CN102812150B - Oxide deposition material and transparent conductive film - Google Patents
Oxide deposition material and transparent conductive film Download PDFInfo
- Publication number
- CN102812150B CN102812150B CN201180014684.5A CN201180014684A CN102812150B CN 102812150 B CN102812150 B CN 102812150B CN 201180014684 A CN201180014684 A CN 201180014684A CN 102812150 B CN102812150 B CN 102812150B
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- Prior art keywords
- oxygen
- film
- evaporation material
- oxide
- oxide evaporation
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- 230000008021 deposition Effects 0.000 title abstract description 32
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 151
- 239000001301 oxygen Substances 0.000 claims abstract description 151
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 150
- 238000004519 manufacturing process Methods 0.000 claims abstract description 59
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims abstract description 58
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 28
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- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
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- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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- C23C14/28—Vacuum evaporation by wave energy or particle radiation
- C23C14/30—Vacuum evaporation by wave energy or particle radiation by electron bombardment
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
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- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
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- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
- C01P2006/62—L* (lightness axis)
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3286—Gallium oxides, gallates, indium oxides, indates, thallium oxides, thallates or oxide forming salts thereof, e.g. zinc gallate
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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3293—Tin oxides, stannates or oxide forming salts thereof, e.g. indium tin oxide [ITO]
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/658—Atmosphere during thermal treatment
- C04B2235/6583—Oxygen containing atmosphere, e.g. with changing oxygen pressures
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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Abstract
The disclosed oxide deposition material comprises a sintered oxide that consists primarily of indium oxide and also contains tin, with the number of tin atoms being between 0.001 and 0.614 times the number of indium atoms. Said oxide deposition material is characterized by an L* value, in the CIE 1976 color space, between 54 and 75. Due to an optimal oxygen content, said oxide deposition material with an L* value between 54 and 75 allows the manufacture, via vacuum deposition, of a transparent conductive film with low resistance and high transparency in the visible-light region, even if the amount of oxygen gas introduced into the film-formation vacuum chamber is low. A low amount of introduced oxygen gas reduces the difference in composition between the film and the deposition material, reducing variations in film composition and characteristics during mass production.
Description
Technical field
The present invention relates to a kind of oxide evaporation material using and the nesa coating that utilizes this oxide evaporation material to manufacture when manufacturing nesa coating by various vacuum vapour depositions such as the auxiliary vapour deposition methods of electron beam evaporation plating method, ion plating method or high density plasma, for example, relate to low for the manufacture of the resistance of transparency electrode that can be used as solar cell and in visible region, show the nesa coating of high permeability and the improvement of the oxide evaporation material that uses.
Background technology
Nesa coating has high conductivity and at the high transmission rate of visible region.Therefore, bring into play this characteristic, above-mentioned nesa coating is used in the electrode etc. of solar cell, liquid crystal display device, other various photo detectors, but also bring into play it in the reflection-absorption characteristic of near infrared range, anti-the hazing that is also applied to the hot line reflectance coating using, various antistatic film, refrigerator-freezer etc. on the window glass of automobile or buildings etc. used transparent heater.
In addition, in above-mentioned nesa coating, that be in general widely used is the stannic oxide (SnO containing antimony or fluorine as doping agent
2); Zinc oxide (ZnO) as doping agent containing aluminium, gallium, indium, tin; Indium sesquioxide (the In that contains tin, tungsten, titanium as doping agent
2o
3) etc.The indium oxide film that particularly contains tin as doping agent, i.e. In
2o
3-Sn mesentery, is called as ITO (tin indium oxide, Indium tin oxide) film, because it can easily obtain low-resistance nesa coating, therefore industrial, is widely used so far always.
In addition, as the manufacture method of these nesa coatings, conventionally use the method for vacuum vapour deposition, sputtering method, coating transparency conducting layer formation use coating fluid etc.Wherein, effective means when vacuum vapour deposition and sputtering method maybe need to control accurate thickness while being use low-vapor pressure material, and because operation is very easy, so can be used for industry.In addition, while comparing vacuum vapour deposition and sputtering method, vacuum vapour deposition can be carried out high speed film forming, thereby excellent aspect batch production.
As a rule, vacuum vapour deposition is 10
-3～10
-2in the vacuum of about Pa, to the solid as evaporation source or liquid heats and make it resolve into gas molecule or atom quickly, then, as film, again condense to the method on substrate surface.In addition, for the type of heating of above-mentioned evaporation source, though have variously, be generally electrical resistance heating (RH method), electron beam heating (EB method, electron beam evaporation plating method).In addition, be also known in O
2the reactant gasess such as gas carry out the reactive vapour deposition method of evaporation when importing in filming chamber's (chamber).
In addition, when the such oxide film of deposition ITO, all the time normal in history what utilize is above-mentioned electron beam evaporation plating method.That is, in evaporation source, use ITO oxide evaporation material (also referred to as ITO sheet or ITO particle), to filming chamber's (chamber), import the O as reactant gases
2gas, makes to produce with the thermoelectron that silk (being mainly W line) is emitted and accelerate in electric field from thermoelectron, is radiated on ITO oxide evaporation material, and irradiated part can produce localized hyperthermia and evaporate, and is deposited on substrate.In addition, following priming reaction vapour deposition method (ARE method) is also the method useful to ITO film forming, that is, utilize thermionic electron emitter or RF electric discharge to make it produce plasma body, by this plasma body, makes evaporant, reactant gases (O
2gas etc.) activation thus, can produce low resistance film in low temperature substrates.And, the auxiliary vapour deposition method (HDPE method) of high density plasma of recently clear and definite using plasma rifle is also a kind of to ITO film forming effective means, therefore, industrially starting to be widely used (with reference to non-patent literature 1: " vacuum ", Vol.44, No.4, calendar year 2001, p.435-439).In the method, utilized the arc-over of using plasma generating unit (plasma gun), this arc-over is maintained at and is built between the negative electrode of plasma gun and the crucible of evaporation source (anode).The electronics of emitting from negative electrode is subject to introduction by magnetic field (guiding) and the part of the ITO oxide evaporation material of cover during being put into crucible.Evaporant is the local part evaporation that becomes high temperature from being subject to this electron beam irradiation, and is deposited on substrate.The evaporant of gasification and the O of importing
2gas is activated in this plasma body, therefore can produce the ITO film with good electrology characteristic.In addition, another kind of classification as the various vacuum vapour depositions such as above-mentioned, Ionized method with evaporant or reactant gases is collectively referred to as ion plating method (IP method), this ion plating method can be effective to obtain low resistance and high transmission rate ITO film (with reference to non-patent literature 2: " transparent Guide Electricity Mo Ji Intraoperative " (technology of nesa coating), Ohmsha, 1999 annuals, p.205-211).
In addition, solar cell for any type of applied for transparent conducting film, in the electrode of light-struck face side, above-mentioned nesa coating is indispensable, and what be utilized is above-mentioned ITO film in the past always, doped with zinc oxide (ZnO) film of aluminium, gallium.And these nesa coatings require it to have low resistance and the characteristics such as high transmission rate to sunlight.In addition, as the manufacture method of these nesa coatings, adopt above-mentioned ion plating method or high density plasma to assist vapour deposition method equal vacuum vapour deposition method.
Oxide evaporation material for the auxiliary vapour deposition method equal vacuum vapour deposition method of above-mentioned electron beam evaporation plating method, ion plating method and high density plasma, it uses be small size (for example, diameter is 10～50mm and is highly the cylindrical shape of about 10～50mm) sintered compact, therefore film amount that, can film forming by an oxide evaporation material is limited.In addition, if the consumption of oxide evaporation material is many, residual content tails off, need to interrupt film forming and import atmosphere to the filming chamber in vacuum state, then exchange untapped oxide evaporation material, and again make filming chamber in vacuum state, therefore become the major cause that reduces productivity.
In addition, in the auxiliary vapour deposition method equal vacuum vapour deposition method of electron beam evaporation plating method, ion plating method and high density plasma, indispensable technology during as batch production nesa coating, can enumerate the continuous supply method of above-mentioned oxide evaporation material, as one example, be recorded in non-patent literature 1.In this continuous supply method, in the siege inner side of drum, take in the oxide evaporation material of the cylindrical shape being arranged in rows, at the height of distillation face, keep oxide evaporation material under constant state to be extruded successively and supply with continuously.Therefore,, by the continuous supply method of oxide evaporation material, can realize a large amount of productions of the nesa coating that adopts vacuum vapour deposition.
In addition, for the oxide evaporation material as raw material, in patent documentation 1 (Japanese kokai publication hei 8-104978 communique), introduced ITO deposition material.Following ITO deposition material is disclosed in fact: its In for being comprised of indium, tin and oxygen
2o
3-SnO
2the granulated material of system, wherein, the volume of a particle is 0.01～0.5cm
3and relative density is more than 55%, the apparent density while being filled into container is 2.5g/cm
3below.In addition, also recorded, by thering is above-mentioned formation, thereby can obtain such ITO deposition material, that is, this ITO deposition material can stably form low-resistance ITO film by electron beam evaporation plating, utilising efficiency is more than 80%, and can supply with continuously and can in supplying machine, not stop up.
And, in patent documentation 2 (TOHKEMY 2007-84881 communique), also introduced the ITO deposition material being formed by Indium sesquioxide and stannic oxide.The ITO deposition material that patent documentation 2 is recorded is 4.9g/cm by density
3, diameter is that the oxidate sintered body of 30mm, the thickness cylindrical shape that is 40mm forms, can be damaged in supplying machine, can supply with continuously.
In addition, in the situation that the existing ITO deposition material (oxide evaporation material) of recording in utilizing above-mentioned patent documentation etc. is manufactured low resistances by various vacuum vapour depositions such as the auxiliary vapour deposition methods of electron beam evaporation plating method, ion plating method or high density plasma and is had the nesa coating of high light transmittance, when film forming, need in film forming vacuum tank, (for example import a large amount of oxygen, record with reference to the paragraph 0007 of patent documentation 2 and paragraph 0108 etc.), the therefore main problem that produces the following stated.
First, the composition deviation of nesa coating and oxide evaporation material can become greatly, thereby the design of the composition of nesa coating becomes difficult.In general, this be due to, if it is many to import to the oxygen amount of film forming vacuum tank, the composition difference of nesa coating and oxide evaporation material is easy to become large.In film forming mass-production process, also easily produce the change of the oxygen amount in film forming vacuum tank, be therefore subject to this impact, be also easy to produce the change that film forms, thereby cause the deviation of membrane property.
In addition, in utilizing the reactive evaporation film-forming of oxygen, if oxygen amount increases, not only cause film density to reduce, and cause that film is to problems such as the sticking power of substrate die down.This be because, if the metal oxide of evaporation is oxidized before arriving substrate, make energy disappear, therefore, large if the ratio of oxidation becomes, be difficult to obtain fine and close and substrate there is to the film of high adhesion.
And while forming nesa coating on the substrate that is coated with the easy oxidized metallic membrane in surface and organism film, if it is more to flow to the oxygen of film forming vacuum tank, substrate surface will be oxidized before film forming, thus, cannot manufacture high performance device.The rising of the substrate temperature of this tendency during along with film forming and more obvious.For example, when manufacture is carried out the solar cell of energy transformation to the light of the face incident of the opposition side from substrate, must on film formed PIN element, form nesa coating by metal foil, therefore, in the situation that oxygen import volume is many, carry out in the process of film forming, element is vulnerable to damage and cannot manufactures high performance device.When forming organic thin film solar cell and top emission type organic electroluminescent device, also identical with above-mentioned situation, while forming nesa coating on organism luminescent layer, under the many states of oxygen import volume, organism luminescent layer is oxidized and be damaged, and therefore cannot realize high performance element.
The present invention is conceived to these problems and makes, even if its problem is to provide a kind of less oxide evaporation material that also can stably produce low resistance and have the nesa coating of high light transmittance in visible region of oxygen amount that the Indium sesquioxide that is added with tin imported during as main component, film forming of take, also provide the nesa coating that adopts this oxide evaporation material to manufacture simultaneously.
Summary of the invention
That is, oxide evaporation material of the present invention, is characterized in that, it forms as main component and the oxidate sintered body that contains tin by take Indium sesquioxide, and the content of tin counts 0.001～0.614 with Sn/In atomicity ratio, and the L in CIE1976 colorimeter system
*value is 54～75.
In addition, nesa coating of the present invention, take Indium sesquioxide as main component and contain tin, it is characterized in that, it is by using above-mentioned oxide evaporation material and assisting the crystallinity nesa coating of vapour deposition method film forming to form by electron beam evaporation plating method, ion plating method or high density plasma, and the content of tin counts 0.001～0.614 with Sn/In atomicity ratio.
In addition, the L in CIE1976 colorimeter system
*value is that 54～75 oxide evaporation material of the present invention has optimum oxygen, therefore, by applying this oxide evaporation material, even if the amount of oxygen importing to film forming vacuum tank is few, also can produce low resistance and in visible region, there is the nesa coating of high-permeability by vacuum vapour deposition, and because the amount of oxygen importing to film forming vacuum tank is few, so the composition that can dwindle between film and oxide evaporation material is poor, being easy to obtain target film forms, moreover, film component fluctuation and flutter in the time of also can reducing batch production.In addition, due in the situation that the less film forming of carrying out of amount of oxygen importing to film forming vacuum tank, thus can reduce the infringement of oxygen to substrate, thus can realize high performance device.Particularly, can stably produce the high performance membrane that can be used for solar cell in the mode of wounded substrate not.
Embodiment
Below, embodiments of the present invention are elaborated.
(1) oxide evaporation material
Oxide evaporation material of the present invention has such composition: take Indium sesquioxide as main component, and contain with Sn/In atomicity than the tin of counting 0.001～0.614 ratio.And, composition for the nesa coating that uses oxide evaporation material of the present invention and manufacture by vacuum vapour deposition, the composition of itself and oxide evaporation material is extremely close, so the film of manufacturing forms also to form to take Indium sesquioxide as main component and contain and take Sn/In atomicity than being only the composition of the tin of 0.001～0.614 ratio.The tin that why only contains aforementioned proportion is because can make the mobility of indium oxide film increase.Film forms, is that the tin content (Sn/In atomicity ratio) that oxide evaporation material forms is less than at 0.001 o'clock, and the effect that carrier concn increases (being the effect that mobility increases) is little, cannot obtain low resistance film.In addition, tin content surpasses at 0.614 o'clock, and the tin amount in film is too much, and it is large that neutral impurity degree of scatter when electronics is moved becomes, and is subject to the impact that mobility reduces and cannot obtains low resistance film.In order to bring into play higher carrier concn to obtain low resistance film, preferred tin content counts 0.040～0.163 with Sn/In atomicity ratio, and then its film is crystalline film.
In addition, the nesa coating that the Indium sesquioxide of take is main component is N-shaped semi-conductor, but in order to make its performance high conductivity and high light transmittance, needs appropriate anoxia condition.That is,, when the many and oxygen deficit of oxygen amount in film is few, even if contain doping agent, can not show electroconductibility yet.In order to show electroconductibility, need in film, import anaerobic environment, if but oxygen deficit is too much, and the photoabsorption of visible ray increases, and causes painted.Thus, must make film there is best anaerobic environment.For the oxygen in film, except by supplying with as the oxide evaporation material of raw material, in the time of can also be by film forming, import to the mode that the oxygen of film forming vacuum tank is absorbed in film and supply with.Thereby when the component supplied with from oxide evaporation material is few, the amount of oxygen that imports to film forming vacuum tank must be more, if but to import to the amount of oxygen of film forming vacuum tank many, can produce above-mentioned problem.Therefore, only there is the oxide evaporation material of optimum oxygen just useful.
In addition, the maximum feature of oxide evaporation material of the present invention is, with the L in CIE1976 colorimeter system
*value is stipulated it.At this, so-called CIE1976 colorimeter system is the color space that CIE (International Commission on Illumination) recommended in 1976.It is by brightness L
*with aberration index a
*, b
*on the uniform colour space forming, with coordinate, represent the colorimeter system of color, therefore also brief note is CIELAB.The L that represents brightness
*in, L
*=0 represents black, L
*=100 represent white diffusion look.In addition, a
*during for negative value, show partially green, a
*for on the occasion of time show partially purplish red; b
*during for negative value, show indigo plant partially, b
*for on the occasion of time show partially yellow.
For the L with in CIE1976 colorimeter system
*the oxide evaporation material of the present invention of value regulation, preferably its sintered compact surface is identical with the tone of sintered compact inside, if but the different oxide evaporation material of the inner tone of the color harmony of outmost surface is stipulated the L of sintered compact inside in the present invention
*value.
According to contriver, wait the experiment of carrying out, when the inside of oxide evaporation material L* value is 54～75, even if the oxygen amount importing in film forming vacuum tank is few, also can obtain the nesa coating that there is high conductivity and have high permeability in visible region concurrently.In addition, color is whiter, L
*value is just higher, and opposite color is more black, L
*value is just lower.In addition, consider the L of oxide evaporation material
*oxygen level in value and oxide evaporation material has dependency, thinks L
*be worth greatlyr, oxygen level is just more, L
*be worth littlely, oxygen level is just less.The changes such as the inventor are created conditions and are used and have various L
*the oxide evaporation material of value, attempts producing by vacuum vapour deposition the experiment of nesa coating, finds L
*be worth greatlyr, import to optimum oxygen (for obtaining the oxygen amount of the film of low resistance and high-clarity) in film forming just fewer.This be because, L
*be worth larger oxide evaporation material, the oxygen amount of supplying with from oxide evaporation material self is just more.In addition, oxygen import volume is more, and the composition of performance membrane and oxide evaporation material is poor with regard to larger tendency.Therefore, L
*be worth greatlyr, form and poorly just to become less.
In addition, oxide evaporation material of the present invention has electroconductibility, and the specific conductivity of oxide evaporation material also depends on oxygen level, but also depends on the doping efficiency of density, crystallization particle diameter, tin.Therefore, the specific conductivity of oxide evaporation material and L
*value is not corresponding one to one.
In addition, when vacuum evaporation, from take Indium sesquioxide as main component and the oxide evaporation material of the present invention that contains tin, mainly with In
2o
3-X, SnO
2-Xform produces evaporation particle, and the oxygen in this evaporation particle and chamber absorbs oxygen when reacting, film forming after arrival substrate.In addition, when the energy that evaporation particle has is deposited on substrate after arriving substrate, this energy becomes the drive source that material moves, thereby contributes to the densification of film and strengthen the sticking power to substrate.In addition, the L of oxide evaporation material
*be worth littlely, the oxygen in oxide evaporation material is just fewer, so the aggravation of the anaerobic environment of evaporation particle, so must import more oxygen to vacuum tank, to increase evaporation particle, arrives the ratio of carrying out oxidizing reaction before substrate.Yet evaporation particle because of oxidation consumed energy, thereby imports compared with in the reactive film forming of polyoxy in flight course, is difficult to obtain fine and close and the film high to the closing force of substrate.On the contrary, the few reactive evaporation film-forming of the oxygen of importing more easily obtains high closely sealed and highdensity film, and oxide evaporation material of the present invention can be realized this effect.
At this, if above-mentioned L* value is lower than 54, the oxygen amount in oxide evaporation material is very few, the best oxygen import volume importing in film forming vacuum tank in order to obtain the film of low resistance and high-clarity increases, thereby not only the poor change of the composition of film and oxide evaporation material is large, and can cause in film forming to problems such as the damage change of substrate are large, so be not preferred.On the contrary, if above-mentioned L* value surpasses 75, in oxide evaporation material, contained oxygen amount is too much, and the oxygen being supplied to film from oxide evaporation material is become too much, and its result, cannot obtain the high conductivity film with best anaerobic environment.
In addition, in the Japanese kokai publication hei 5-112866 communique (reference publication) of the related invention of open sputtering method, introduced the sputtering target of the indium oxide sintered body that contains tin, but according to the L* value of the indium oxide sintered body that contains tin of the manufacture method manufacture of recording in reference publication, be 38～49, be lower value (with reference to comparative example 3).Therefore, if by such sintered compact as oxide evaporation material, must increase import to film forming vacuum tank oxygen import volume to obtain best film, so can produce above-mentioned problem, can not reach object of the present invention.
At this, above-mentioned L
*value be 54～75 of the present invention for evaporation oxidate sintered body (oxide evaporation material) can not manufacture by the technology of existing manufacture ITO sintered compact.Be suitable for carrying out the mass-produced oxide evaporation material with appropriate oxygen amount (or oxygen deficit) by vacuum vapour deposition, can manufacture by following method.
; take Indium sesquioxide as main component and the oxidate sintered body that contains tin; can manufacture by following method: using Indium sesquioxide and stannic oxide powder separately as raw material; mix these powder; and make its moulding, form powder compact, at high-temperature firing; make its reaction and sintering, manufacture thus described oxidate sintered body.Indium sesquioxide and stannic oxide powder is separately not the powder of Te Do, uses adopted raw material for oxidate sintered body all the time.In addition, the median size of the powder of use is below 1.5 μ m, is preferably 0.1～1.1 μ m.
During as the above-mentioned oxidate sintered body of manufacture, the hybrid system of general raw material powder, utilizes ball mill hybrid system, and the method is also effective to manufacturing sintered compact of the present invention.Ball mill is that the hard balls such as pottery (sphere diameter 10～30mm) and material powder are put in container and are rotated, on one side thus on one side ground material mix to make the device of fine mixed powder.In ball mill (crushing medium), as tank body, adopt steel, stainless steel, nylon etc., as liner, adopt aluminum oxide, magnetic material, natural silica, rubber, urethanum etc.Ball has take alumina balls, the natural silica that aluminum oxide is main component, the nylon ball that adds iron core, zirconia ball etc.Have wet type and dry type breaking method, the method is widely used in as obtaining mixing and the pulverizing of the raw material powder that sintered compact carries out.
In addition, the method outside mixing as ball mill, bead mill method and jet mill method are also effective.Particularly, because stannic oxide powder is mechanically resistant material, so the method is when being used the larger raw material of median size, or very effective must be pulverized and mixed at short notice time.Bead mill method refers to, fills 70～90% bead (crushing medium, bead diameter 0.005～3mm) in the container that is called vessel (vessel), and the turning axle of vessel central authorities is rotated so that bead motion with the circumferential speed of 7～15 meter per seconds.At this, utilize pump, raw material powder etc. is blended in liquid by crushed material and the slurry forming is sent in container, and itself and bead are collided, carry out thus Crushing of Ultrafine and dispersion.When using bead mill, according to reduced bead diameter by crushed material, can raise the efficiency.In general, bead mill can be realized Crushing of Ultrafine and mixing with the acceleration of nearly 1,000 times of ball mill.The bead mill of this structure is called as various titles, for example, knownly there are sand mill, batch-type wet type pearl agitator mill (ア Network ア マ イ ザ イ ー), attritor (attritor), pearl shredder (pearl mill), ABEX type shredder, Ultra-micro-grinding machine (Ultra visco mill), wear promise grinding machine (DYNO-mill), agitator mill (ア ジ テ ー タ ー ミ Le), Double cone shape sand mill (Coball-Mill), spike mill (ス パ イ Network ミ Le), SC shredder etc., in the present invention, can use any.In addition, jet mill refers to, the high-pressure air or the steam that from nozzle, with the speed of velocity of sound left and right, spray are carried out to ultra-high speed injection, and it is collided by crushed material raw material powder etc., is ground into the method for particulate by the collision between particle.
As mentioned above, first indium oxide powder and stannic oxide powder are put into ball mill with in tank in required ratio, and modulate mixed powder by dry type or wet mixing.Then, in order to obtain oxidate sintered body of the present invention, the blending ratio of above-mentioned raw materials powder is modulated so that the content of indium and tin counts 0.001～0.614 with Sn/In atomicity ratio.
In the mixed powder of so modulation, add the organism such as water, dispersing material and binding agent to manufacture slurry.The viscosity of slurry is preferably 150～5000cP, more preferably 400～3000cP.
Use the slurry obtain like this, utilize spray-drier etc. to make it dry, obtain thus prilling powder.But, in order to obtain more evenly and the good sintered compact of coking property, carry out following utilizing being pulverized and mixed while processing of bead mill more effective.
That is the container of, resulting slurry and bead being put into bead mill is pulverized and mixed processing.As bead material, can enumerate zirconium white, aluminum oxide etc., but from the viewpoint of wear resistance, preferential oxidation zirconium.From the viewpoint of crush efficiency, the diameter of bead is preferably 1～3mm.Number of pass times also can be for once, yet more than preferably twice, five times following can obtain sufficient effect.In addition, as the treatment time, preferably below 10 hours, more preferably 4～8 hours.
By this processing, the indium oxide powder in slurry and stannic oxide powder are pulverized well and are mixed.
Next, use the slurry through above-mentioned processing to carry out moulding.As forming method, can adopt any in casting moulding, compression molding method.While carrying out cast molding, resulting slurry is injected into cast molding with manufacturing formed body in mould.Time from the processing of bead mill to cast molding is preferably in 10 hours.This is because can prevent that thus gained slurry from showing thixotropy.In addition, while carrying out compression molding, in resulting slurry, add the binding agents such as polyvinyl alcohol etc., carry out as required moisture adjusting, then adopt that spray-drier etc. is dried, granulation.The prilling powder of gained is filled in the metal die with specified dimension, thereafter, utilizes pressing machine at 9.8～98MPa (100～1000kg/cm
2) pressure under carry out single shaft extrusion forming to form formed body.The thickness of formed body now, considers in its ablating work procedure afterwards and can shrink, and therefore preferably thickness is set as accessing the thickness of the sintered compact of specified dimension.
If utilize the formed body of being made by above-mentioned mixed powder, can obtain oxidate sintered body of the present invention by normal pressure-sintered method.In addition, while firing to obtain oxidate sintered body by normal pressure-sintered method, as follows.
First, at the temperature of 300～500 ℃, heat resulting formed body about 5～20 hours, take off adhesive treatment.Thereafter, heat up and carry out sintering, in order effectively inner air blister defect to be discharged into outside, heat-up rate is below 150 ℃/h, is preferably below 100 ℃/h, more preferably below 80 ℃/h.Sintering temperature is 1150～1300 ℃, is preferably 1200～1250 ℃, and sintering time is 1～20 hour, is preferably 2～5 hours.In de-adhesive treatment～sintering circuit, importantly with every 0.1m
35 liters/min of above ratios of furnace volume import oxygen in stove.Why in above-mentioned sintering circuit, carrying out the importing of oxygen, is because sintered compact above easily dissociates oxygen and is easy to enter superfluous reduced state at 1150 ℃, so import oxygen in order to prevent above-mentioned state.Once in this operation, form the superfluous sintered compact that imports anaerobic environment, after be difficult to adjust the best oxygen deficit of sintered compact in the oxygen amount adjustment operation proceeded.If the temperature that surpasses 1300 ℃ at firing temperature is carried out above-mentioned operation, even under oxygen environment as described above, dissociating of oxygen also becomes violent, easily enters superfluous reduced state, therefore because of same reasons preferred aforesaid way.In addition, not enough if firing temperature lower than 1150 ℃, causes sintering because temperature is too low, be difficult to obtain having the sintered compact of sufficient intensity, so be not preferred.
After sintering, carry out the oxygen amount of sintered compact and adjust operation.In oxygen amount is adjusted operation, importantly 900～1100 ℃, preferably under the Heating temperature of 950～1050 ℃, carry out, and be more than 10 hours heat-up time.Temperature is cooled to above-mentioned oxygen amount and adjusts the cooling importing oxygen that continues of the Heating temperature of operation on one side and carry out, with 0.1～20 ℃/min, preferably the cooling rate of scope of 2～10 ℃/min is lowered the temperature.
Oxygen amount at sintered compact is adjusted in operation, to the control of furnace inner environment also particularly important, imports in the gas in stove, and the ratio of mixture of oxygen and argon gas (volume ratio) is controlled to O
2in the scope of/Ar=40/60～90/10, with every 0.1m
35 liters/min of above ratios of furnace volume import in stove, and this is important.Such temperature and environment, time are carried out to fine setting, can obtain thus the sintered compact with the L* value of stipulating in the present invention that can effectively use as oxide evaporation material.
When above-mentioned oxygen amount is adjusted Heating temperature in operation lower than 900 ℃, it is slow that the dissociation reaction of oxygen and absorption reaction become, reduction processing uniformly will proceed to sintered compact inside needs spended time, so be not preferred, if and in the temperature that surpasses 1100 ℃, carry out, dissociating excessively acutely of oxygen, cannot obtain the best reduction of carrying out in above-mentioned environment and process, so be not preferred.In addition, if oxygen amount is adjusted the Heating temperature of operation, be less than 10 hours, reduction is processed and cannot be proceeded to sintered compact inside uniformly, so be not preferred.In addition, flow to the ratio of mixture (O of the importing gas in stove
2/ Ar) lower than 40/60, the reducing advantage of dissociating based on oxygen is excessive, thereby forms L
*the sintered compact that value is less than 54, so be not preferred.On the contrary, flow to the ratio of mixture (O of the importing gas in stove
2/ Ar) surpass 90/10, be oxidized advantage excessive, thereby form L
*value surpasses 75 sintered compact, so be not preferred.
In order to obtain oxide evaporation material of the present invention, importantly as mentioned above with argon gas under the atmosphere surrounding of accurate dilution oxygen, carry out anneal under the environment controlled by precision in oxygen amount, but the environmental gas mixed gas of oxygen and argon gas not necessarily.For example, while, replacing other rare gas elementes such as argon gas use helium or nitrogen also effective.In addition, when using atmosphere to replace argon gas, in its whole mixed gas, as long as oxygen level is critically controlled at fixed value, be exactly effective.But, as described in the prior art, oxygen is imported in the stove of firing in atmosphere, now cannot control the oxygen level of environment in stove is accurate, so be not effective.As described in the technical scheme proposing as the present invention, oxygen is obtained to the accurate oxygen of controlling and the mixed gas of rare gas element imports and is full of in stove containing proportional, can obtain having thus the oxide evaporation material of best reduced state.
Then, finish oxygen amount and adjust after operation, be cooled to room temperature with 10 ℃/min, in room temperature, from stove, take out sintered compact.The sintered compact of gained is waited and is processed into specified dimension by grinding, thereby can be used as oxide evaporation material.In addition, also consider the shrinking percentage of sintering, if used, fire the big or small formed body of rear formation specified dimension, even if do not carry out attrition process after sintering, also can be used as oxide evaporation material.
As the method that obtains high-density sintered body of one of manufacture method of sputtering target, known pressure sintering is effective.But, in the situation of material applied heat platen press of the present invention, only obtain L
*value is the excessively strong sintered compact of reductibility below 40.Such sintered compact cannot be reached object of the present invention.
In addition, for oxide evaporation material of the present invention, for example, also can use sheet or the particulate state of cylindrical shape of diameter 10～50mm, height 10～50mm, but also can utilize the particulate state of pulverizing 1～10mm left and right that such sintered compact forms.
In addition, for oxide evaporation material of the present invention, as other elements except indium, tin, oxygen, such as containing tungsten, molybdenum, zinc, cadmium, cerium etc., take and do not damage characteristic of the present invention as condition, can be allowed to.But in metal ion, when the vapour pressure of its oxide compound, compare with the vapour pressure of Indium sesquioxide and stannic oxide when very high, be difficult to adopt various vacuum vapour depositions to make its evaporation, therefore preferably do not contain above-mentioned element.For example, for aluminium, titanium, the such metal of silicon, the vapour pressure of these oxide compounds is compared very high with the vapour pressure of Indium sesquioxide and stannic oxide, so it is while being included in oxide evaporation material, is difficult to evaporate together with stannic oxide with Indium sesquioxide.Therefore, remain in oxide evaporation material and high density, evaporation that finally can hinder Indium sesquioxide and stannic oxide etc. causes detrimentally affect, so must not contain.
In addition, if applicable oxide evaporation material of the present invention is also manufactured nesa coating by various vacuum vapour depositions, the oxygen level in above-mentioned oxide evaporation material is adjusted to optimum content, even if it is few therefore to flow to the oxygen import volume of film forming vacuum tank, also can obtain the nesa coating under best anoxia condition.Therefore, there is following advantage: the composition between nesa coating and oxide evaporation material is poor little, be difficult to be subject to follow the impact of the characteristic deviation that the change of oxygen import volume causes.
(2) nesa coating
Oxide evaporation material of the present invention forms as main component and the oxidate sintered body that contains tin by take Indium sesquioxide, the content of tin counts 0.001～0.614 with Sn/In atomicity ratio, and the L* value in CIE1976 colorimeter system is 54～75, adopt oxide evaporation material of the present invention and by various vacuum vapour depositions such as the auxiliary vapour deposition methods of electron beam evaporation plating method, ion plating method or high density plasma, can manufacture the Indium sesquioxide crystalline film (nesa coating) that contains tin.
By being crystalline film, when the displacement solid solution of the indium position of the oxidized indium of tin, can bring into play high mobility.Above-mentioned crystalline film (nesa coating) is to obtain at 180 ℃ of above temperature by the base plate heating in film forming, yet, also can adopt at more than 180 ℃ temperature, the method for the film by the non-heating film forming of heated substrates does not obtain being carried out to anneal obtains.
In addition, crystallinity nesa coating of the present invention can be manufactured by forming of film and oxide evaporation material of poor less oxide evaporation material, so this crystallinity nesa coating is to contain with Sn/In atomicity than the indium oxide film of counting 0.001～0.614 tin.If the tin content of film (Sn/In atomicity ratio) is lower than 0.001, carrier concn increase effect (being that mobility increases effect) is little, cannot obtain low-resistance film.In addition, if tin content surpasses 0.614, the tin amount in film is too much, and it is large that neutral impurity degree of scatter when electronics is moved becomes, and is subject to the impact that mobility reduces and cannot obtains low resistance film.In order to obtain the nesa coating of higher carrier concn, as preferred tin content, with Sn/In atomicity ratio, count 0.040～0.163, and film is crystalline film.By obtaining the crystalline film of such compositing range, can realize carrier concn is 7.2 * 10
20cm
-3than resistance, be 3.5 * 10 above,
-4nesa coating below Ω cm.In addition, the average transmittances of nesa coating of the present invention film self in wavelength 400～800nm is more than 90%, very high.
Below, for embodiments of the invention, be specifically described.
[embodiment 1～4]
[making of oxide evaporation material]
By median size, be the In of 0.8 μ m
2o
3powder and median size are the SnO of 1 μ m
2powder, as raw material powder, is concocted these according to the atomicity of Sn/In than the ratio that is 0.048
2o
3powder and SnO
2powder, and put in resin tank, with wet-type ball mill, mix.Now, use hard ZrO
2ball, mixing time is made as 20 hours.
After mixing, take out slurry, in resulting slurry, add the binding agent of polyvinyl alcohol, with dry and granulations such as spray-driers.
Use this granules at 98MPa (1ton/cm
2) pressure under carry out single shaft extrusion forming, obtain the formed body of the cylindrical shape of diameter 30mm, thickness 40mm.
Then, in the following manner the formed body of gained is carried out to sintering.
That is, in the atmosphere in sintering oven, under the temperature condition of 300 ℃, heat about 10 hours, carry out the de-adhesive treatment of formed body, then, with every 0.1m
3the ratio that furnace volume is 5 liters/min imports under the environment of oxygen, heats up, in 1250 ℃ of sintering 2 hours (normal pressure-sintered method) with the speed of 1 ℃/min.Now, when cooling after sintering, also limit imports oxygen limit and is cooled to 1000 ℃ with the speed of 10 ℃/min.
Then, will import gas and be replaced by the mixed gas of oxygen and argon gas, 1000 ℃ of heating, keep, after 15 hours (after, this operation is called to sintered compact oxygen amount and adjusts operation), with the speed of 10 ℃/min, being cooled to room temperature.
Then, by changing the blending ratio of oxygen and the argon gas of above-mentioned mixed gas, can obtain various L
*the oxidate sintered body (oxide evaporation material) of value.
; under the condition that the oxide evaporation material of embodiment 1 is is [40/60] in oxygen/argon throughput ratio (being volume ratio), manufacture; under the condition that the oxide evaporation material of embodiment 2 is is [60/40] in above-mentioned volume ratio, manufacture; under the condition that the oxide evaporation material of embodiment 3 is is [80/20] in above-mentioned volume ratio, manufacture, and the oxide evaporation material of embodiment 4 is to manufacture under the condition for [90/10] in above-mentioned volume ratio.
In addition, the volume and weight of the oxidate sintered body of gained (oxide evaporation material) is measured, calculating density is 4.8～5.7g/cm
3.In addition, by scanning electron microscope, observe the surface of fracture of above-mentioned oxidate sintered body, thereby obtain the mean value of 100 crystallization particle diameters in oxidate sintered body, be 3～10 μ m.In addition, utilize four probe method resistivity meter, the electron beam irradiation face of oxidate sintered body is measured to surface resistivity, calculating than resistance is below 1k Ω cm.And, with ICP luminescence analysis, all oxidate sintered bodies are carried out to compositional analysis, known have a composition that feeds intake.In addition, utilize colour-difference meter (Spectro-Guide, E-6834 that BYK-Gardner GmbH society manufactures) to measure sintered compact surface and the L of sintered compact inside in CIE1976 colorimeter system
*value, its result shows almost identical value.
By the oxygen/argon throughput ratio (being volume ratio) of mixed gas importing in sintered compact oxygen amount adjustment operation and the L of the oxidate sintered body (oxide evaporation material) of gained
*value representation is in following table 1 (a), table 1 (b) and table 1 (c).
Table 1 (a)
Table 1 (b)
Table 1 (c)
[making of nesa coating and membrane property evaluation, film forming evaluation]
(1) in the making of nesa coating, use magnetic core logical circuit deflection type electron beam evaporation plating device.
Vacuum evacuating system consists of with the high-vacuum exhaust system with cryopump the rough vacuum exhaust system with rotor pump, can vacuum exhaust to 5 * 10
-5pa.Electron beam is by the thermogenesis that adds of filament, and is applied in the electric field acceleration between K-A, after being bent, is irradiated on the oxide evaporation material being arranged in tungsten crucible processed in the magnetic field of Permanent magnet.Electron beam intensity can be applied to and be applied voltage adjustment on filament by change.In addition, if change the acceleration voltage between K-A, can make the irradiation position of electron beam change.
Film forming is implemented by following condition.
By Ar gas and O
2gas imports in vacuum chamber, thereby keep pressure, is 1.5 * 10
-2pa.Now, change and import to Ar gas and the O in vacuum chamber
2the blending ratio of gas, obtains nesa coating, and its characteristic is evaluated.The cylindric oxide evaporation material of embodiment 1～4 is erected and is configured in tungsten crucible processed, rounded face central part irradiating electron beam to oxide evaporation material, thus the nesa coating of thickness 200nm on the glass substrate that is Corning7059 in the model of thickness 1.1mm, formed.The setting voltage of electron beam gun is that 9kV, current value are 150mA, base plate heating to 250 ℃.
(2) in the following order the characteristic of the film of gained (nesa coating) is evaluated.
First, with four probe method resistivity meter LORESTA EP (manufacture of Dia Instruments society, MCP-T360 type), the surface resistivity of film (nesa coating) is measured, utilize contact surfaceness meter (manufacture of Tencor society) measure into membrane portions and become the thickness difference of membrane portions in order to evaluate the thickness of film (nesa coating), calculate [than resistance (μ Ω cm)].And then, using Hall effect determinator (ResiTest that Dongyang Technica society manufactures), the film of mensuration based on vanderburg (Van der Pauw) method is at [carrier concn (the cm of room temperature
-3)], [hall mobility (cm
2/ Vs)].
Secondly, utilize spectrophotometer (manufacture of Hitachi society, U-4000) to measure the transmitance [T of the film (with the glass substrate B of film L) that comprises glass substrate
l+B(%)], adopt identical method to measure only the transmitance [(T of glass substrate (glass substrate B)
b(%)], then by [T
l+B÷ T
bthe transmitance of membrane self is calculated in] * 100 (%).
In addition, by X-ray diffraction, measure the crystallinity of evaluated for film.X-ray diffraction device is used X, PertPROMPD device (manufacture of PANalytical society), and condition determination is wide area test, uses CuK alpha-ray, and measures under the condition of voltage 45kV, electric current 40mA.According to having or not X-ray diffraction peak to carry out the crystallinity of evaluated for film.Its result is also shown in table 1 (c) [crystallinity of film] hurdle.
Secondly, the composition of film (the atomicity ratio of Sn/In) is measured with ICP luminescence analysis.In addition, film is evaluated according to JIS C0021 the sticking power of substrate.While not having film to peel off, be evaluated as good (by force), while existing film to peel off, be evaluated as insufficient (weak).These results are also illustrated in table 1 (c) [the atomicity ratio of Sn/In] and [sticking power of film to substrate] each hurdle.
The ratio resistance of each film (nesa coating) and transmitance depend on and in film process, import to Ar gas and the O in film forming vacuum tank
2the blending ratio of gas.Make O
2blending ratio [the O of gas
2/ (Ar+O
2) (%)] in 0～50% scope, change every 1%, will show the O of low resistivity
2the blending ratio of gas is defined as best oxygen combined amount.This result is illustrated in to [best oxygen combined amount] hurdle of table 1 (a).
Be less than not only poorly conductive and also low in the transmitance of visible region of the film (nesa coating) made under the oxygen amount of best oxygen combined amount.Not only electroconductibility is good for the film of making under best oxygen combined amount (nesa coating), and also high in the transmitance of visible region.
(3) use the oxide evaporation material of embodiment 1～4, obtain the ratio resistance of best oxygen combined amount when implementing above-mentioned film forming evaluation, film now, the average transmittances of the film self of (wavelength 400～800nm) in visible region.
These evaluation results are illustrated respectively in table 1 (b) [than resistance (μ Ω cm)] and [transmitance of the visible region of film self (%)] hurdle.
In the film forming of the oxide evaporation material of use embodiment 1～4, in order to obtain the nesa coating of most low-resistance and high-permeability, the best oxygen combined amount that requirement imports in film forming vacuum tank is considerably less.This is because each oxide evaporation material contains optimum oxygen.In addition, the film of manufacturing under best oxygen combined amount shows the composition identical with oxide evaporation material, thereby not only shows low-downly than resistance, and in visible region, also shows high permeability.In addition, confirm that film is the Indium sesquioxide crystalline film of bixbyite type structure, it is also strong to the sticking power of substrate, is sufficient in practicality.
And the setting voltage of electron beam gun is that 9kV, current value are 150mA.With electron beam irradiation, after 60 minutes, observe oxide evaporation material, whether range estimation oxide evaporation material there is breakage or crackle (oxide evaporation material long duration test).For the oxide evaporation material of embodiment 1～4, even if use continuously, do not crack (evaluation of [without damaged]) yet.
Such nesa coating can be said very useful as the transparency electrode of solar cell.
[comparative example 1～2]
As embodiment 1～4, but only change the ratio of mixture that sintered compact oxygen amount is adjusted the importing gas in operation, manufacture oxidate sintered body.That is, in comparative example 1, by O
2/ Ar throughput ratio is set as 30/70, in comparative example 2 by O
2/ Ar throughput ratio is set as 100/0.For the sintered compact of gained similarly evaluate density, than resistance, crystallization particle diameter, composition, its result and embodiment 1～4 peer-level.The surface of the oxidate sintered body of gained and inner tone peer-level, measure its L
*during value, the value shown in indicator gauge 1 (a).
Next, same with embodiment 1～4, implement film forming evaluation.
Its result is also illustrated in above-mentioned table 1 (a)～(c).
Comparative example 1 has following characteristics: oxide evaporation material is L
*value shows the oxide evaporation material of the value (49) that is less than specialized range of the present invention (54～75), and compares with the oxide evaporation material of embodiment 1～4, and the best oxygen combined amount (15) during film forming is many.The characteristic of the film under best oxygen combined amount is compared with embodiment 1～4, although transmitance is peer-level, higher than resistance.Its major cause is thought the large cause of composition deviation of film.And the film of comparative example 1 is weaker than embodiment 1～4 to the sticking power of substrate.Its reason is thought, carries out the cause of film forming during film forming in the situation that importing compared with polyoxy.Such oxide evaporation material, because the composition deviation of the film of gained is large, forms so be difficult to design film.In addition, owing to more oxygen need to being imported in film forming vacuum tank, institute during for film forming mass-production process, is subject to the impact of the oxygen concn change in vacuum tank, forms or the change of characteristic can strengthen.Therefore, the oxide evaporation material of comparative example 1 is confirmed to be and is not suitable for film forming batch production.
In addition, comparative example 2 is examples that L* value shows the oxide evaporation material of the value (79) that is greater than specialized range of the present invention.Although best oxygen combined amount during film forming is 0%, the ratio resistance of film is higher than the ratio resistance of embodiment 1～4.Its reason is thought, by oxide evaporation material, is offered the hyperoxia of film and is made the oxygen amount in film many, therefore cannot import best oxygen deficit.Therefore, can confirm, even if utilize such oxide evaporation material film forming, also cannot obtain bringing into play the film that this deposition material forms the high conductivity originally having.
[comparative example 3]
Next, according to the sintered compact manufacturing technology of the sputtering target of introducing in Japanese kokai publication hei 5-112866 communique (reference publication), manufacture the indium oxide sintered body that contains tin.
First, by median size, be the In below 1 μ m
2o
3powder and median size are the SnO below 1 μ m
2powder, as raw material powder, is concocted according to the atomicity of Sn/In than the ratio that is 0.048
2o
3powder and SnO
2powder, and put in resin tank, with wet-type ball mill, mix.Now, use hard ZrO
2ball, mixing time is 20 hours.After mixing, take out slurry, filter, dry after by its granulation.
Then, use the pelletizing of gained, applying 196MPa (2ton/cm
2) the condition of pressure under by cold isostatic press, implement moulding, and then the formed body of gained is put into sintering oven, in atmosphere in 1520 ℃ of sintering 5 hours.
The sintered compact of gained is processed into the cylindrical shape of diameter 30mm, thickness 40mm size.The density of sintered compact is 6.0g/cm
3, than resistance, be 0.6m Ω cm.In addition, crystallization particle diameter is 12～15 μ m, forms with the composition that feeds intake roughly the same.The surface of resulting sintered compact and inner tone are peer-levels, measure its L
*value, as shown in table 1 (a), shows extremely low value (38).This represents that the oxygen amount in oxide evaporation material is considerably less.
In addition, same with embodiment 1～4, implement film forming evaluation.
Its result is also illustrated in above-mentioned table 1 (a)～(c).
In comparative example 3, L
*value shows the value (38) that is significantly less than specialized range of the present invention (54～75).Compare the best oxygen combined amount very many (42) during film forming with the oxide evaporation material with the embodiment 1～4 of same composition.The characteristic of the film under best oxygen combined amount is compared with embodiment 1～4, although transmitance is peer-level, higher than resistance.Its major cause is thought the large cause of composition deviation of film.And the film of comparative example 3 is weaker than embodiment 1～4 to the sticking power of substrate.Its reason is thought, carries out the cause of film forming during film forming in the situation that importing volume oxygen.Such oxide evaporation material, because the composition deviation of the film of gained is large, forms so be difficult to design film.In addition, owing to more oxygen need to being imported in film forming vacuum tank, institute during for film forming mass-production process, is subject to the impact of the oxygen concn change in vacuum tank, forms or the change of characteristic can strengthen.In addition, under the condition identical with embodiment 1～4, carry out oxide evaporation material long duration test, its result, cracks (evaluation of [breakage]) on the oxide evaporation material after continuous film forming.If use such generation the oxide evaporation material of crackle carry out continuously film forming, produce the problems such as film forming speed change is large and cannot stablize film forming.
Therefore, the oxide evaporation material of comparative example 3 is confirmed to be the batch production that is not suitable for film forming.
[embodiment 5～8]
At blending In
2o
3powder and SnO
2during powder, take the atomicity of Sn/In than concocting as 0.102 ratio, in addition, comprise the condition that sintered compact oxygen amount is adjusted, condition is identical with embodiment 1～4, makes the oxidate sintered body (oxide evaporation material) of embodiment 5～8.
; under the condition that the oxide evaporation material of embodiment 5 is is [40/60] in oxygen/argon throughput ratio (being volume ratio), manufacture; under the condition that the oxide evaporation material of embodiment 6 is is [60/40] in above-mentioned volume ratio, manufacture; under the condition that the oxide evaporation material of embodiment 7 is is [80/20] in above-mentioned volume ratio, manufacture, and the oxide evaporation material of embodiment 8 is to manufacture under the condition for [90/10] in above-mentioned volume ratio.
Then, the oxidate sintered body (oxide evaporation material) to the embodiment 5～8 of gained, similarly evaluates density, than resistance, crystallization particle diameter, composition, result all with embodiment 1～4th, peer-level.In addition, the surface of the oxidate sintered body of gained and inner tone are also peer-levels.Measure its L
*value, shows the result in above-mentioned table 1 (a).
In addition, same with embodiment 1～4, implement film forming evaluation.
Its result is also illustrated in above-mentioned table 1 (a)～(c).
In the film forming of the oxide evaporation material of use embodiment 5～8, in order to obtain the nesa coating of most low-resistance and high-permeability, same with embodiment 1～4, the best oxygen combined amount that should import in film forming vacuum tank is considerably less.This is because oxide evaporation material contains optimum oxygen.In addition, the film of manufacturing under best oxygen combined amount shows the composition identical with oxide evaporation material, thereby not only shows low-downly than resistance, and in visible region, also shows high permeability.In addition, the crystalline film of the bixbyite type crystalline texture that whole films is Indium sesquioxide, film is also strong to the sticking power of substrate, is sufficient in practicality.And then, even if use continuously the oxide evaporation material of embodiment 5～8, do not crack yet.
Such nesa coating can be said very useful as the transparency electrode of solar cell.
[comparative example 4～5]
As comparative example 1～2, but will concoct In
2o
3powder and SnO
2sn/In atomicity ratio during powder is set as 0.102, in addition, under the condition identical with comparative example 1～2, manufactures oxide evaporation material.That is condition O in comparative example 4 that, sintered compact oxygen amount is adjusted
2/ Ar throughput ratio is 30/70, O in comparative example 5
2/ Ar throughput ratio is 100/0.For the density of the sintered compact of gained, than resistance, crystallization particle diameter, form and similarly evaluate, its result and embodiment 5～8th, peer-level.In addition, the surface of the sintered compact of gained and inner tone are peer-levels, while measuring its L* value, and the value shown in indicator gauge 1 (a).
Next, same with embodiment 1～4, implement film forming evaluation.
Its result is also illustrated in table 1 (a)～(c).
Comparative example 4 is L
*value shows the example of the oxide evaporation material of the value (50) be less than specialized range of the present invention (54～75), with use embodiment 5～8 oxide evaporation material time compare, the best oxygen combined amount (15) during film forming is many.The characteristic of the film under best oxygen combined amount is compared with embodiment 5～8, although transmitance is roughly the same, higher than resistance.Its reason thinks that the composition deviation of film is large, the excessive cause that contains tin in film.And the film of comparative example 4 is weaker than embodiment 5～8 to the sticking power of substrate.Large composition deviation like this and the major cause of low sticking power are all when film forming, in the situation that importing compared with polyoxy, to carry out the cause of film forming.Such oxide evaporation material, because the composition deviation of the film of gained is large, forms so be difficult to design film.In addition, owing to more oxygen need to being imported in film forming vacuum tank, institute during for film forming mass-production process, is subject to the impact of the oxygen concn change in vacuum tank, makes to form or the change of characteristic becomes obviously easily.Therefore, the oxide evaporation material of comparative example 4 is also confirmed to be and is not suitable for film forming batch production.
In addition, comparative example 5 is examples that L* value shows the oxide evaporation material of the value (82) that is greater than specialized range of the present invention.Best oxygen combined amount during film forming is 0%, but the ratio resistance of film is higher than the ratio resistance of embodiment 5～8.Its reason is thought, is offered the hyperoxia of film and is made the oxygen amount in film many, thereby cannot import best oxygen deficit by oxide evaporation material.Therefore, can confirm, even if utilize such oxide evaporation material film forming, also cannot obtain bringing into play the film that this oxide evaporation material forms the high conductivity originally having.
[comparative example 6]
As comparative example 3, but will concoct In
2o
3powder and SnO
2sn/In atomicity ratio during powder is set as 0.102, in addition, with the same condition of comparative example 3 under manufacture oxide evaporation material.For the sintered compact of gained similarly evaluate density, than resistance, crystallization particle diameter, composition, its result and comparative example 3 are peer-levels.In addition, the surface of the sintered compact of gained and inner tone are peer-levels, measure its L
*during value, the value shown in indicator gauge 1 (a).
Next, same with embodiment 1～4, implement film forming evaluation.
Its result is also illustrated in above-mentioned table 1 (a)～(c).
L in comparative example 6
*value also shows the value (49) that is significantly less than specialized range of the present invention (54～75).Compare with the oxide evaporation material of the embodiment 5～8 of same composition, the best oxygen combined amount (42) during film forming is very many.The characteristic of the film under best oxygen combined amount is compared with embodiment 5～8, although transmitance is peer-level, higher than resistance.Its major cause is thought the large cause of composition deviation of film.And the film of comparative example 6 is weaker than embodiment 5～8 to the sticking power of substrate.This is because carry out the cause of film forming during film forming in the situation that importing compared with polyoxy.Such oxide evaporation material, because the composition deviation of the film of gained is large, forms so be difficult to design film.In addition, owing to more oxygen need to being imported in film forming vacuum tank, institute during for film forming mass-production process, is subject to the impact of the oxygen concn change in vacuum tank, forms or the change of characteristic can strengthen.In addition, under the condition identical with embodiment 1～4, carry out oxide evaporation material long duration test, its result, cracks (evaluation of [breakage]) on the oxide evaporation material after continuous film forming.If use such generation the oxide evaporation material of crackle carry out continuously film forming, produce the problems such as film forming speed change is large and cannot stablize film forming.
By above content, can confirm that the oxide evaporation material of comparative example 6 is also not suitable for the batch production of film forming.
[embodiment 9～14]
Change blending In
2o
3powder and SnO
2blending ratio during powder is so that Sn/In atomicity ratio is 0.001 (embodiment 9), 0.009 (embodiment 10), 0.028 (embodiment 11), 0.163 (embodiment 12), 0.230 (embodiment 13) and 0.614 (embodiment 14), in addition, at the lower oxidate sintered body (oxide evaporation material) of manufacturing embodiment 9～14 of the condition identical with embodiment 2 (that is, oxygen/argon throughput ratio is the condition of [60/40]).
Then, the oxidate sintered body (oxide evaporation material) to the embodiment 9～14 of gained, similarly evaluates density, than resistance, crystallization particle diameter, composition, and result is all peer-levels with embodiment 2.In addition, the surface of the oxidate sintered body of gained and inner tone are peer-levels.Measure its L* value, show the result in table 1 (a).
In addition, same with embodiment 1～4, implement film forming evaluation.
Its result is also illustrated in above-mentioned table 1 (a)～(c).
In the film forming of the oxide evaporation material of use embodiment 9～14, in order to obtain the nesa coating of most low-resistance and high-permeability, same with embodiment 1～4, the best oxygen combined amount that should import in film forming vacuum tank is considerably less.This is because oxide evaporation material contains optimum oxygen.In addition, the film of manufacturing under best oxygen combined amount shows the composition identical with oxide evaporation material, thereby not only shows low-downly than resistance, and shows high permeability in visible region.In addition, confirm that whole films is the crystalline film of the bixbyite type crystalline texture of Indium sesquioxide, film is also strong to the sticking power of substrate, is sufficient in practicality.In addition, under the condition identical with embodiment 1～4, carry out oxide evaporation material long duration test, consequently, even if the oxide evaporation material of embodiment 9～14 is used continuously, also do not crack.
Such nesa coating can be said very useful as the transparency electrode of solar cell.
[comparative example 7]
Next, manufacture the ITO oxide evaporation material of introducing in Japanese kokai publication hei 8-104978 communique (patent documentation 1), and carry out same evaluation.
That is, in the indium oxide powder of median size 0.1 μ m, coordinate the stannic oxide powder of median size 1 μ m so that Sn/In atomicity than 0.102, is added the vinyl-acetic ester of 2 quality % is binding agent.It is mixed in wet-type ball mill 16 hours, after being dried and pulverizing, make prilling powder.And then, use this prilling powder, with cold isostatic press, apply 49MPa (500kgf/cm
2) pressure, make columned formed body.This formed body is carried out in atmosphere to sintering.In sintering circuit, make temperature be increased to 600 ℃ from room temperature with 10 hours, with 4 hours 40 minutes, be increased to 1450 ℃.Then, in 1450 ℃ of maintenances 10 hours, obtain sintered compact.
The sintered compact of gained is processed into the cylindrical shape of diameter 30mm, thickness 40mm size, as ITO oxide evaporation material.The density of sintered compact is 4.4g/cm
3, than resistance, be 1.2m Ω cm.Crystallization particle diameter is 12～16 μ m, forms with the composition that feeds intake roughly the same.The surface of sintered compact and inner tone are peer-levels, measure its L
*value, as table 1 (a) is depicted as extremely low value (49).This represents that the oxygen amount in oxide evaporation material is considerably less.
In addition, same with embodiment 1～4, implement film forming evaluation.
Its result is also illustrated in above-mentioned table 1 (a)～(c).
In comparative example 7, L* value also shows the value (49) that is significantly less than as mentioned above specialized range of the present invention (54～75), compares with the oxide evaporation material of embodiment 5～8, and the best oxygen combined amount (42) during film forming is very many.The characteristic of the film under best oxygen combined amount is compared with embodiment 5～8, although the transmitance of visible region is peer-level, higher than resistance.Its major cause is thought the large cause of composition deviation of film.And the film of comparative example 7 is weaker than embodiment 5～8 to the sticking power of substrate.This is because carry out film forming during film forming in the situation that importing volume oxygen.Such oxide evaporation material, because the composition deviation of the film of gained is large, forms so be difficult to design film.In addition, owing to more oxygen need to being imported in film forming vacuum tank, institute during for film forming mass-production process, is subject to the impact of the oxygen concn change in vacuum tank, forms or the change of characteristic can strengthen.In addition, under the condition identical with embodiment 1～4, carry out oxide evaporation material long duration test, its result, cracks (evaluation of [breakage]) on the oxide evaporation material after continuous film forming.If use such generation the oxide evaporation material of crackle carry out continuously film forming, produce the problems such as film forming speed change is large and cannot stablize film forming.
By above content, can confirm that the oxide evaporation material of comparative example 7 is also not suitable for the batch production of film forming.
[comparative example 8]
In addition, manufacture the ITO oxide evaporation material of introducing in TOHKEMY 2007-84881 communique (patent documentation 2), and carry out same evaluation.
That is, coordinate the stannic oxide powder below median size 1 μ m so that Sn/In atomicity ratio is 0.102 in the indium oxide powder below median size 1 μ m, the vinyl-acetic ester that adds 2 quality % is binding agent.Use hard ZrO
2ball mixes it 18 hours in wet-type ball mill, after being dried and pulverizing, makes prilling powder.And then, use this prilling powder, with cold isostatic press, apply 94MPa (3ton/cm
2) pressure, make columned formed body.
The formed body of gained is put into sintering oven, every 0.1m
3furnace volume imports oxygen with the ratio of 5 liters/min, forms environment, normal pressure-sintered 2 hours in 1100 ℃.Now, with the speed of 1 ℃/min, heat up, when cooling after sintering, stop importing oxygen, with 10 ℃/min, be cooled to 1000 ℃.
Use vertical machining centre to be processed into the cylindrical shape of diameter 30mm, thickness 40mm size the oxidate sintered body of gained, measure volume and weight, calculate density.
The density of sintered compact is 4.8g/cm
3.In addition, the surface of sintered compact and inner tone are peer-levels, measure its L
*value, as shown in table 1 (a), compares with specialized range of the present invention (54～75), shows higher value (79).This represents that the oxygen amount in oxide evaporation material is very many.
Use the oxide evaporation material of so making, similarly implement film forming evaluation with embodiment 1～4.
Best oxygen combined amount during film forming is identical with comparative example 2, is 0%, but film than the height of resistance ratio embodiment 5～8.Its reason is thought, is offered the hyperoxia of film and is made the oxygen amount in film many, thereby cannot import best oxygen deficit by oxide evaporation material.Therefore, can confirm, even if utilize such oxide evaporation material film forming, also cannot obtain bringing into play the film that this deposition material forms the high conductivity originally having.
Industrial applicibility
The oxide evaporation material of the application of the invention, adopt vacuum vapour deposition can produce the nesa coating in visible region demonstration high light transmittance and demonstration high conductivity, therefore, the oxide evaporation material that can be used as the transparency electrode that is used to form various solar cells is applied, and has industrial practicality.
Claims (5)
1. an oxide evaporation material, it is characterized in that, it forms as main component and the oxidate sintered body that contains tin by take Indium sesquioxide, and the content of tin counts 0.001～0.614 with Sn/In atomicity ratio, and the L* value in CIE1976 colorimeter system is 54～75.
2. oxide evaporation material as claimed in claim 1, is characterized in that, the content of described tin counts 0.040～0.163 with Sn/In atomicity ratio.
3. a nesa coating, it be take Indium sesquioxide as main component and contains tin, it is characterized in that, it is by requiring the oxide evaporation material described in 1 as raw material right to use and assisting the crystallinity nesa coating of vapour deposition method film forming to form by electron beam evaporation plating method, ion plating method or high density plasma, and the content of tin counts 0.001～0.614 with Sn/In atomicity ratio.
4. nesa coating as claimed in claim 3, it is characterized in that, it is by requiring the oxide evaporation material described in 2 as raw material right to use and assisting the crystallinity nesa coating of vapour deposition method film forming to form by electron beam evaporation plating method, ion plating method or high density plasma, and the content of tin be take Sn/In atomicity ratio and is counted 0.040～0.163, is 3.5 * 10 than resistance
-4below Ω cm.
5. a manufacture method for oxide evaporation material, the oxide evaporation material that it is manufactured described in claim 1, is characterized in that having following operation:
Prilling powder manufacturing process, this prilling powder manufacturing process adopts ball mill hybrid system, bead mill method or jet mill method, so that the content of tin with Sn/In atomicity than the mode of counting 0.001～0.614, indium oxide powder and stannic oxide powder are obtained by mixing to mixed powder as raw material, and, in resulting mixed powder, add water, dispersing material and binding agent to manufacture after slurry, make slurry drying and carry out granulation to obtain prilling powder;
Formed body preparation section, this formed body preparation section adopts casting moulding, compression molding method to carry out moulding to manufacture formed body to the prilling powder obtaining;
De-binding agent and sintering circuit, this de-binding agent and sintering circuit are with every 0.1m
3the above ratios of 5 liters/min of furnace volumes when importing oxygen in stove, heat and within 5～20 hours, take off adhesive treatment above-mentioned formed body at the temperature of 300～500 ℃, and with every 0.1m
3the above ratios of 5 liters/min of furnace volumes when importing oxygen in stove, after heating up, are carried out sintering processes 1～20 hour the temperature of 1150～1300 ℃ with 150 ℃/h of following heat-up rates;
Refrigerating work procedure, is cooled to the Heating temperature of following oxygen amount adjustment operation while this refrigerating work procedure continues to import oxygen after sintering with the cooling rate of 0.1～20 ℃/min;
Oxygen amount is adjusted operation, and it is O in the ratio of mixture of oxygen and argon gas that this oxygen amount is adjusted operation
2under the condition of the scope of/Ar=40/60～90/10, and with every 0.1m
3the above ratios of 5 liters/min of furnace volumes when importing the mixed gas of oxygen and argon gas in stove, are carried out above oxygen amount adjustment in 10 hours to sintered compact with the temperature of 900～1100 ℃, and this ratio of mixture is volume ratio; And,
Cooling process, after finishing oxygen amount adjustment operation, is cooled to room temperature with 10 ℃/min.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010-071801 | 2010-03-26 | ||
| JP2010071801A JP5224073B2 (en) | 2010-03-26 | 2010-03-26 | Oxide deposition material and method for producing the same |
| PCT/JP2011/054413 WO2011118334A1 (en) | 2010-03-26 | 2011-02-21 | Oxide deposition material and transparent conductive film |
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| CN102812150A CN102812150A (en) | 2012-12-05 |
| CN102812150B true CN102812150B (en) | 2014-09-17 |
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| CN201180014684.5A Expired - Fee Related CN102812150B (en) | 2010-03-26 | 2011-02-21 | Oxide deposition material and transparent conductive film |
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| Country | Link |
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| JP (1) | JP5224073B2 (en) |
| KR (1) | KR101322800B1 (en) |
| CN (1) | CN102812150B (en) |
| MY (1) | MY159313A (en) |
| TW (1) | TWI422696B (en) |
| WO (1) | WO2011118334A1 (en) |
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| TWI480953B (en) * | 2012-03-30 | 2015-04-11 | Hannstouch Solution Inc | Composite transparent oxide film and manufacturing method for the same |
| CN103999166B (en) * | 2012-06-07 | 2018-01-09 | 日东电工株式会社 | Transparent and electrically conductive film |
| EP2881379A4 (en) * | 2012-07-31 | 2016-03-02 | Sumitomo Metal Mining Co | Oxide sintered body and tablet obtained by processing same |
| WO2017082229A1 (en) * | 2015-11-09 | 2017-05-18 | 日東電工株式会社 | Optically transparent electroconductive film and light control film |
| JP2017154910A (en) * | 2016-02-29 | 2017-09-07 | 住友金属鉱山株式会社 | Oxide sintered body and sputtering target |
| JP6841088B2 (en) * | 2017-03-01 | 2021-03-10 | 堺化学工業株式会社 | Conductive material and electrode material |
| CN114975635A (en) | 2017-05-31 | 2022-08-30 | 乐金显示有限公司 | Thin film transistor, gate driver including the same, and display device including the gate driver |
| CN107266041B (en) * | 2017-06-16 | 2019-06-28 | 福建阿石创新材料股份有限公司 | A kind of conductive material and preparation method thereof |
| CN109148592B (en) | 2017-06-27 | 2022-03-11 | 乐金显示有限公司 | Thin film transistor including oxide semiconductor layer, method of manufacturing the same, and display device including the same |
| JP7378938B2 (en) * | 2019-02-22 | 2023-11-14 | 日東電工株式会社 | Light-transparent conductive film |
| JP7378937B2 (en) * | 2019-02-22 | 2023-11-14 | 日東電工株式会社 | Light-transparent conductive film |
| JP7205313B2 (en) * | 2019-03-11 | 2023-01-17 | セイコーエプソン株式会社 | Cables and ultrasound equipment |
| CN112466509B (en) * | 2020-11-20 | 2022-04-15 | 无锡晶睿光电新材料有限公司 | Low-temperature high-wear-resistance conductive silver paste and preparation method thereof |
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| JPS6340756A (en) * | 1986-08-07 | 1988-02-22 | 旭硝子株式会社 | Indium oxide sintered body for tin-containing physical vapor deposition |
| JPH0765167B2 (en) * | 1989-07-13 | 1995-07-12 | 株式会社ジャパンエナジー | Sputtering target for ITO transparent conductive film |
| JPH06239659A (en) * | 1991-04-24 | 1994-08-30 | Tosoh Corp | Metal oxide sintered product and its production and sputtering target using the same |
| JP4736032B2 (en) * | 2005-08-26 | 2011-07-27 | ハクスイテック株式会社 | Ion plating target for manufacturing zinc oxide-based conductive film and its manufacturing method, and manufacturing method of zinc oxide-based conductive film |
| JP4475209B2 (en) * | 2005-09-22 | 2010-06-09 | 住友金属鉱山株式会社 | Oxide sintered tablet for deposition |
| JP4617506B2 (en) * | 2006-03-24 | 2011-01-26 | Ｄｏｗａエレクトロニクス株式会社 | ITO powder and manufacturing method thereof, coating material for ITO conductive film, and transparent conductive film |
| CN103030381B (en) * | 2007-07-06 | 2015-05-27 | 住友金属矿山株式会社 | Oxide sintered body and production method therefor, target, and transparent conductive film and transparent conductive substrate obtained by using the same |
-
2010
- 2010-03-26 JP JP2010071801A patent/JP5224073B2/en not_active Expired - Fee Related
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2011
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- 2011-02-21 MY MYPI2012700666A patent/MY159313A/en unknown
- 2011-03-03 TW TW100107019A patent/TWI422696B/en not_active IP Right Cessation
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| JP昭63-40756A 1988.02.22 |
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| JP5224073B2 (en) | 2013-07-03 |
| KR20130008023A (en) | 2013-01-21 |
| TWI422696B (en) | 2014-01-11 |
| MY159313A (en) | 2016-12-30 |
| WO2011118334A1 (en) | 2011-09-29 |
| KR101322800B1 (en) | 2013-10-29 |
| JP2011202246A (en) | 2011-10-13 |
| TW201200610A (en) | 2012-01-01 |
| CN102812150A (en) | 2012-12-05 |
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