CN109837512A - IZO target and its manufacturing method - Google Patents
IZO target and its manufacturing method Download PDFInfo
- Publication number
- CN109837512A CN109837512A CN201811055653.4A CN201811055653A CN109837512A CN 109837512 A CN109837512 A CN 109837512A CN 201811055653 A CN201811055653 A CN 201811055653A CN 109837512 A CN109837512 A CN 109837512A
- Authority
- CN
- China
- Prior art keywords
- target
- izo
- powder
- izo target
- grain
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
- C04B35/457—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 based on tin oxides or stannates
-
- 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
-
- 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
-
- 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
- C04B2235/3293—Tin oxides, stannates or oxide forming salts thereof, e.g. indium tin oxide [ITO]
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Structural Engineering (AREA)
- Physical Vapour Deposition (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The IZO target that oxygen concentration when the film resistance that the present invention provides a kind of sputtered film is not easily susceptible to sputtering influences.A kind of IZO target, with following entirety composition: containing In, Sn and Zn, meet Zn/ (In+Sn+Zn)=0.030~0.250, Sn/ (In+Sn+Zn)=0.002~0.080 with atomic ratio measuring, surplus is made of O and inevitable impurity, the IZO target has target tissue, and the Sn that the partial size specific, containing In, Sn and O by FE-EPMA is 200nm or more is dispersed in the target tissue and is segregated grain.
Description
Technical field
The present invention relates to a kind of indium-zinc oxide (IZO) target and its manufacturing methods.In addition, the invention further relates to a kind of indiums
Zinc oxide (IZO) target and the film build method for having used the target.
Background technique
With indium-zinc oxide (In2O3- ZnO: commonly referred to as IZO) sintered body is that the sputtering target material of material is widely used in
Multiple electronic components such as the transparent conducting film or gas sensor of liquid crystal display device.With as representative electrically conducting transparent
Property film ito film compare, IZO film has the advantage that etching speed is fast, the generation of particle is few, can get amorphous film etc..So
And IZO has the following problems: volume resistivity is compared with ITO high, and the visible deviation in film resistance.Therefore, especially in DC magnetic
It controls in sputtering process, the electric discharge in sputtering becomes unstable sometimes.
It recites in patent document 1 (Japanese Unexamined Patent Publication 6-234565 bulletin): having by adulterating Sn etc. in IZO
The element of valence more than positive trivalent, can be obtained the transparent conductive film of excellent electric conductivity.
In patent document 2 (International Publication No. 2000/68456), recite to provide a kind of transparent conductive film and be formed
With the invention for the purpose of IZO sputtering target material, the IZO sputtering target material reduces volume resistance by adding very micro Sn
Value, and can steadily discharge in sputtering.Specifically, recite it is a kind of made with In and Zn oxide it is as main component
Bright conductive film, which is formed, uses IZO sputtering target material, it is characterised in that the Sn containing 100~2000ppm.
It recites in patent document 3 (Japanese Unexamined Patent Publication 2017-014534 bulletin): being sputtered documented by patent document 2
In target, target material surface is easy to produce color spot, needs lapped face until color spot disappears.And, it is also proposed that the content of Sn is set
For more than 2000ppm and at 20000ppm or less (more than 2000ppm~20000ppm), to eliminate color spot.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 6-234565 bulletin;
Patent document 2: International Publication No. 2000/68456;
Patent document 3: Japanese Unexamined Patent Publication 2017-014534 bulletin.
Summary of the invention
Technical problem
However, specifying that the film resistance of sputtered film is easy to rely on when using IZO target documented by Patent Documents 1 to 3
The oxygen concentration in atmosphere when sputtering.More specifically, when being sputtered using these IZO targets, when with sputtering
The reduction of oxygen concentration in atmosphere, the film resistance of sputtered film are in the trend obviously increased.In addition, having the further insight that: even if addition Sn,
Also volume resistance may not be can reduce.By application, sputtering in low oxygen concentration and then under anaerobic can be sought, therefore
Want to mitigate the oxygen concentration dependence of film resistance.Especially since the organic EL to attract attention in recent years not oxytolerant, therefore
It is required that forming a film under anaerobic importing, it is advantageous so film resistance low sputtered film can be obtained under low oxygen concentration.
The present invention creates in view of the foregoing, it will thus provide a kind of oxygen that the film resistance of sputtered film is not easily susceptible to when sputtering is dense
The IZO target influenced is spent as one of project.The present invention is using the manufacturing method of IZO target as providing as another project.
The present invention has used the film build method of IZO target according to the present invention as another project to provide.
Solution to problem
The present inventor recognizes when furtheing investigate in order to solve the above problems: having and disperses in the parent phase of IZO
The IZO target of tissue of sintered body of the Sn segregation grain containing In and Sn be effective.Such IZO target can by
ITO powder is added in the raw material powder of IZO target to manufacture.The IZO target with the tissue is used to form a film as sputtering target material
Shi Kezhi: relative to the variation of the oxygen concentration in sputtering atmosphere, film resistivity is not susceptible to change.Although the oxygen concentration in sputtering
It is often different according to used purposes, but in terms of the sputtered film for obtaining stay in grade, film resistivity, which is not easy to depend on, splashes
The oxygen concentration emanated in atmosphere is advantageous.
With the above-mentioned present invention for perceiving as basis and completing, one side is related to a kind of IZO target, IZO target tool
It is made of following entirety: containing In, Sn and Zn, Zn/ (In+Sn+Zn)=0.030~0.250, Sn/ being met with atomic ratio measuring
(In+Sn+Zn)=0.002~0.080, and surplus is made of O and inevitable impurity, which has target tissue,
The Sn that the partial size specific, containing In, Sn and O by FE-EPMA is 200nm or more is dispersed in the target tissue to be segregated
Grain.
In one embodiment, IZO target according to the present invention contains In, Sn and Zn, meets Sn/ with atomic ratio measuring
(In+Sn+Zn)=0.010~0.030.
In another embodiment, IZO target according to the present invention contains In, Sn and Zn, meets Zn/ with atomic ratio measuring
(In+Sn+Zn)=0.040~0.200.
In the another embodiment of IZO target according to the present invention, partial size be 200nm or more Sn be segregated grain with
0.003/μm2Above a number density is present in target tissue.
In the another embodiment of IZO target according to the present invention, partial size be 1000nm or more Sn be segregated grain with
0.0003/μm2Above a number density is present in target tissue.
In yet another embodiment, the relative density of IZO target according to the present invention is 90% or more.
In yet another embodiment, the volume resistance of IZO target according to the present invention is 0.3m Ω cm or more and not
Sufficient 7.0m Ω cm.
In the another embodiment of IZO target according to the present invention, the average grain diameter of above-mentioned Sn segregation grain is 450nm
Above and 9000nm or less.
In the another embodiment of IZO target according to the present invention, partial size be 10000nm or more Sn be segregated grain with
0.0002/μm2A number density below is present in target tissue.
In the another embodiment of IZO target according to the present invention, also contain B, B/ (In+ is met with atomic ratio measuring
Sn+Zn+B)=0.036 or less.
Another side of the invention be IZO target according to the present invention manufacturing method, this method include by ITO powder,
In2O3The process of the mixture sintering of powder and ZnO powder.
In an embodiment of the manufacturing method of IZO target according to the present invention, each particle for constituting ITO powder contains
In and Sn meets 6≤In/Sn≤36 with atomic ratio measuring.
Another side of the invention be IZO target according to the present invention manufacturing method, this method include by ITO powder,
In2O3Powder, ZnO powder and B2O3The process of the mixture sintering of powder.
Another side of the invention is related to a kind of film build method, and this method includes using IZO target according to the present invention
The process sputtered.
It is 0.1vol% atmosphere gas below in oxygen concentration in an embodiment of film build method according to the present invention
Implement sputtering process in body.
Invention effect
IZO target according to the present invention has the property that the variation relative to the oxygen concentration in sputtering atmosphere, gained
Film resistance variation it is small.Thus, it is possible to obtain the sputtered film of stay in grade, and it is unrelated with oxygen concentration.The present invention is for as having
Machine EL require in this way anaerobic import under form a film using particularly useful.
Detailed description of the invention
Fig. 1 shows that the element of embodiment 3 maps image.
Fig. 2 shows that the element of comparative example 2 maps image.
Fig. 3 shows that the smoothed out element of the Sn surface analysis result of embodiment 3 maps image.
Fig. 4 shows that the element after the binaryzation of the Sn surface analysis result of embodiment 3 maps image.
Specific embodiment
(1. whole composition)
IZO target according to the present invention has following whole composition in one embodiment: containing In, Sn and Zn,
Make to meet Zn/ (In+Sn+Zn)=0.030~0.250, Sn/ (In+Sn+Zn)=0.002~0.080 with atomic ratio measuring, and remaining
Amount is made of O and inevitable impurity.Including whole composition refers to the segregation grain of the Sn in the tissue for being dispersed in sintered body
Sintered body whole composition.
Zn/ (In+Sn+Zn) reason for being set as 0.030 or more is:, can by making the amount of Zn be in range appropriate
Obtain sputtered film with good conductivity.Zn/ (In+Sn+Zn) is preferably 0.030 or more, and more preferably 0.040 or more.In addition, will
The reason that Zn/ (In+Sn+Zn) is set as 0.250 or less is: if the amount of Zn is excessive, the electric conductivity of sputtered film can be deteriorated.Zn/
It (In+Sn+Zn) is preferably 0.250 hereinafter, more preferably 0.200 or less.
Sn/ (In+Sn+Zn) reason for being set as 0.002 or more is: making the reduction of volume resistance and inhibits relative to splashing
The significant effect of the variation of the film resistance of oxygen concentration variation in atmosphere of emanating plays.Sn/ (In+Sn+Zn) is preferably 0.002 or more,
More preferably 0.005 or more, further preferably 0.010 or more.In addition, Sn/ (In+Sn+Zn) is set as 0.080 original below
Because being: if adding the amount or more, sintered density is excessively reduced, so that volume resistance is easy to increase, is in addition also worried
The adverse effect for sputtering such as increase of grain.Sn/ (In+Sn+Zn) be preferably 0.065 hereinafter, more preferably 0.060 hereinafter,
Further preferably 0.030 or less.
Inevitable impurity refers to present in raw material or the inevitably mixed substance in manufacturing process,
Originally it was unwanted substance, but because its is micro and will not bring and significantly affects to the characteristic of sintered body, therefore was acceptable
Impurity.
IZO target according to the present invention also contains B in one embodiment, makes B/ (In+Sn+Zn+B) with atomic ratio measuring
It is 0.036 or less.B is for example from B2O3.Due to B2O3Fusing point down to 450 DEG C, therefore be sintered in liquid is generated in sintered body
Phase improves agglutinating property, and density can be improved.In order to preferentially play the effect for improving agglutinating property, B/ (In+Sn+Zn+B) is preferred
0.004 or more, if excessively addition, volume resistance are substantially increased, therefore preferably B/ (In+Sn+Zn+B)=0.036 or less.
(2.Sn is segregated grain)
IZO target according to the present invention has tissue of sintered body in one embodiment, and the tissue of sintered body is main
By indium oxide (In2O3) and indium and zinc composite oxides (ZnkIn2Ok+3, k=2~7 (k is integer)) constitute parent phase in point
It dissipates the Sn that containing In, Sn and O and partial size is 200nm or more and is segregated grain.It may include times of indium oxide and zinc oxide in parent phase
One or two kinds of oxides.Partial size is scattered in parent phase as the tissue of sintered body of the Sn segregation grain of 200nm or more using having
Sputtering target material when, sputtered film reduces the dependence of the oxygen concentration in sputtering atmosphere.Therefore, even if the oxygen in sputtering atmosphere is dense
Degree changes depending on the application, but can also obtain the sputtered film of stable film resistivity.
In order to significantly play electric conductivity improvement effect and inhibit the film resistance relative to the oxygen concentration variation in sputtering atmosphere
Variation effect, preferable particle size be 200nm or more Sn be segregated grain with 0.003/μm2Above a number density is present in burning
In knot body tissue, preferably with 0.0045/μm2Above a number density is present in tissue of sintered body, more preferably with 0.01/
μm2Above a number density is present in tissue of sintered body.But if the number for the Sn segregation grain that partial size is 200nm or more is close
Spend it is surplus, then when being compared in the identical situation of the atomic concentration of the Sn in target, due to Sn segregation grain one by one
The decline of Sn concentration, therefore with SnO2Form addition and the state that is spread close to Sn, it is possible to it is special to be not easy to obtain original sputtering
Property.Therefore, the Sn that partial size is 200nm or more is segregated grain preferably with 0.1/μm2A number density below is present in sintered body group
In knitting, more preferably with 0.08/μm2A number density below is present in tissue of sintered body, still more preferably with 0.04/
μm2A number density below is present in tissue of sintered body.
In addition, in order to significantly play electric conductivity improvement effect and inhibit the film relative to the oxygen concentration variation in sputtering atmosphere
The effect of the variation of resistance, the Sn that preferable particle size is 1000nm or more are segregated grain with 0.0003/μm2Above a number density is deposited
It is in tissue of sintered body, preferably with 0.001/μm2Above a number density is present in tissue of sintered body, more preferably with
0.003/μm2Above a number density is present in tissue of sintered body.But if the Sn that partial size is 1000nm or more is segregated grain
A number density it is superfluous, then agglutinating property declines, and sintered density reduces, and volume resistance rises, or worries to become the original of particle
Cause.Therefore, the Sn that partial size is 1000nm or more is segregated grain preferably with 0.03/μm2A number density below is present in sintered body
In tissue, more preferably with 0.026/μm2A number density below is present in tissue of sintered body, further preferably with 0.02
A/μm2A number density below is present in tissue of sintered body.
In addition, the reason of excessive Sn segregation grain is likely to become arc discharge, therefore preferable particle size is 10000nm's or more
Sn is segregated grain with 0.0002/μm2A number density below is present in tissue of sintered body, preferably with 0.0001/μm2Below
A number density be present in tissue of sintered body, more preferably with 0.00005/μm2A number density below is present in sintered body
In tissue.
In order to significantly play the effect for the variation for inhibiting the film resistance relative to the oxygen concentration variation in sputtering atmosphere, Sn is inclined
The average grain diameter for analysing grain is preferably 450nm or more, and more preferably 800nm or more is still more preferably 900nm or more.If Sn
The average-size for being segregated grain is excessive, then volume resistance increases, it is also possible to the reason of becoming arc discharge, therefore Sn segregation grain is flat
Equal partial size is preferably 9000nm hereinafter, more preferably 6000nm is hereinafter, be still more preferably 3000nm or less.
In the present invention, Sn is segregated the partial size of grain and a number density is measured by the following method.As determining instrument,
It uses FE-EPMA (electric field emission type probe-microanalyser).JXA-8500F (Japan Electronics is used in embodiment
The FE-EPMA of manufacture).
It measures sample: cutting sputtering target material perpendicular to sputter face, pair cross-section carries out mirror ultrafinish, observes the portion of 1/2 thickness
Point.
Observation method: the incidental surface analysis function of FE-EPMA is utilized, implements surface analysis under the following conditions.
Acceleration voltage: 15.0kV
Irradiation electric current: 1.0~2.5 × 10-7A
Multiplying power: 2000 times
Mensuration mode: light beam scanning
Beam diameter (μm): 0
Minute (ms): 5
Accumulation: 1
Measure element and analyzing crystal: In (PETH), Zn (LIFH), Sn (PETH), O (LDE1)
It measures in the visual field (each visual field): 50 50 μm of μ ms
Pixel: 256 × 256
Implement surface analysis in the order described above, when element mapping image is carried out gray scale display, obtains Fig. 1 (embodiment
Or the determination data of Fig. 2 (comparative example 2) 3).Although Lv can also directly be calculated using machine automatization by operating manually
Lv.In embodiment 3, it is seen that Sn segregation is at coarse-grained position (the most shallow part of the element mapping image of Sn), in contrast,
Coarse-grained segregation is had no in comparative example 4.Think not seeing that the reason of Sn is segregated grain is in comparative example 4: working as investment
SnO2When powder is as raw material, Sn diffuses to In2O3In grain, the Monitoring lower-cut concentration below of FE-EPMA is reached.Another party
Face, although being not intended to limit the present invention, about the reason of Sn is not spread when adding coarse ITO powder, although only
Speculate, but consider as follows: thinking the driving force of diffusion dependent on concentration gradient, in SnO2In powder and ITO powder, due in ITO powder
Sn concentration it is low, therefore in ITO powder Sn be not easy around spread.
Using particle measurement function, grain is segregated by each partial size and Sn of the gray level image measurement Sn segregation grain of resulting Sn
A number density.Although also can be used same in the following, being the implementation sequence in the incidental analysis software of JXA-8500F
Image processing software.Firstly, coming into effect smothing filtering from filter project.The example of embodiment 3 is shown in Fig. 3.Then, implement two
Value.About the threshold value in binaryzation, the Sn in surface analysis is set to be segregated being obtained without for particle shape shape although manually setting threshold value
It is excessive or insufficient, but with grain merges, shape is obtained without with excessive or insufficient side with biggish Sn segregation in gray level image
Formula given threshold.The example of embodiment 3 is shown in Fig. 4.
Later, the label of binary image is carried out.In this software, mark processing selection items selection " 3 connection ",
" particle of periphery is not marked ".Then, the measurement of image is marked, the circle equivalent that machinery calculates each Sn segregation grain is straight
Diameter.Using each Sn segregation grain equivalent circle diameter as Sn segregation grain partial size, respectively to partial size for 200nm or more, 1000nm with
Upper and 10000nm or more particle number counts, and finds out 2500 μm as the measurement visual field2Present in particle number, with a
Number divided by measurement field area, thus obtain number density (it is a/μm2).In addition, the average grain diameter of Sn segregation grain is calculated by machinery
Each Sn out is segregated the equivalent circle diameter of grain and acquires.Said sequence is carried out in 5 or more the measurement visuals field, it is average with it
Value is used as measurement result.
(3. volume resistivity)
IZO target involved in one embodiment of the present invention is dispersed due to Sn segregation grain in the tissue, so with existing
IZO target compared to volume resistivity can be greatly reduced.Specifically, IZO target according to the present invention is in an embodiment party
It can have the volume resistivity less than 7.0m Ω cm in formula.The volume resistivity of IZO target according to the present invention is preferred
For 3.0m Ω cm hereinafter, more preferably 2.0m Ω cm or less.The lower limit of volume resistivity is not limited, but from IZO's
From the point of view of substance boundary, the volume resistivity of IZO target according to the present invention is usually 0.3m Ω cm or more, typically
0.5m Ω cm or more.
In the present invention, the volume resistivity of target is to be measured using Instrument Measuring Resistivity of Carbon Products by four probe method.By
In the metamorphic layer few there are Zn amount on sintered body surface, so grinding 0.5mm, is refined with pouncing paper to #400.In embodiment,
It is measured using device below.
Instrument Measuring Resistivity of Carbon Products: model FELL-TC-100-SB- Σ 5+ (manufacture of NPS Co., Ltd.)
Measure fixture RG-5
(4. relative density)
In terms of carrying out the few stable sputtering of arc discharge, the preferred high target of relative density.IZO according to the present invention
Relative density is 90% or more to target in one embodiment.Relative density is preferably 92% or more, and more preferably 95% or more,
Still more preferably it is 96% or more, such as can be 90~99%.Relative density is by Archimedes density relative to root
It is found out according to the ratio of the determining reference density of composition.
Here, the constituent analysis for carrying out sputtering target material, according to thus obtained In, Zn, Sn and B respectively relative to In, Zn,
The atomic ratio (at%) of the total 100at% of Sn and B converts, using obtained oxide weight ratio (weight %) and
In2O3、ZnO、SnO2And B2O3Monomer density calculate reference density.Specifically, In2O3Monomer density be 7.18 (g/
cm3), the monomer density of ZnO be 5.61 (g/cm3)、SnO2Monomer density be 6.95 (g/cm3)、B2O3Monomer density be
1.85、In2O3Weight ratio be set as WIn2O3The weight ratio of (weight %), ZnO are set as WZnO(weight %), SnO2Weight ratio be set as
WSnO2(weight %), B2O3Weight ratio be set as WB2O3, according to reference density (g/cm37.18 × W of)=(In2O3+5.61×WZnO+
6.95×WSnO2+1.85×WB2O3)/100 calculate.Wherein, when being not added with B, by WB2O3It is set as 0 and carrys out calculating benchmark density.
In addition, the relative density is to assume sputtering target material for In2O3, ZnO and SnO2Mixture and counted benchmark is close
Density on the basis of degree, the true value of the density of the sputtering target material as object can also be higher than above-mentioned reference density sometimes, because
This relative density mentioned here can also be more than 100% sometimes.
(5. manufacturing method)
Next, successively illustrating the preference of the manufacturing method of IZO target according to the present invention.
(preparation of 5-1ITO powder)
Firstly, carrying out the standard of the powder (ITO powder) for the oxidate sintered body being made of Sn, In, O and inevitable impurity
It is standby.ITO sintered body is manufactured using well known method, then is crushed, can be obtained ITO powder.Alternatively, in order to be easy to carry out powder
It is broken, it can also be by by In2O3And SnO2Mixing powder sintering (referred to as interim sintering), crush to make ITO powder.
ITO powder is finally segregated the raw material of grain in sintered body as above-mentioned Sn.Group about each particle for constituting ITO powder
At for the reason of improve electric conductivity, the atomic ratio of preferably In and Sn are 6≤In/Sn, more preferably 7≤In/Sn, more into one
Step is preferably 9≤In/Sn.In addition, even if the amount of Sn is very few, electric conductivity can also decline, therefore the original of In and Sn in ITO powder
Son is still more preferably In/Sn≤15 than being preferably In/Sn≤36, more preferably In/Sn≤25.
ITO sintered body can be by by SnO2Powder and In2O3Powder is sintered again after being pulverized and mixed with defined proportion
And it is made.SnO as raw material2Powder and In2O3Powder, from prevent it is unexpected it is bad from the point of view of, it is preferable to use high-purity
Raw material, such as purity are 99 mass % or more, are further the raw material of 99.9 mass % or more.The average grain diameter of raw material powder is for example
It can be set to 0.5 μm~2.5 μm.Here, in the present specification, when mentioning the average grain diameter of powder, refer to and spread out by laser
It penetrates, the median particle diameter (D50) when scattering method is found out the cumulative distribution of granularity by volume reference.The method of being pulverized and mixed has various sides
Method, but the case of wet attrition mixing using the wet medias Ball-stirring mill such as ball mill may be appropriately used.When carrying out case of wet attrition mixing,
The uniformity of slurry can also be improved by being properly added dispersing agent.Even other methods, as long as being that by raw material
The method for uniformly mixing this main idea.
Mixed powder by obtaining after being pulverized and mixed is press-formed.Extrusion forming be by by mixed powder fill to
Metal mold is simultaneously for example kept for carry out within 1~3 minute with the pressure of 30~60MPa.It, as needed can be real before extrusion forming
Apply granulation.Improve the mobility of powder by being granulated, to can uniformly fill out powder in the extrusion forming of subsequent processing
It is charged to metal mold, obtains uniform formed body.Granulation there are various ways, but obtain being suitble to the pelletizing of extrusion forming method it
One has the method using atomizing-type drying device (spray dryer).In addition, by adding polyvinyl alcohol (PVA) etc. in the slurry
Adhesive and be contained in it in pelletizing, formed body intensity can be improved.In addition, isostatic cool pressing can be carried out after extrusion forming
It is press-formed (CIP).
The sintering of formed body can be used electric furnace and implement in oxygen atmosphere.It is preferred that sintering temperature is set as 1300~1600
It DEG C is sintered.In terms of obtaining highdensity sintered body, preferably sintering temperature is 1300 DEG C or more.In addition, from oxidation is passed through
Tin volatilization come prevent sintered density decline or generate composition deviation from the point of view of, sintering temperature be preferably 1600 DEG C with
Under.When formed body include adhesive when, the heating for reaching sintering temperature on the way, unsticking mixture work can be imported as needed
Sequence.
Retention time under sintering temperature suitably selects according to formed body size, it is, in general, that if shorter than 5 hours,
Sintering is unable to fully carry out, and the density of sintered body does not have sufficiently to get higher or sintered body warpage.Even if the retention time is more than
30 hours, and the unnecessary energy of waste and time, in production not preferably.
By crushing resulting ITO sintered body, ITO powder is obtained.As breaking method, such as alms bowl pestle can be enumerated and ground
Combination, hammer mill and the pot mill of alms bowl, wherein the preferred pot mill from the point of view of productivity.In addition, more preferably using wet
Formula sand mill etc. is further levigate.It is sieved to remove the big particle of ITO powder.Sieve can be used for example aperture and be
150 μm of sieves below.The average grain diameter (D50) of ITO powder after screening preferably reaches 10 μm hereinafter, more preferably up to 5 μm or less.
In addition, and In2O3The average grain diameter of ITO powder before powder and the mixing of ZnO powder preferably reaches 0.4 μm or more, more preferably up to 0.9 μm
More than.
(manufacture of 5-2IZO target)
IZO target according to the present invention can manufacture as follows: by In2O3Powder, ZnO powder and ITO powder obtained above carry out powder
Broken mixing makes above-mentioned Zn/ (In+Sn+Zn) and Sn/ (In+Sn+Zn) reach defined atomic ratio, is sintered later
It is made.In addition, B can be added as needed2O3Powder.Sintering can carry out after interim sintering.Specific sequence is illustrated
The explanation of property.Firstly, weighing In with defined proportion2O3Powder, ZnO powder and the B to depend on the needs2O3Powder carries out Crushing of Ultrafine later
Mixing.In order to mix ITO powder uniformly as far as possible and without Crushing of Ultrafine, preferably in In2O3It powder, ZnO powder and depends on the needs
B2O3ITO powder is directly mixed in slurry form before 5~10 minutes that the Crushing of Ultrafine mixing of powder stops.It is unexpected bad from preventing
From the point of view of, the In as raw material2O3Powder, ZnO powder and B that is as needed and adding2O3It is preferable to use the powder of high-purity for powder
End, such as purity are 99 mass % or more, are further the powder of 99.9 mass % or more.As mixed method, can enumerate
The method for carrying out case of wet attrition mixing using the wet medias Ball-stirring mill such as sand mill.When carrying out case of wet attrition mixing, by appropriate
Dispersing agent is added, the uniformity of slurry can also be improved.Even other methods, as long as being that by the uniform mixing of raw material
The method of this main idea.
Mixed powder mixed for Crushing of Ultrafine, in order to improve its agglutinating property, preferably by average grain diameter be set as 2 μm hereinafter,
More preferably it is set as 1.5 μm or less.It will increase the contaminant capacity from bead etc. due to excessively crushing, Crushing of Ultrafine is mixed mixed
The average grain diameter for closing powder is preferably set to 0.3 μm or more, is more preferably set as 0.5 μm or more.In addition, above-mentioned average grain diameter refer to including
Average grain diameter including ITO powder.
The mixed mixed powder of Crushing of Ultrafine is press-formed.Extrusion forming is by filling mixed powder to metal
Mould is simultaneously for example kept for carry out within 1~3 minute with the pressure of 30~60MPa.By being press-formed obtained formed body, Ke Yizai
Using etc. static pressure intensifiers (CIP) pressurize at 140~200MPa.As a result, can get more evenly and density it is high at
Type body.
Before extrusion forming, granulation can be implemented as needed.The mobility that powder is improved by being granulated, thus next
Powder is uniformly filled to metal mold when the extrusion forming of process, uniform formed body can be obtained.Granulation there are various ways, but obtain
One of the method for pelletizing to suitable extrusion forming has the method using atomizing-type drying device (spray dryer).In addition,
Make that it includes formed body intensity in pelletizing, can be improved by adding the adhesives such as polyvinyl alcohol (PVA) in the slurry.
The sintering of formed body can be used electric furnace and implement in oxygen atmosphere.It is preferred that sintering temperature is set as 1300~1500
It DEG C is sintered.In terms of obtaining highdensity sintered body, preferably sintering temperature is 1300 DEG C or more.In addition, from oxidation is passed through
Zinc volatilization come prevent sintered density decline or occur composition deviation from the point of view of, sintering temperature be preferably 1500 DEG C with
Under.When formed body include adhesive when, the heating for reaching sintering temperature on the way, unsticking mixture work can be imported as needed
Sequence.
Retention time under sintering temperature suitably selects according to formed body size, if shorter than 5 hours, it is sintered not sufficiently
It carries out, the density of sintered body does not get higher sufficiently or is sintered body warpage.Even if the retention time is more than 30 hours and white
Whitecap takes unnecessary energy and time, in production not preferably.
By the processing instrument of IZO sintered body flat surface grinding machine, cylinder milling drum, machining obtained from such operation etc.
It is processed into desired shape, so as to make sputtering target material.The shape of sputtering target material is not particularly limited.Such as it can be with
Form discoid, rectangle, cylindrical shape etc..Sputtering target material uses after being engaged as needed by grafting material with backboard.
(6. film forming)
A side of the invention provides a kind of film build method, and this method includes using IZO target according to the present invention
The process sputtered.IZO target according to the present invention has the property that the change relative to the oxygen concentration in sputtering atmosphere
Change, the variation of resulting film resistance is small.When therefore, using IZO target according to the present invention, splashing for stay in grade can be obtained
Film is penetrated, and it is unrelated with oxygen concentration.In one embodiment, the oxygen concentration in atmosphere gas when sputtering is 2vol% or less.?
In another embodiment, the oxygen concentration in atmosphere gas when sputtering is 1vol% or less.In yet another embodiment, when sputtering
Atmosphere gas in oxygen concentration be 0.5vol% or less.In yet another embodiment, the oxygen in atmosphere gas when sputtering is dense
Degree is 0.1vol% or less.In yet another embodiment, the oxygen concentration in atmosphere gas when sputtering is 0vol%.As sputtering
When atmosphere gas, the mixed gas of argon (Ar) and oxygen can be enumerated.
Embodiment
In the following, provide examples and comparative examples of the present invention simultaneously, but these embodiments are this hairs in order to better understand
Bright and its advantage and provide, be not intended to limit invention.
The preparation > of < 1.ITO powder
With SnO2: In2O3=10:90 (wherein, SnO in embodiment 162: In2O3SnO in=15:80, embodiment 172:
In2O3=5:95) mass ratio mixing SnO2Powder and In2O3Powder carries out the mixing of wet type Crushing of Ultrafine later and (uses ZrO2Bead).?
Polyvinyl alcohol (PVA) is added in the slurry being mixed to get by wet type Crushing of Ultrafine to be granulated as adhesive, and pelletizing is obtained.
Pelletizing is press-formed to Φ 280mm × 20mmt at 30MPa, is sintered 20 in the electric furnace of oxygen atmosphere, at 1500 DEG C
Hour, to manufacture ITO sintered body.Resulting ITO sintered body is crushed using alms bowl pestle and mortar, is crushed using pot mill,
It reuses ball mill and carries out wet type Crushing of Ultrafine, sieved with the sieve that aperture is 150 μm, obtain ITO powder.According to test number,
The average grain diameter of screening adjustment ITO powder.
The manufacture > of 2. sintered body of <
Prepare according to the test number recorded in table 1-12O3Powder, ZnO powder, SnO2Powder, B2O3Powder.Next, by wet
The crushing that declines (uses ZrO2Bead) these powder are pulverized and mixed.It is quasi- before being added before 5 minutes that this is pulverized and mixed stopping
Standby ITO powder makes to be finally reached the ratio of metallic atom documented by table 1-1.The average grain of slurry (mixed powder) after being pulverized and mixed
Diameter is 0.3~0.8 μm of range in all test examples.It is granulated by adding PVA in the slurry after being pulverized and mixed,
Obtain pelletizing.But the test example for being denoted as " having " " interim sintering " in table, by In2O3Powder, ZnO powder and ITO powder are micro-
It is mixed before crushing, makes to reach the metallic atom ratio of table 1-1 record, at 1300 DEG C, interim sintering 5 hours in an atmosphere,
Resulting piece is ground with alms bowl pestle and mortar, carries out wet type Crushing of Ultrafine using ball mill, until average grain diameter is 0.3~0.8 μm
Range.PVA is added in gained slurry to be granulated, and pelletizing is made.
Later, in each test example, pelletizing is press-formed at 30MPa to Φ 280mm × 20mmt, in 140MPa
Lower progress isostatic cool pressing pressurization forms formed body, and sintering 10 is small in the electric furnace of air atmosphere, at 1400 DEG C of temperature later
When.In addition, analysis sintered body at being grouped as, as a result confirm identical as the proportion of raw material powder.
The average grain diameter of powder refers to, the LA-960 manufactured using Horiba Ltd, using laser diffraction,
Scattering method calculates the median particle diameter (D50) when the cumulative distribution of granularity according to volume reference.
The average grain diameter > of < 3.Sn segregation grain
About the sintered body of each test example obtained by the above-mentioned manufacture method, measurement is dispersed in tissue according to the method described above
In Sn segregation grain average grain diameter.It the results are shown in Table 1-2.
A number density > of < 4.Sn segregation grain
About the sintered body of each test example obtained by above-mentioned manufacturing method, measurement is dispersed in group according to the method described above
A number density of Sn segregation grain in knitting.It the results are shown in Table 1-2.
5. volume resistivity > of <
Four probes are utilized using device below for the sintered body of each test example obtained by the above-mentioned manufacture method
Method measures volume resistivity at room temperature.
Instrument Measuring Resistivity of Carbon Products: model FELL-TC-100-SB- Σ 5+ (manufacture of NPS Co., Ltd.)
Measure fixture: RG-5
It the results are shown in Table 1-2.
6. relative density > of <
About the sintered body of each test example obtained by above-mentioned manufacturing method, density is measured using Archimedes method,
It is found out relative to the ratio (%) by forming determining reference density, as relative density.
The sputtering test of < 7. >
The sintered body of each test example obtained by above-mentioned manufacturing method is machined, being finish-machined to diameter is
8 inches, with a thickness of the disc-like spattering target material of 5mm.About cylindrical shape, essence is carried out by cylinder grinding and lathe process
Processing.Next, being sputtered using the sputtering target material.Sputtering condition is as follows.Change the oxygen concentration in atmosphere, is splashed twice
Penetrate test.In addition, substrate heating when sputtering or the annealing after sputtering do not carry out.
Sputtering power: 1W/cm2
Air pressure: 0.5Pa (abs)
Atmosphere: (1) Ar: air pressure of the oxygen containing 0vol% is 0.5Pa (abs)
(2) Ar: air pressure of the oxygen containing 2vol% is 0.5Pa (abs)
Film thickness:
The model FELL-TC-100-SB- Σ 5+ film resiativity analyzer manufactured using NPS Co., Ltd., is passed through
The film resistivity of four probe method measurement gained sputtered film.It the results are shown in Table 1-2.
Table 1-1
Table 1-2
Comparative example 4 and comparative example 5 are to be not added with SnO in the feed2With the example of any one of ITO, relative to sputtering
The variation of oxygen concentration in atmosphere, film resistance dramatically change.
Comparative example 1~3 is to be added to SnO in the feed2Example.Relative to the variation of the oxygen concentration in sputtering atmosphere,
The variation of film resistance is big, and volume resistivity is also big.Show SnO2Addition and the decline of volume resistance do not contact directly.
Examples 1 to 21 is the example for being added to ITO in the feed.The Sn in tissue due to forming and being dispersed in target
The size for being segregated grain is appropriate, therefore volume resistivity declines.In addition, the variation relative to the oxygen concentration in sputtering atmosphere, film electricity
The variation of resistance rate is also few.
In addition, embodiment 18 is since Sn ratio shared in the whole composition of target is big, so with other embodiments phase
Than relative density is lower, and volume resistivity is big.In addition, embodiment 19 is segregated grain due to the Sn being dispersed in the tissue of target
Average grain diameter is big, therefore compared with other embodiments, volume resistivity is big.
Claims (15)
1. a kind of IZO target, wherein
With following entirety composition: containing In, Sn and Zn, with atomic ratio measuring meet Zn/ (In+Sn+Zn)=0.030~
0.250, Sn/ (In+Sn+Zn)=0.002~0.080, surplus are made of O and inevitable impurity, which has target
Material tissue, it is 200nm's or more that the partial size specific, containing In, Sn and O by FE-EPMA is dispersed in the target tissue
Sn is segregated grain.
2. IZO target according to claim 1, wherein
The IZO target contains In, Sn and Zn, meets Sn/ (In+Sn+Zn)=0.010~0.030 with atomic ratio measuring.
3. IZO target according to claim 1 or 2, wherein
The IZO target contains In, Sn and Zn, meets Zn/ (In+Sn+Zn)=0.040~0.200 with atomic ratio measuring.
4. IZO target described in any one of claim 1 to 3, wherein
The Sn that partial size is 200nm or more is segregated grain with 0.003/μm2Above a number density is present in target tissue.
5. IZO target according to any one of claims 1 to 4, wherein
The Sn that partial size is 1000nm or more is segregated grain with 0.0003/μm2Above a number density is present in target tissue.
6. IZO target according to any one of claims 1 to 5, wherein
The relative density of the IZO target is 90% or more.
7. IZO target described according to claim 1~any one of 6, wherein
The volume resistance of the IZO target is 0.3m Ω cm or more and less than 7.0m Ω cm.
8. IZO target according to any one of claims 1 to 7, wherein
The average grain diameter of the Sn segregation grain is 450nm or more and 9000nm or less.
9. IZO target described according to claim 1~any one of 8, wherein
The Sn that partial size is 10000nm or more is segregated grain with 0.0002/μm2A number density below is present in target tissue.
10. IZO target described according to claim 1~any one of 9, wherein
The IZO target also contains B, meets B/ (In+Sn+Zn+B)≤0.036 with atomic ratio measuring.
11. the manufacturing method of IZO target according to any one of claims 1 to 9, wherein
This method comprises: by ITO powder, In2O3The process that the mixture of powder and ZnO powder is sintered.
12. the manufacturing method of IZO target according to claim 11, wherein
Each particle for constituting ITO powder contains In and Sn, meets 6≤In/Sn≤36 with atomic ratio measuring.
13. the manufacturing method of IZO target described in any one of claim 10, wherein
This method comprises: by ITO powder, In2O3Powder, ZnO powder and B2O3The process that the mixture of powder is sintered.
14. a kind of film build method, wherein
This method comprises: using the process that IZO target is sputtered described in any one of claim 1~10.
15. film build method according to claim 14, wherein
It is to implement sputtering process in 0.1vol% atmosphere gas below in oxygen concentration.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2017227269A JP6637948B2 (en) | 2017-11-27 | 2017-11-27 | IZO target and method for manufacturing the same |
JP2017-227269 | 2017-11-27 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN109837512A true CN109837512A (en) | 2019-06-04 |
CN109837512B CN109837512B (en) | 2021-02-12 |
Family
ID=66845055
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201811055653.4A Active CN109837512B (en) | 2017-11-27 | 2018-09-11 | IZO target and method for producing the same |
Country Status (4)
Country | Link |
---|---|
JP (1) | JP6637948B2 (en) |
KR (1) | KR102164172B1 (en) |
CN (1) | CN109837512B (en) |
TW (1) | TWI683018B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20240013218A (en) * | 2021-06-04 | 2024-01-30 | 제이엑스금속주식회사 | Sputtering target and its manufacturing method |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006249554A (en) * | 2005-03-14 | 2006-09-21 | Fuji Electric Holdings Co Ltd | Sputtering target, preparing method therefor and sputtering method |
CN101268211A (en) * | 2005-09-20 | 2008-09-17 | 出光兴产株式会社 | Sputtering target, transparent conductive film, and transparent electrode |
JP2011108873A (en) * | 2009-11-18 | 2011-06-02 | Idemitsu Kosan Co Ltd | In-Ga-Zn-BASED OXIDE SINTERED COMPACT SPUTTERING TARGET AND THIN-FILM TRANSISTOR |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2695605B2 (en) | 1992-12-15 | 1998-01-14 | 出光興産株式会社 | Target and manufacturing method thereof |
JP2000068456A (en) | 1998-08-21 | 2000-03-03 | Nec Corp | Semiconductor device and manufacture of the same |
KR100603128B1 (en) * | 1999-05-10 | 2006-07-20 | 닛코킨조쿠 가부시키가이샤 | Sputtering target |
KR100849258B1 (en) * | 1999-11-25 | 2008-07-29 | 이데미쓰 고산 가부시키가이샤 | Sputtering target and transparent conductive oxide |
EP1693483B1 (en) * | 2002-08-02 | 2009-10-07 | Idemitsu Kosan Co., Ltd. | Sputtering target, sintered article, conductive film fabricated by utilizing the same, organic el device, and substrate for use therein |
KR102142845B1 (en) * | 2012-05-31 | 2020-08-10 | 이데미쓰 고산 가부시키가이샤 | Sputtering target |
JP5695221B2 (en) * | 2012-07-13 | 2015-04-01 | Jx日鉱日石金属株式会社 | Sintered body and amorphous film |
JP2017014534A (en) * | 2013-10-09 | 2017-01-19 | 出光興産株式会社 | Sputtering target and production method thereof |
JP6159867B1 (en) * | 2016-12-22 | 2017-07-05 | Jx金属株式会社 | Transparent conductive film forming target, transparent conductive film forming target manufacturing method, and transparent conductive film manufacturing method |
-
2017
- 2017-11-27 JP JP2017227269A patent/JP6637948B2/en active Active
-
2018
- 2018-09-11 CN CN201811055653.4A patent/CN109837512B/en active Active
- 2018-09-12 KR KR1020180108709A patent/KR102164172B1/en active IP Right Grant
- 2018-09-14 TW TW107132416A patent/TWI683018B/en active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006249554A (en) * | 2005-03-14 | 2006-09-21 | Fuji Electric Holdings Co Ltd | Sputtering target, preparing method therefor and sputtering method |
CN101268211A (en) * | 2005-09-20 | 2008-09-17 | 出光兴产株式会社 | Sputtering target, transparent conductive film, and transparent electrode |
JP2011108873A (en) * | 2009-11-18 | 2011-06-02 | Idemitsu Kosan Co Ltd | In-Ga-Zn-BASED OXIDE SINTERED COMPACT SPUTTERING TARGET AND THIN-FILM TRANSISTOR |
Also Published As
Publication number | Publication date |
---|---|
CN109837512B (en) | 2021-02-12 |
KR20190062155A (en) | 2019-06-05 |
JP6637948B2 (en) | 2020-01-29 |
TWI683018B (en) | 2020-01-21 |
JP2019094550A (en) | 2019-06-20 |
KR102164172B1 (en) | 2020-10-12 |
TW201925501A (en) | 2019-07-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR100957733B1 (en) | Gallium oxide-zinc oxide sputtering target, method of forming transparent conductive film and transparent conductive film | |
TWI768130B (en) | Target material for deposition of molybdenum oxide layers | |
CN101326304B (en) | Gallium oxide/zinc oxide sputtering target, method of forming transparent conductive film and transparent conductive film | |
KR101004981B1 (en) | Gallium oxide-zinc oxide sputtering target, method for forming transparent conductive film, and transparent conductive film | |
JP5808513B1 (en) | Sputtering target material | |
JP4022676B2 (en) | High-density ITO sintered body, method for producing the same, and sputtering target | |
KR102166104B1 (en) | Sputtering target, method of producing sputtering target, method of producing amorphous film, method of producing amorphous film, method of producing crystalline film and crystalline film | |
CN109837512A (en) | IZO target and its manufacturing method | |
CN108350564A (en) | Oxidate sintered body sputtering target and its manufacturing method | |
CN103849842B (en) | Sputtering target and conductive metal oxide film | |
CN107531576A (en) | Alumina sintered body and basal substrate used for optical elements | |
CN106460160B (en) | W-Ti sputtering targets | |
JP4918738B2 (en) | ITO sputtering target and manufacturing method thereof | |
EP3875443A1 (en) | Sintered body | |
JP7110749B2 (en) | MoNb target material | |
JP4524577B2 (en) | Transparent conductive film and sputtering target | |
JP2007254282A (en) | Process of preparing sintered ito compact | |
JP3870446B2 (en) | ITO sintered body manufacturing method and sputtering target | |
JP2007231381A (en) | Ito sputtering target and production method therefor | |
TWI564420B (en) | Sputtering target and manufacturing method of sputtering target | |
TWI697458B (en) | Sputtering target | |
JP5424140B2 (en) | Sputtering target for forming transparent conductive film | |
JPH08246142A (en) | Oxide sintered compact |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |