al 2O 3With SiO 2Comparison reference example 8～11 in, the more or target of paradoxical discharge number of times does not have electroconductibility and can't carry out the DC sputter.In addition, relatively in the reference example 1～7, density is all less than 100% of theoretical density.
In addition, the SiO in utilizing the comparison reference example of hot pressing 2Content is less than in the comparison reference example 12 of the scope of the invention, can't obtain low-refraction, at SiO 2In the comparison reference example 13 of content more than the scope of the invention, target does not have electroconductibility and can't carry out the DC sputter.And, at Al 2O 3In the comparison reference example 14 of content more than the scope of the invention, the paradoxical discharge number of times is more and can't carry out stable DC sputter.In addition, relatively in the reference example 8,12,14, in XRD, observe ZnO(101) and Zn 2SiO 4(410) two peaks, but the content of Al or Si exceeds scope of the present invention, therefore produces above-mentioned undesirable condition.
With respect to this, this reference example is all observed ZnO(101 in XRD) and Zn 2SiO 4(410) two peaks can stably carry out good DC sputter because the paradoxical discharge number of times is few, with regard to specific refractory power, all can obtain to be lower than the specific refractory power of AZO film.And, with regard to density, in this reference example all in 100～108% scope of theoretical density.
Then, about the reference example 3(SiO shown in the table 1 2: 20wt%), will be with the Fig. 9 that the results are shown in of X-ray diffraction method (XRD) observation.In this reference example 3, observe composite oxides Zn 2SiO 4The diffraction peak of (410) and the diffraction peak of ZnO (101) all show higher intensity.With respect to this, be grouped into atmosphere by the one-tenth identical with reference example 3 and burn till in the comparison reference example of producing, as shown in figure 10, can't obtain the diffraction peak of ZnO (101).So, in order to obtain electroconductibility, need as this reference example, to make composite oxides Zn 2SiO 4Coexist in tissue with ZnO.

Claims (6)

1. a transparent oxide film is characterized in that,
This transparent oxide film has with respect to total metal ingredient amount and contains the Al of 0.9～20.0at% and Si and the remainder of 25.5～68.0at% is grouped into by the one-tenth that Zn and inevitable impurity consist of, and is amorphousness.
2. transparent oxide film according to claim 1 is characterized in that,
Transmissivity was more than 93% when wavelength was 750nm.
3. transparent oxide film according to claim 1 is characterized in that,
Specific refractory power mean value in the visible region is 1.59～1.80, thickness be 50nm when above water vapor transmission rate (WVTR) be 0.01g/ (m 2My god) below.
4. the manufacture method of a transparent oxide film is characterized in that, it is the method for manufacturing transparent oxide film claimed in claim 1,
In oxygen containing inert gas atmosphere and under at least a environment in the state of heated substrates, utilize sputtering target, the input direct-current electric current carries out sputter, and wherein, this sputtering target is made of oxidate sintered body, and has composite oxides Zn in this tissue of sintered body 2SiO 4And ZnO, this oxidate sintered body has with respect to total metal ingredient amount and contains the Al of 0.3～4.0wt% and Si and the remainder of 6.0～14.5wt% is grouped into by the one-tenth that Zn and inevitable impurity consist of.
5. the manufacture method of transparent oxide film according to claim 4 is characterized in that,
Described substrate is the resin film base material, and the Heating temperature of described substrate is set in 100～200 ℃ of scopes.
6. the manufacture method of transparent oxide film according to claim 4 is characterized in that,
The dividing potential drop of oxygen with respect to the whole atmosphere gas of described oxygen and rare gas element is made as more than 0.05.
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Cited By (5)

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CN111902561A (en) * 2018-04-26 2020-11-06 三菱综合材料株式会社 Shield layer, method for producing shield layer, and oxide sputtering target

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5730729B2 (en) * 2011-09-20 2015-06-10 株式会社カネカ Substrate with transparent electrode
JP6070194B2 (en) * 2011-10-28 2017-02-01 東レ株式会社 Gas barrier film
JP5550768B1 (en) * 2012-07-03 2014-07-16 Ｊｘ日鉱日石金属株式会社 Sintered body and amorphous film
WO2014069367A1 (en) * 2012-10-30 2014-05-08 Jx日鉱日石金属株式会社 Electrically conductive oxide sintered body, and low-refractive-index film produced using said electrically conductive oxide
JP2014114467A (en) * 2012-12-07 2014-06-26 Toray Ind Inc Method for producing gas barrier film
US10829643B2 (en) * 2013-01-11 2020-11-10 Toray Industries, Inc. Gas barrier film
JP6866065B2 (en) * 2016-01-29 2021-04-28 日東電工株式会社 Laminated film
JP6945965B2 (en) * 2016-01-29 2021-10-06 日東電工株式会社 Optical laminate
JP6938112B2 (en) * 2016-01-29 2021-09-22 日東電工株式会社 Optical laminate
KR102040234B1 (en) 2016-11-28 2019-11-06 주식회사 후본 Different material convergence 3d printer and method for printing using it
JPWO2018110272A1 (en) * 2016-12-15 2019-10-24 東レフィルム加工株式会社 Gas barrier film and organic EL device
JP2018195512A (en) * 2017-05-19 2018-12-06 国立大学法人東京工業大学 Organic EL element
JP2019143245A (en) 2018-02-22 2019-08-29 三菱マテリアル株式会社 Oxide film and manufacturing method of oxide film and nitrogen containing oxide sputtering target
CN114127029A (en) * 2019-10-23 2022-03-01 三菱综合材料株式会社 Oxide sputtering target

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007311041A (en) * 2006-05-16 2007-11-29 Bridgestone Corp Film-forming method of crystalline zno system transparent conductive thin film, crystalline zno system transparent conductive thin film and film, as well as resistance film type touch panel
CN101189358A (en) * 2005-05-30 2008-05-28 日矿金属株式会社 Sputtering target and process for producing 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

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3841388B2 (en) * 1998-02-16 2006-11-01 日鉱金属株式会社 Protective film for optical disk and sputtering target for forming protective film of optical disk
JPH11236219A (en) * 1998-02-20 1999-08-31 Sumitomo Metal Mining Co Ltd Zinc oxide-base sintered compact and its production
JPH11322332A (en) * 1998-05-21 1999-11-24 Sumitomo Metal Mining Co Ltd Zno-based sintered product and its production
JP2000040429A (en) * 1998-07-24 2000-02-08 Sumitomo Metal Mining Co Ltd Manufacturing of zinc oxide transparent conductive film
JP2007327079A (en) * 2006-06-06 2007-12-20 Sony Corp Transparent conductive laminate film, and its manufacturing method
WO2009078330A1 (en) * 2007-12-19 2009-06-25 Hitachi Metals, Ltd. Zinc oxide sintered compact, process for producing the zinc oxide sintered compact, sputtering target, and electrode formed using the sputtering target
JPWO2009078329A1 (en) * 2007-12-19 2011-04-28 日立金属株式会社 Zinc oxide sintered body and manufacturing method thereof, sputtering target, electrode
JP4670877B2 (en) * 2008-02-25 2011-04-13 住友金属鉱山株式会社 Zinc oxide based transparent conductive film laminate, transparent conductive substrate and device
TW201013709A (en) * 2008-09-17 2010-04-01 Mitsui Mining & Smelting Co Zinc oxide group transparent conductive film and process for making same
EP2415597A4 (en) * 2009-03-31 2014-12-31 Teijin Ltd Transparent conductive laminate and transparent touch panel

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101189358A (en) * 2005-05-30 2008-05-28 日矿金属株式会社 Sputtering target and process for producing the same
JP2007311041A (en) * 2006-05-16 2007-11-29 Bridgestone Corp Film-forming method of crystalline zno system transparent conductive thin film, crystalline zno system transparent conductive thin film and film, as well as resistance film type touch panel
WO2009145152A1 (en) * 2008-05-27 2009-12-03 株式会社カネカ Transparent conductive film and method for producing the same

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105849929A (en) * 2013-12-26 2016-08-10 国立研究开发法人科学技术振兴机构 Metal oxide thin film, organic electroluminescent element provided with same, solar cell, and organic solar cell
TWI651433B (en) * 2013-12-26 2019-02-21 國立研究開發法人科學技術振興機構 Metal oxide film, organic electroluminescence device having the film, solar cell and organic solar cell
US11094909B2 (en) 2013-12-26 2021-08-17 Japan Science And Technology Agency Thin film of metal oxide, organic electroluminescent device including the thin film, photovoltaic cell including the thin film and organic photovoltaic cell including the thin film
CN106103381A (en) * 2014-05-30 2016-11-09 住友金属矿山株式会社 Oxidate sintered body and its manufacture method and oxidation film
CN108602315A (en) * 2016-01-29 2018-09-28 日东电工株式会社 Conductive laminated film
CN111902561A (en) * 2018-04-26 2020-11-06 三菱综合材料株式会社 Shield layer, method for producing shield layer, and oxide sputtering target
CN111902561B (en) * 2018-04-26 2022-04-08 三菱综合材料株式会社 Shield layer, method for producing shield layer, and oxide sputtering target
CN110793937A (en) * 2018-08-03 2020-02-14 张家港康得新光电材料有限公司 Membrane type determination method

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