CN107779821A - Sintered body, sputtering target and its manufacture method - Google Patents
Sintered body, sputtering target and its manufacture method Download PDFInfo
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- CN107779821A CN107779821A CN201710734442.2A CN201710734442A CN107779821A CN 107779821 A CN107779821 A CN 107779821A CN 201710734442 A CN201710734442 A CN 201710734442A CN 107779821 A CN107779821 A CN 107779821A
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- sintered body
- sputtering target
- specific insulation
- depth location
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
- C04B35/453—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 based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- 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
- C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- 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
- C04B2235/3286—Gallium oxides, gallates, indium oxides, indates, thallium oxides, thallates or oxide forming salts thereof, e.g. zinc gallate
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
Abstract
The present invention provides a kind of sintered body, sputtering target and its manufacture method, and the sintered body can effectively suppress the deviation of sintered body surface and internal specific insulation in IZO targets.The sintered body of the present invention is the sintered body of the oxide comprising In, Zn, O, the specific insulation Rd of the specific insulation Rd of specific insulation Rs from the surface through-thickness 1mm of the sintered body depth location and surface through-thickness 4mm from sintered body depth location difference divided by the depth location of 4mm ratio, i.e. the absolute value of (Rs Rd)/Rd expressed as a percentage is less than 20%.
Description
Technical field
A kind of use for being referred to as so-called IZO targets the present invention relates to sintered body comprising In, Zn, O, comprising the sintered body
In the sputtering target and its manufacture method that form nesa coating etc., especially propose that a kind of can aid in forms stabilization during sputtering
The technology of IZO films.
Background technology
For example, the liquid crystal display (LCD) on personal computer or word processor etc., electroluminescent are mounted in manufacture
During film electrode of device (EL) and other various display device electrode, touch panel and Electronic Papers etc. etc., use sometimes
Sputtering method forms the nesa coating for including composite oxide of metal on the film forming substrate of the glass of sputtering target or plastics etc..
As this nesa coating, photopermeability and the ITO of excellent electric conductivity (Indium Tin Oxide, indium at present
Tin-oxide) film is main flow, in order to generate the ito film for including In, Sn, O, widely use ITO targets.
But due to the moisture-proof of ito film is relatively low, have because moisture cause resistance value to increase the shortcomings that, therefore as above-mentioned
Nesa coating, studying and this is replaced with IZO (Indium Zinc Oxide, indium-zinc oxide) films comprising In, Zn, O
Ito film, and using IZO targets to generate IZO films.
However, for the film forming stablized, in addition to requiring sputtering target high density, low resistance, the density and electricity of target
Resistance is uniform also critically important on the whole in target.
Particularly resistance, if the deviation of the specific insulation on the thickness direction of target is big, module feature occurs in sputtering
While change, it is also easy to occur the deviation of the specific insulation between block in by the sputtering target of multiple pieces of combinations, so as to damage
The overall quality stability of evil target.Therefore, in sputtering target, therefore, to assure that the uniformity of the specific insulation on thickness direction.
In conventional IZO targets, because the deviation of the specific insulation of thickness direction is big, therefore presence can not form stable IZO films
The problem of.
In addition, specific insulation typically has following trend, compared with forming the inside of sintered body of sputtering target, sintering
The surface of body uprises.But think that even if the specific insulation of sintered body is uneven in a thickness direction, by increasing sintered body
The stock removal on surface prepares sputtering target, can also ensure the uniformity of specific insulation to a certain extent.But in this feelings
Under condition, manufactured due to needing to thicken the thickness for setting sintered body according to the increase of stock removal, therefore worry in thickness direction
Middle position density reduction or cause the decline of finished product rate because of the increase of stock removal.
On this specific insulation, following content has been recorded in patent document 1, manufacture at least containing indium oxide and
During the sputtering target of zinc oxide, after firing process, " for obtained sintered body, in order to which the volume resistance of entirety is homogenized, though
It is so any process, but preferably carries out reduction treatment in process is reduced ".
In addition, following content has been recorded in patent document 2, the sputtering target of the low-resistance In-Sn-Zn-Al systems of high density
Specific insulation when being preferably the cooling after the sintering below 10m Ω cm, and when manufacturing the target, in order to prevent crackle
Generation, and obtain defined crystal formation, its cooling rate be set to less than 10 DEG C/minute, be further set to 5 DEG C/minute it is such as the following.
In addition, patent document 3 is related to ITO targets rather than IZO targets, it discloses the specific insulation of the thickness direction of target
Difference is less than 20% sputtering target.Following content is recorded in the patent document 3, in order to reduce the body of the thickness direction of target
The difference of product resistivity, mainly by the way that environment when cooling is set into atmospheric environment, average cooling rate be set to 0.1~3.0 DEG C/
Point.And show the specific insulation in sintered body difference and using target come between the difference of the resistance of the film of film forming exist compared with
The high degree of correlation.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2011-68993 publications
Patent document 2：Japanese Unexamined Patent Publication 2014-218706 publications
Patent document 3：International Publication No. 2014/156234
The content of the invention
Problems to be solved by the invention
In above-mentioned patent document 1, do not record in any deviation on reducing the specific insulation of thickness direction
Hold.In addition, it is assumed that even if carrying out reduction treatment by being used as other processes after sintering, the uniform of specific insulation can be realized
Change, because the importing of other this processes can cause the increase of cost and the increase in man-hour, therefore from the viewpoint of production is upper
It is undesirable.
Although patent document 2 refer to the content low on preferred volume resistivity, the volume on thickness direction
The deviation of resistivity does not carry out any discussion, and the record on cooling process with the stabilization of specific insulation nor turn to mesh
.
Because patent document 3 is related to ITO targets rather than IZO targets, its technology proposed is not directly applicable IZO targets.It is special
It is not that IZO targets are different from ITO targets, because damaged surface layer be present in sintered body surface, the specific insulation near damaged surface layer
It can further increase, therefore in IZO targets, pass through the technology of the cooling process described in patent document 3, it is impossible to fully reduce
The deviation of its specific insulation.
Problem of the invention is that solve conventional art present in this problem, and it is an object of the present invention to provide a kind of sintered body,
Sputtering target and its manufacture method, the sintered body can effectively suppress sintered body surface and internal volume resistance in IZO targets
The deviation of rate.
The solution used to solve the problem
When manufacturing IZO targets, when being formed into the formed body progress heat-agglomerating of regulation shape, in order to improve sintered body
Density and excellent membrane property is realized, in temperature-rise period, be preferably imported with the oxygen sintering or air sintering of oxygen.But send out
Result of the person of good sense by further investigation is to have obtained following opinion, if in temperature-fall period and being imported with the environment of oxygen,
As the result of the oxygen loss reduction of the near surface of sintered body, the difference of the specific insulation on the thickness direction of sputtering target
It is widely different.
Consequently found that it is different when environment during cooling after the heat-agglomerating of formed body is from heating, by being arranged to nitrogen
Environment or ar gas environment, the reduction of the oxygen loss of the near surface of sintered body can be suppressed, suppress the volume on thickness direction
The deviation of resistivity, sputtering target of the manufacture with more uniform bulk properties.
On the basis of the opinion, sintered body of the invention is the sintered body of the oxide comprising In, Zn, O, from the burning
The surface through-thickness of knot body be 1mm depth location specific insulation Rs with from the surface of the sintered body along thickness side
The specific insulation Rd of the depth location of difference divided by the 4mm to the specific insulation Rd of the depth location for 4mm ratio, i.e.,
(Rs-Rd)/Rd absolute value expressed as a percentage is less than 20%.
Here, it is preferably less than 15% that the absolute value of ratio (the Rs-Rd)/Rd is expressed as a percentage, further, more
Preferably less than 10%.
Above-mentioned sintered body can be the burning containing 7at%~20at%, preferably 10at%~17at% Zn/ (In+Zn)
Knot body.
In addition, the sputtering target of the present invention is the sputtering target of the oxide comprising In, Zn, O, from the surface edge of the sputtering target
The depth that the specific insulation Rf for the depth location that thickness direction is 0mm is 3mm with the surface through-thickness from the sputtering target
Spend the specific insulation Ra of the specific insulation Ra of position difference divided by the depth location of 3mm ratio, i.e. (Rf-Ra)/Ra
Absolute value it is expressed as a percentage be less than 20%.
Here, it is preferably less than 15% that above-mentioned ratio (Rf-Ra)/Ra absolute value is expressed as a percentage, further, more
Preferably less than 10%.
Above-mentioned sputtering target can be containing 7at%~20at%, and preferably 10at%~17at% Zn/ (In+Zn) splashes
Shoot at the target.
The manufacture method of the sputtering target of the present invention includes：Powder stock containing indium oxide powder and Zinc oxide powder is entered
Row is mixed and is molded；Thus obtained formed body is subjected to heat-agglomerating, formed body is subjected to the cooling after heat-agglomerating in nitrogen
Carried out under compression ring border or ar gas environment.
In the manufacture method, preferably the cooling rate during cooling is set to, more than 1 DEG C/minute, to be more preferably set to 3
DEG C/minute.
In addition, in the manufacture method, the heat-agglomerating of formed body is carried out preferably under air or oxygen atmosphere.
Invention effect
According to the present invention, due to the surface of sputtering target and the difference of internal specific insulation can be reduced, therefore during sputtering
The change of membrane property reduce, can realize to form stable film.Further, since required for the sputtering target of manufacture stabilised quality
The stock removal on sintered body surface tail off, therefore the yield rate of material can be improved.
Embodiment
Embodiments of the present invention are described in detail below.
The sintered body of an embodiment of the invention is the sintered body for including indium, zinc and oxygen, from the sintered body
The specific insulation Rs for the depth location that surface through-thickness is 1mm is with the surface through-thickness from the sintered body
The specific insulation Rd of the specific insulation Rd of 4mm depth location difference divided by the depth location of 4mm ratio, i.e. (Rs-
Rd)/Rd absolute value expressed as a percentage is less than 20%.
In addition, the sputtering target of an embodiment of the invention is the sputtering target for including sintered body, the sintered body includes
Indium, zinc and oxygen.The depth location (that is, the surface location of sputtering target) for being 0mm from the surface through-thickness of the sputtering target
Specific insulation Rf and depth location that surface through-thickness from the sputtering target is 3mm specific insulation Ra difference
Divided by the specific insulation Ra of the depth location of 3mm ratio, i.e. the absolute value of (Rf-Ra)/Ra is expressed as a percentage to be
Less than 20%.
(composition)
The sintered body for forming sputtering target includes In, Zn and O, such as comprising with formula In2O3(ZnO)mThe noncrystalline of expression
Oxide.Here, the m in formula is integer, the m values can take the value in the range of 3~20.
Zinc represented sometimes with 7at%~20at% with the atomic ratio Zn/ (In+Zn) of zinc, typically sometimes with
10at%~17at%.The amount of zinc can suitably be changed according to the electric conductivity of target film.
The content of In, Zn etc. composition can be measured by x-ray fluorescence analysis (XRF).
Above-mentioned sintered body can also contain others in addition to In and Zn in the range of the characteristic of the present invention is not damaged
Element.For example, in the case of containing at least one of Fe, Al, Si, Cu and Pb element, the content energy of these each elements
Enough it is set as below 100wtppm.In addition, in the case of containing at least one of Sn and Zr element, these each elements contain
Amount can be set as below 1000wtppm.
(specific insulation)
In the embodiment of sintered body, as described below, the surface of the sintered body obtained after heat-agglomerating and cooling
The specific insulation Rs in face (1mm depth location) that through-thickness is ground 1mm and exposed with from the surface of the sintered body
The specific insulation Rd difference in the face (4mm depth location) that through-thickness is ground 4mm and exposed divided by the depth position of the 4mm
The specific insulation Rd for the target surface put ratio, i.e. the absolute value of (Rs-Rd)/Rd expressed as a percentage is less than 20%.
If ratio (the Rs-Rd)/Rd, more than 20%, the film in sputtering during due to sintered body being used in sputtering target is special
Property change and the film forming that can not stablize, therefore in order that be used for sputtering target, it is necessary to largely be ground to sintered body surface
Cut.As a result, in order to manufacture the sputtering target of specific thickness, it is necessary to the stock removal is predicted in advance, prepares the thick sintered body of thickness,
In this case, the reduction of the density of the middle position of thickness direction is worried, in addition, causing finished product because of the increase of stock removal
The decline of rate.
Therefore, from this viewpoint, (Rs-Rd)/Rd ratio is more preferably less than 15%, especially more preferably 10% with
Under.
In addition, in the embodiment of sputtering target, it is preferable that the surface of sputtering target obtained from being ground to sintered body
The face that the specific insulation Rf of (0mm depth location) is ground 3mm and exposed with the surface through-thickness from the sputtering target
The specific insulation Ra of (3mm depth location) difference divided by the 3mm depth location specific insulation Ra ratio, i.e.,
(Rf-Ra)/Ra absolute value expressed as a percentage is less than 20%.
Thereby, it is possible to realize stable film forming in sputtering.In other words, if the ratio is more than 20%, in sputtering, with
The reduction of thickness, membrane property also changes, therefore film forming is unstable.
Ratio (Rf-Ra)/Ra is preferably less than 15%, and more preferably less than 10%.
The measurement of the above-mentioned specific insulation of sintered body or sputtering target can be directed to following face and carry out.By JIS R6001
(1998) after the grinding of the granularity of #400 specified in is finished with the grinding part of micro mist with 0.2mm grinding thichness
Face.
Above-mentioned specific insulation can measure according to the four probe method described in JIS 1637.More specifically, exist
By the measuring surface of sintered body or sputtering target along vertical and horizontal with the region and center in four corners after 3 × 3 nine deciles of progress
Totally 5 places measure in region.Can be using the average value of 5 local measured values as specific insulation of the invention.
Measurement point for example can be as the center of regional.
(crystallization particle diameter)
By setting the resistance difference of thickness direction described above, so as to which the tissue in 1mm face will be ground from surface
Crystal grain size Ds with from surface grinding 4mm face (such as face of the center of thickness direction) crystal grain size
Dd difference is set as less than 20%.The size of crystal grain selects to be seen at any 4 from the 5mm at the center on target surface angle
Examine.Afterwards, the average value of crystal grain size is obtained from the photo of 300 times of SEM images using compiling method.The difference of above-mentioned crystal grain
Different is that will be compared from surface grinding 1mm face and from surface grinding 4mm face (such as face of mid-depth position), will be each
Difference from relative mistake (Ds-Dd)/Dd of size absolute value as crystallization particle diameter.
In addition, form sputtering target sintered body average crystallite particle diameter for example can be 1.0 μm~5.0 μm, preferably 2.0
μm~3.0 μm.Crystallization particle diameter can be after it the part cut-out of sintered body and will carry out mirror ultrafinish to section, by right
SEM image is observed and measured.
(density)
Sintered body, the relative density of sputtering target can be more than 95%, preferably more than 98%.
Particularly in the present invention, due to the deviation of the specific insulation by reducing thickness direction, can reduce by burning
Knot body prepares amount of grinding during sputtering target, therefore can also improve the density in the center of thickness direction.In other words, it is if thick
The deviation of the specific insulation in degree direction is big, then amount of grinding when being expected to prepare sputtering target can become more, it is necessary to previously prepared thickness
Thick sintered body.But in this case, because thickness is thick, in heat-agglomerating heat be difficult to be transmitted to thickness direction center it is attached
Closely, it is low so as to cause the density of the center of the thickness direction of obtained sintered body or sputtering target.
Relative density can be by the solid density calculated according to the density of raw material powder and the burning using Archimedes method measurement
The density of knot body is calculated by below equation：Relative density=(utilizing the density of Archimedes method measurement) ÷ (solid density) ×
100 (%).In addition, IZO 10.7% solid density is 7.00g/cm3。
(manufacture method)
Above-described sintered body, sputtering target, such as can be manufactured by method described below.
First, such as by the material powder at least containing indium oxide powder and Zinc oxide powder bonded as needed with shaping
Agent mixes.
Then, the powder stock of mixing is filled into mould and be press-formed, and prepare the formed body of regulation shape.
This, such as 400~1000kgf/cm can be made2Pressure act on 1 minute~3 minutes.
Afterwards by the formed body in sintering furnace, such as it is heated to 1350 DEG C~1500 DEG C of temperature and is sintered.Should
The retention time of heating-up temperature can be 1 hour~100 hours, preferably 5 hours~30 hours.Can obtain density it is high,
The aspect of the excellent sputtering target of membrane property, the heat-agglomerating are preferably carried out under the oxidation environment of air or oxygen atmosphere etc..
Cooling after above-mentioned heat-agglomerating is importantly, not under air or oxygen atmosphere and in nitrogen environment or argon gas ring
Cooled down under border.By being cooled down in a nitrogen environment, it is suppressed that the reduction of the oxygen loss of the near surface of sintered body,
The deviation of the specific insulation of the thickness direction of sintered body can be suppressed to above-mentioned degree.In other words, in atmospheric environment or
In the case of carrying out the cooling under oxygen atmosphere, the oxygen loss of near surface is reduced, and thus causes the volume electricity of thickness direction
Resistance rate changes big and becomes uneven.
For the effect of the reduction for the oxygen loss that is further inhibited, the cooling rate after heat-agglomerating is preferably more than
The speed of the speed of 1 DEG C/minute of speed, more preferably more than 3 DEG C/minute, especially more preferably more than 5 DEG C/minute.Thus, one is entered
Step inhibits the deviation of the specific insulation on the thickness direction of sintered body, has more uniform volume electricity so as to manufacture
The sintered body of resistance rate.
Cooling can for example be carried out by the preferred nitrogen of cold air after the importing adjustment temperature into sintering furnace, argon gas.
Above-mentioned environment, cooling rate are preferably at least carried out in the range of 1400 DEG C~1000 DEG C, less than 1000 DEG C
Temperature fall can be carried out.This is due in IZO targets, and particularly the cooling rate of high-temperature area, cooling environment can be to its bodies
Product characteristic produces a very large impact.
By the single side surface of the sintered body obtained after cooling, along the thickness direction of sintered body, pass through mechanical grinding or chemistry
The known method of grinding etc. is for example ground 1%~20%, preferably 1%~10% to its thickness.Specifically, the stock removal,
For example can be 0.1mm~2.0mm, preferably 0.1mm~1.0mm on the thickness direction of sintered body.But manufacture sputtering target
When stock removal be not limited to this scope, can be arbitrary amount.The grinding can be used in JIS R6001 (1998) and provided
The #80 grinding of granularity carried out with the grinding part of micro mist.
In this embodiment, the deviation of specific insulation as described above in a thickness direction is small, it is therefore desirable to
Stock removal tails off.Thereby, it is possible to improve the yield rate of material.
Embodiment
Then, sputtering target is manufactured experimently according to the present invention, and confirms its performance, therefore be illustrated below.But herein
The purpose of explanation is only example, however it is not limited to this.
Indium oxide powder and Zinc oxide powder are mixed and crushed with each form as shown in table 1, is put into
In mould, make 800kgf/cm2Pressure act on 1 minute and obtain formed body.The formed body is heated to 1400 in electric furnace
DEG C, kept for 10 hours and cooled after sintering.
Here, the cooling after heat-agglomerating is to carry out in a nitrogen environment in embodiment 1~7, and in comparative example 1~5
In be to be carried out under atmospheric environment.In addition, in embodiment 1~7 and comparative example 1~5, as shown in table 1, when making heat-agglomerating
Rise, keep environment and cooling rate to change.When cooling rate shown in table 1 is between 1400 DEG C~1000 DEG C
Speed, temperature be reduced to less than 1000 DEG C after be Temperature fall.
For so obtained sintered body, using the sand paper of #80 grinding micro mist, from the surface of sintered body along thickness side
Sputtering target is prepared to manual grinding 1mm.Further, same method for grinding, most the surface grinding of sintered body at last are passed through
5mm or so is arrived, wherein each depth location on way, the resistivity measurement device (model manufactured using NPS Co., Ltd.：∑-5+)
Specific insulation is measured, measures apart from the surface of sintered body the specific insulation Rs of 1mm depth location, distance sintering respectively
The specific insulation Rd of the surface 4mm of the body depth location and specific insulation Rb on the surface of sintered body.Measuring each body
Before product resistivity, using the sand paper of #400 grinding micro mist, by measuring surface manual grinding finishing 0.2mm thickness.Separately
Outside, using these data, the ratio of the difference of ratio (Rs-Rd)/Rd × 100, Rb and Rd of Rs and Rd difference is calculated respectively
(Rb-Rd)/Rd×100.It the results are shown in table 1.
In addition, in this embodiment, apart from the surface of sintered body, the specific insulation Rs of 1mm depth location splashes with distance
The specific insulation Rf of the surface 0mm to shoot at the target depth location is equal.In addition, apart from the surface of sintered body 4mm depth location
Specific insulation Rd it is equal with the specific insulation Ra of the depth location of the 3mm apart from the surface of sputtering target.
In table 1, " maximum (%) of difference ratio " is to calculate each depth before 5mm or so depth location is reached
The ratio of the minimum and maximum difference of volume resistance measured by opening position.In addition, the stock removal (mm) of when " confirm 20% ",
Refer to the volume resistance ratio using the specific insulation of stock removal 4mm depth location as benchmark, with from the surface to the deep part,
Stock removal when being changed into 20%.
In addition, being measured the crystal grain in embodiment 1, the grinding surface apart from sintered body surface 1mm is 2.45 μm,
4mm grinding surface is 2.59 μm, and relative mistake (Ds-Dd)/Dd absolute value is 5.4%.
[table 1]
As shown in table 1, in the embodiment 1~7 that cooling environment is nitrogen is made, no matter heat up, keep environment to be oxygen
Or air, and no matter it is formed, the specific insulation Rs of the 1mm depth locations of sintered body and the 4mm depth position of sintered body
The ratio of the specific insulation Rd put difference is less than 20%, realizes the reduction of specific insulation and the suppression of deviation.
Particularly, being carried out at high speed in the embodiment 3 and 6 of cooling more than 5 DEG C/minute is being utilized, is realizing further body
The reduction of product resistivity and the suppression of deviation.
In contrast, in comparative example 1~5, after formed body is carried out into heat-agglomerating, because being dropped under atmospheric environment
The specific insulation Rd of temperature, the specific insulation Rs of the 1mm depth locations of sintered body and the 4mm depth locations of sintered body difference
Ratio becomes quite big, turns into the larger sintered body of the deviation of specific insulation more than 20%.
By described above, by means of the invention it is possible to effectively suppress sintered body surface and internal specific insulation
Deviation.
Claims (14)
1. a kind of sintered body, it is the sintered body of the oxide comprising In, Zn, O, from the surface through-thickness of the sintered body
The specific insulation Rs of 1mm depth location and the depth location of the surface through-thickness 4mm from the sintered body volume
The specific insulation Rd of resistivity Rd difference divided by 4mm depth location ratio, i.e. (Rs-Rd)/Rd absolute value with
Percentage is expressed as less than 20%.
2. sintered body according to claim 1, wherein, the ratio, i.e., (Rs-Rd)/Rd absolute value is with percentage table
It is shown as less than 15%.
3. sintered body according to claim 1, wherein, the ratio, i.e., (Rs-Rd)/Rd absolute value is with percentage table
It is shown as less than 10%.
4. according to sintered body according to any one of claims 1 to 3, wherein, the Zn/ (In+ containing 7at%~20at%
Zn)。
5. according to sintered body according to any one of claims 1 to 3, wherein, the Zn/ (In+ containing 10at%~17at%
Zn)。
6. a kind of sputtering target, it is the sputtering target of the oxide comprising In, Zn, O, from the surface through-thickness of the sputtering target
The specific insulation Rf of 0mm depth location and the depth location of the surface through-thickness 3mm from the sputtering target volume
The specific insulation Ra of resistivity Ra difference divided by 3mm depth location ratio, i.e. (Rf-Ra)/Ra absolute value with
Percentage is expressed as less than 20%.
7. sputtering target according to claim 6, wherein, the ratio, i.e., (Rf-Ra)/Ra absolute value is with percentage table
It is shown as less than 15%.
8. sputtering target according to claim 6, wherein, the ratio, i.e., (Rf-Ra)/Ra absolute value is with percentage table
It is shown as less than 10%.
9. the sputtering target according to any one of claim 6~8, wherein, the sputtering target contains 7at%~20at%'s
Zn/(In+Zn)。
10. the sputtering target according to any one of claim 6~8, wherein, the sputtering target contains 10at%~17at%
Zn/ (In+Zn).
11. a kind of manufacture method of sputtering target, including：
Powder stock containing indium oxide powder and Zinc oxide powder is mixed and is molded, thus obtained formed body is entered
Row heat-agglomerating；
The cooling that the formed body is carried out after heat-agglomerating is carried out under nitrogen environment or ar gas environment.
12. the manufacture method of sputtering target according to claim 11, wherein, the cooling rate during cooling is more than 1
DEG C/minute speed.
13. the manufacture method of sputtering target according to claim 11, wherein, the cooling rate during cooling is more than 3
DEG C/minute speed.
14. the manufacture method of the sputtering target according to any one of claim 11~13, wherein, in air or oxygen atmosphere
The lower heat-agglomerating for carrying out formed body.
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| JP2016167135A JP6267297B1 (en) | 2016-08-29 | 2016-08-29 | Sintered body, sputtering target and manufacturing method thereof |
| JP2016-167135 | 2016-08-29 |
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| CN109072417A (en) * | 2017-03-31 | 2018-12-21 | Ｊｘ金属株式会社 | Sputter target and its manufacturing method |
| CN114574824A (en) * | 2018-03-30 | 2022-06-03 | Ｊｘ金属株式会社 | Sputtering target member and method for producing same |
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| JP2020143359A (en) * | 2019-03-08 | 2020-09-10 | Ｊｘ金属株式会社 | Manufacturing method of sputtering target member, and sputtering target member |
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| CN102187009A (en) * | 2009-05-01 | 2011-09-14 | 株式会社爱发科 | Sintered body for zno-ga2o3 sputtering target and method for producing same |
| JP2015021165A (en) * | 2013-07-19 | 2015-02-02 | 三菱マテリアル株式会社 | Sputtering target and production method thereof |
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| JPH10297962A (en) * | 1997-04-28 | 1998-11-10 | Sumitomo Metal Mining Co Ltd | Zno-ga2o3-based sintered compact for sputtering target and production of the sintered compact |
| JPH11302835A (en) * | 1998-04-21 | 1999-11-02 | Sumitomo Metal Mining Co Ltd | Production of zinc oxide base sintered compact |
| KR100603128B1 (en) * | 1999-05-10 | 2006-07-20 | 닛코킨조쿠 가부시키가이샤 | Sputtering target |
| CN1195886C (en) * | 1999-11-25 | 2005-04-06 | 出光兴产株式会社 | Sputtering target, transparent conductive oxide and method for producing the sputtering target |
| JP2008156708A (en) * | 2006-12-25 | 2008-07-10 | Idemitsu Kosan Co Ltd | Method for producing transparent electroconductive film |
| JP5096250B2 (en) * | 2008-07-18 | 2012-12-12 | 出光興産株式会社 | Oxide sintered body manufacturing method, oxide sintered body, sputtering target, oxide thin film, thin film transistor manufacturing method, and semiconductor device |
| TWI602939B (en) * | 2013-01-15 | 2017-10-21 | 出光興產股份有限公司 | Sputtering targets, oxide semiconductor films, and methods of making them |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102187009A (en) * | 2009-05-01 | 2011-09-14 | 株式会社爱发科 | Sintered body for zno-ga2o3 sputtering target and method for producing same |
| JP2015021165A (en) * | 2013-07-19 | 2015-02-02 | 三菱マテリアル株式会社 | Sputtering target and production method thereof |
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| CN109072417A (en) * | 2017-03-31 | 2018-12-21 | Ｊｘ金属株式会社 | Sputter target and its manufacturing method |
| CN109072417B (en) * | 2017-03-31 | 2020-06-16 | Ｊｘ金属株式会社 | Sputtering target and method for producing same |
| CN114574824A (en) * | 2018-03-30 | 2022-06-03 | Ｊｘ金属株式会社 | Sputtering target member and method for producing same |
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| CN107779821B (en) | 2020-12-18 |
| TWI649293B (en) | 2019-02-01 |
| KR20180025225A (en) | 2018-03-08 |
| KR101921827B1 (en) | 2019-02-13 |
| JP2018035013A (en) | 2018-03-08 |
| JP6267297B1 (en) | 2018-01-24 |
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