CN105358734B - Sputtered target material - Google Patents
Sputtered target material Download PDFInfo
- Publication number
- CN105358734B CN105358734B CN201580001209.2A CN201580001209A CN105358734B CN 105358734 B CN105358734 B CN 105358734B CN 201580001209 A CN201580001209 A CN 201580001209A CN 105358734 B CN105358734 B CN 105358734B
- Authority
- CN
- China
- Prior art keywords
- copper
- sputtered target
- powder
- target material
- phase
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physical Vapour Deposition (AREA)
- Powder Metallurgy (AREA)
Abstract
The present invention provides a kind of sputtered target material, and which can be discharged by DC source, and suitable for forming the blackening layer of the touch panel colorimetric sensor films of capacitance-type.A kind of relevant sputtered target material of the present invention, which has the line and staff control of copper system metal phase and oxide phase, and oxygen content is the 5 atom % of atom % to 30, and relative density is more than 85%, and volumetric resistivity value is 1.0 × 10‑2Below Ω cm.It is preferred that the mean diameter of its copper system metal phase is 0.5 μm to 10.0 μm, and the mean diameter of oxide phase is 0.05 μm to 7.0 μm.
Description
Technical field
The present invention is related to the sputtered target material containing copper or copper alloy and oxide, in particular to suitable for formed adopt
With the sputtered target material of the blackening layer of copper mesh purpose contact panel colorimetric sensor films.
Background technology
In recent years, for the display device of liquid crystal display etc., on market it is existing many with directly contact picture implementing
The so-called touch panel of operation.Also, for this kind of contact panel, typically perceive as the contact panel using electrostatic capacity type
Use colorimetric sensor films.
The contact panel colorimetric sensor films of this kind of electrostatic capacity type, are the ELDs using such as PET film base material
(ito film：100 Ω of resistance value/ or so).Using the contact panel colorimetric sensor films of this kind of ito film, due to the electricity of ito film
The problem of resistance, it is difficult to make large-area contact panel.Therefore, used using the copper mesh mesh contact panel for being capable of achieving low-resistance value
The exploitation of colorimetric sensor films grows up then.
Using this kind of copper mesh purpose contact panel colorimetric sensor films, it is that copper is formed by vapour deposition method on PET film base material
Film, and the copper film is processed into into cancellate mesh.Using this kind of copper mesh purpose colorimetric sensor films, its copper mesh purpose resistance value is
1 Ω/ or so, therefore can fully tackle large area contact panel.Using the specifics of this copper mesh purpose touch-control colorimetric sensor films
Preparation method, is that copper film is formed on PET film base material by vapour deposition method, and on its copper film surface, is further formed and be referred to as melanism
The thin film to adjust colorimetric sensor films brightness of layer.
For the prior art for forming this blackening layer, being typically known as copper is carried out at surface by galvanoplastic or sputtering method
The method managed and formed, or using copper or the sputtered target material of copper alloy, supply oxygen or nitrogen etc. in sputter and pass through reaction
Property sputter formed method (for example, referring to patent documentation 1 to 3).
In the formation technology of the blackening layer of these prior arts, it is noted in surface preparation and is not suitable for copper mesh purpose
The point of graph thinning, in reactive sputtering method, because of the impact of the supplies such as oxygen, with the tendency that rate of film build is reduced, so as to put
Electricity is unstable.Therefore, in reactive sputtering method, in order to be able to only blackening layer be formed with Ar gas, also increase the sputters such as copper in research
The oxygen content of target, if however, increasing the oxygen content of sputter material, the volume resistance of target itself can rise, unidirectional current
The electric discharge (sputter) in source becomes difficult.
[prior art literature]
[patent documentation]
Patent documentation 1：Japanese Patent Laid-Open 2013-129183 publication
Patent documentation 2：No. 3969743 description of Japanese Patent No.
Patent documentation 3：Japanese Patent Laid-Open 2008-311565 publication
The content of the invention
[the be intended to problem for solving of invention]
The present invention is developed using above-mentioned situation as background, it is therefore intended that is provided and a kind of can be discharged with DC source
Sputtered target material containing copper or copper alloy and oxide, and, there is provided a kind of touch-control suitable for forming capacitance-type
With the sputtered target material of the blackening layer of colorimetric sensor films.
[to the means to solve the problem]
A kind of relevant sputtered target material of the present invention, which has the line and staff control of copper system metal phase and oxide phase, and oxygen content is 5
The atom % of atom % to 30, relative density are more than 85%, and volumetric resistivity value is 1.0 × 10-2More than Ω cm.
If according to the sputtered target material of the present invention, due to the volumetric resistivity value of target itself it is relatively low, therefore can be with cheap direct current
Power supply is discharged, and can lift rate of film build.Also, due to the oxygen containing high concentration in sputtered target material, therefore sputter gas can be reduced
In oxygen amount and carry out sputter, and form stable blackening layer.Copper system metal phase in sputtered target material of the present invention, refers to only copper
Single-phase or copper alloy phase, for copper alloy phase, can enumerate：Copper-nickel alloy phase, copper-titanium alloy are equal.Oxide only mutually refers to
Oxide phase with copper (copper oxide phase) or containing copper alloy as composition oxide phase (copper alloy oxide phase).Copper is closed
During golden oxide phase, its metal ingredient can be it is identical with copper alloy, it is alternatively different.So oxide can mutually be enumerated：Copper oxide
Phase, copper-nickel alloy copper close oxide phase, copper-titanium alloy copper alloy oxide it is equal.Also, by becoming this oxide
The tissue mixed with copper system metal phase, in splashing in the tissue for crossing target, forms the network produced by copper system metal phase, and
Its network becomes conductive path, even if oxygen content is the 5 atom % of atom % to 30, remains to realize low volumetric resistivity value.
About the oxygen content of sputtered target material of the present invention, it is the 5 atom % of atom % to 30, preferably 10 atom % are former to 25
Sub- %, the more preferably 10 atom % of atom % to 20.If oxygen content becomes below 5 atom %, it is necessary to led in sputter gas in a large number
Enter oxygen, if more than 30 atom %, electric discharge being carried out with DC source and becoming difficult.When in the sputtered target material of the present invention containing nickel, nickel
Content preferably below 61.0 atom %, more preferably below 57.0 atom %.If nickel content is closed more than 61.0 atom %, copper-nickel
Metallographic shows ferromagnetism, relevant with rate of film build reduction during sputter.Also, when containing titanium in the sputtered target material of the present invention, then titanium
Content preferably below 7.50 atom %, more preferably below 6.25 atom %.If Ti content is more than 7.50 atom %, oxidation is formed
Titanium phase, easily produces cracking in sintering.
Also, the relative density of the sputtered target material of the present invention is more than 85%, preferably 90%, more preferably more than 95%.Phase
To density closer to 100% better.If relative density becomes less than 85%, sputtered target material void increases, so that easily inhaling
Receive the gas in air.Also, the seminess using its space as the paradoxical discharge of starting point or sputtered target material is susceptible to.
Furthermore, sputtered target material for the present invention, in order to stably implement to discharge with DC source, volumetric resistivity value is
1.0×10-2Below Ω cm.It is preferred that 1.0 × 10-3Below Ω cm, more preferably 5.0 × 10-4Below Ω cm.
Sputtered target material for the present invention, the mean diameter of preferred copper system metal phase at 0.5 μm to 10.0 μm, oxide phase
Mean diameter at 0.05 μm to 7.0 μm.The more preferably mean diameter of copper system metal phase at 1.0 μm to 8.0 μm, oxide phase
Mean diameter is at 0.5 μm to 6.0 μm.Mean diameter to make copper system metal phase is less than 0.5 μm, it is necessary to will be used as sputtered target material
The copper or copper alloy of raw material, the metal raw feed powder that can form alloy with copper are set to minor diameter, if but too small using mean diameter
Raw material powder, then because of the impact of oxide-film formed on raw material powder surface, the sintering when sputtered target material is manufactured becomes incomplete,
So that the oxygen content of sputtered target material easily changes.If the mean diameter of copper system metal phase easily produces oxidation more than 10.0 μm
The cohesion of thing phase, is difficult to form conductive path with the network for showing copper system metal phase.If also, produce oxide phase cohesion,
With which it has been thus paradoxical discharge has been produced in sputter easily.Also, the mean diameter to make oxide phase is less than 0.05 μm,
The oxidate powder of the raw material as sputtered target material must be set to minor diameter, but due to the too small oxidate powder of mean diameter it is easy
Generation is condensed, therefore is difficult to the manufacture of sputtered target material.If the mean diameter of oxide phase is more than more than 7.0 μm, in sputter
Paradoxical discharge is produced easily.If the tissue mutually blended with oxide of the copper system metal phase with this kind of mean diameter, can be steady
Surely realize that volumetric resistivity value is 1.0 × 10-2The sputtered target material of below Ω cm.Also, the net to form aforesaid copper system metal phase
Network is constructed, when observing the section of sputtered target material, in 60 μ m, 60 μ m, the area of copper system metal phase than preferably 0.32 with
On, more preferably more than 0.44.If area ratio is less than 0.32, it is difficult to form the net structure of copper system metal phase.
Sputtered target material for the present invention, preferred oxides are mutually copper oxide phase or copper alloy oxide phase.With copper system gold
Symbolic animal of the birth year and the line and staff control of oxide phase, are the 5 atom % of atom % to 30 using oxygen content, and relative density are more than 85%,
Volumetric resistivity value is 1.0 × 10-2The sputtered target material of below Ω cm, if forming blackening layer in copper surface, can make to be formed is black
The surface brightness L* for changing layer side is less than 40.If surface brightness L* is more than 40, the copper mesh purpose surface of colorimetric sensor films is constituted
Reflection can become strong, and the contrast of display device can be reduced.
For the sputtered target material of the present invention, can be by by copper powder and/or copper alloy powder or copper powder and to form copper alloy
Copper beyond metal powder mix with oxidate powder, under vacuum atmosphere, and low compared with the fusing point of copper or copper alloy 450 DEG C
Sintering temperature within the temperature range of 200 DEG C is sintered and manufactures.If being low 450 DEG C less than the fusing point compared with copper or copper alloy
Sintering temperature, then sinter it is insufficient, if more than the sintering temperature that the fusing point compared with copper or copper alloy is low 200 DEG C, due to connecing
The fusing point of nearly copper or copper alloy, it is difficult to form the line and staff control that copper system metal phase is coordinated with oxide.Splash in for the present invention
In the manufacture method of plating target, can carry out：The only mixing of copper powder and oxidate powder, or only copper alloy powder is mixed with oxidate powder
Close, also, copper powder and the mixing with copper alloy powder and oxidate powder, and copper powder and to form the metal beyond the copper of copper alloy
Powder and the mixing of oxidate powder, are manufactured.Then, by adjustment copper powder and/or copper alloy powder or to form copper alloy
The combined amount of metal powder and oxidate powder beyond copper, can manufacture the sputtered target material of specific oxygen content.Here, with regard to copper alloy powder
For, such as copper-nickel alloy powder, copper-Titanium Powder etc. can be enumerated.Also, for oxidate powder, can enumerate as cupric oxide powder, copper-
Nickel alloy oxidate powder, copper-titanium alloy oxidate powder etc..Furthermore, for the metal powder beyond the copper to form copper alloy,
Can enumerate such as nikel powder：Titanium valve etc..
The manufacture method of the sputtered target material of the present invention, it is applicable using copper powder and/or copper alloy powder with oxidate powder as original
The powder metallurgic method of material.This kind of powder metallurgic method, the applicable method that article shaped is burnt till after single shaft compression molding, pressure sintering,
Electric sintering process etc., but most preferably using electric sintering process.According to electric sintering process, then the current-carrying part in mixed raw material powder is excellent
First circulating current, is sintered, i.e. to copper powder or the part of copper alloy powder, or the preferential circulating current in part to both, shape
Copper particle or copper alloy particles into copper system metal phase easily preferentially carries out granular growth.As a result, in composition sputtered target material
In copper system metal phase and the line and staff control of oxide phase, the company of the copper particle or copper alloy particles of copper system metal phase is formed really
Knot, reduces positively the volumetric resistivity value of sputtered target material itself.
[The effect of invention]
If according to the present invention, being capable of achieving the sputter with copper or copper alloy and oxide that can be discharged with DC source
Target, and stably can easily form the blackening layer of the contact panel colorimetric sensor films of capacitance-type.
Description of the drawings
Fig. 1 is observed for the section of embodiment 1.
Fig. 2 is observed for the section of embodiment 4.
Specific embodiment
[the most preferred embodiment of invention]
Hereinafter, illustrate the embodiment of the present invention.First, illustrate the manufacture of the sputtered target material of this embodiment.
In this embodiment, the sputtered target material (embodiment 1 to 3) of each oxygen content is made.In order to compare, also comparison
Example 1 to 3.In table 1, the data of each sputtered target material are represented.Hereinafter, illustrate the manufacturing condition of each sputtered target material.
Embodiment 1：With mean diameter D50=3.0 μm of copper powder and mean diameter D50=3.0 μm of copper oxide (I) powder is made
For raw material.Consider that the oxygen content in copper oxide (I) powder becomes stoichiometric proportion (Cu：O=2：1), 20 are become with oxygen content former
The mode of sub- % is weighed.Weighed raw material powder and zirconium oxide crushing medium are devoted in tank (pot), using ball milling
Machine mixes 3 hours.Then, after being mixed dressing sieve point, it is filled in the graphite mold of diameter 174mm.Will be filled with mixed powder
Graphite mold be placed in electric sintering equipment (DR.SINTER/SPS Syntax (stock) systems) after, be sintered according to following condition.
<Sintering condition>
Atmosphere (atmosphere)：Vacuum (pressure：40Pa (handkerchief))
Heating-up time：30 DEG C/min (minute)
Sintering temperature：850℃
The sintering retention time:30 minutes
Pressure：25MPa (MPa)
Cooling：Natural cooling
Machining will be carried out according to the sintered body obtained by above-mentioned sintering condition, make diameter 101.6mm, thickness 5mm and splash
Plating target.
Embodiment 2：Weighed in the way of the oxygen content of raw material powder becomes 15 atom %.Remaining manufacturing condition and enforcement
Example 1 is identical.
Embodiment 3：Weighed in the way of the oxygen content of raw material powder becomes 10 atom %.Remaining manufacturing condition and enforcement
Example 1 is identical.
Embodiment 4：With mean diameter D50=9.6 μm of nikel powder and mean diameter D50=2.5 μm of copper oxide (II) powder is made
For raw material.Consider that the oxygen content in copper oxide (II) powder becomes stoichiometric proportion (Cu：O=1：1), 30 are become with copper content former
Sub- %, nickel content become 40 atom %, oxygen content and become the mode of 30 atom % and weighed.Remaining manufacturing condition and embodiment
1 is identical.
Embodiment 5：By mean diameter D50=9.6 μm of nikel powder, mean diameter D50=3.0 μm of copper powder and average grain
Footpath D50=2.5 μm of copper oxide (II) powder is used as raw material.Consider that the oxygen content in copper oxide (II) powder becomes stoichiometric proportion
(Cu：O=1：1), becoming 34 atom %, nickel content by copper content becomes in the way of 46 atom %, oxygen content become 20 atom %
Weighed.Which is same as Example 1 in manufacturing condition.
Comparative example 1：To with the mixing of ball mill, mode is implemented similarly to Example 1, with single shaft compression molding (plus
Press pressure：500kgf (4 gram force)/cm2) make diameter 140mm press-powder thing.Then, entered according to following condition using firing furnace
Row burns till.
<Firing condition>
Atmosphere：Air
Heating-up time：50 DEG C/hr (about 0.83 DEG C/min)
Sintering temperature：900℃
The sintering retention time：4 hours
Cooling：50 DEG C/hr (about 0.83 DEG C/min)
Machining will be carried out with the sintered body obtained by above-mentioned sintering condition, and make diameter 101.6mm, thickness 5mm and splash
Plating target.
Comparative example 2：Vacuum (pressure is set to except firing atmosphere is made：Beyond 40Pa), remaining is identical with comparative example 1.
Comparative example 3：Copper oxide (I) powder is used only as raw material powder.Its oxygen content is 33.3 atom % (Cu：O=2：1).
Cupric oxide powder is directly filled in the graphite mold of diameter 174mm.Later condition reality in the way of similarly to Example 1
Apply.
For made each sputtered target material, implement oxygen content, relative density, volumetric resistivity value, mean diameter evaluation.
Will be as a result, being shown in table 1 and table 2.Also, each evaluation methodology is as follows.
Oxygen content：The surface of sintered body is cut by machining, powder is cut from gained, using oxygen nitrogen analysis device
(EMGA-550/ (stock) holes field makes made), determines oxygen content.
Relative density：By the weight (g) of sputtered target material divided by its volume (cm3), calculate the reason according to following theoretical formulas (number 1)
By density p (g/cm3) percentage rate, be set to relative density (%).
[number 1]
In formula, C (Cu), C (Cu2O) represent that the copper system metal phase in sputtered target material is (heavy with the content of oxide phase respectively
Amount %), ρ (Cu), ρ (Cu2O density, the density of oxide of copper or copper alloy) are represented respectively.Copper system metal phase and oxide
The content (weight %) of phase, it is assumed that the oxygen in the sintered body surveyed is completely formed copper oxide (I) or copper alloy oxide and calculates
Go out.
Volumetric resistivity value：Using low-resistivity meter (LorestaHP/ (stock) Mitsubishi Chemical Analytech systems) and four probes
Method detector, determines the volumetric resistivity value of the sputtered target material after processing.
Mean diameter：The surface of grinding sputtered target material is made smooth.For the smooth surface, by being equipped with power dissipation
Type X light analysis (EDS)/electric wire backscattering diffraction analysis (EBSD) device (Pegasus System/Ametek (stock) systems)
FE gun shaped sweep electron microscope (SUPRA55VP/Carl Zeiss company systems) and determine the EDS light of copper and nickel and oxygen
Spectrum and EBSD patterns.Condition determination is set to accelerating potential 20kV, 60 × 60 μm of viewing area, 0.5 μm of measuring interval.With index
Crystalline phase be copper system metal phase (copper phase or copper alloy phase) and oxide phase, from the difference of EDS spectrum both.For the number of gained
According to, the analytical bibliography " Grain Size " of EBSD analysis programs (OIMAnalysis/ (stock) TSLSolutions systems) is selected, with
Calculate the average crystallite particle diameter (μm) of copper system metal phase and the out of the ordinary attached area weight of oxide phase.Now, more than 5 ° are detected
Gun parallax when, be recognized as general grain circle person, for copper, be<111>Around axle, in the twin crystal of the position relation of 60 ° of rotations
Grain circle is not intended as the mode of general grain circle and implements.Also, the area ratio of copper system metal phase, following manner is calculated.
The area ratio of copper system metal phase：Using value use above-mentioned analysis program, with " Color Coded Map
Style " selects " Phase (phase) ", and other settings then calculate " Total Fraction " by being set to initial setting
Value.
[table 1]
As shown in table 1, in embodiment 1 to 3, the oxygen content of made sputtered target material, the rough level into for the purpose of.In
During comparative example 1, due to implementing in an atmosphere to burn till process, therefore oxygen content is significantly increased (relative to the oxygen content 20.0 in raw material
Atom %, increases to 46.8 atom % after manufacture).In comparative example 2, although firing temperature higher (900 DEG C), firing time compared with
Long (4hr), but still become the low person of relative density.In contrast, understanding Jing using the relative of the embodiment 1 to 3 of electric sintering process
Density becomes more than 85%, according to electric sintering process, can acceleration of sintering.Even if the embodiment containing nickel 4,5, made sputter
The oxygen content of the target also level slightly into for the purpose of.But, such as compared with embodiment 1 to 3, compared with the oxygen content in raw material powder,
Slightly reduce.It is thought that as the nickel oxide formed by nikel powder and the reaction of Indium sesquioxide. (II) powder mutually has the event of oxygen defect.
On the other hand, with regard to relative density, embodiment 4,5 becomes more than 85%.
Secondly, in embodiment 1 to 3, it is known that volumetric resistivity value is 1.0 × 10-2The scope of below Ω cm, can be with unidirectional current
Discharged in source.On the other hand, comparative example 1,3 becomes insulant, it is impossible to implement the measure of volumetric resistivity value.For comparative example 2,
Also because volumetric resistivity value is very big and measured value is unstable, therefore fail specific resistance value.Also, for comparative example 2, although with one
Fixed electric conductivity, but still be difficult to discharge with stabilizing it by DC source.
In Fig. 1, the sputtered target material that embodiment 1 is observed with electric wire backscattering diffraction assay set-up (EBSD devices) is represented
Section result.Show in thinking Fig. 1 black part be copper phase, remainder be oxide phase.Copper is seen mutually to link
Into network-like state, therefore conductive path is formed in material internal.Therefore, in the situation of embodiment, it is believed that volumetric resistivity value becomes
It is low.Furthermore, it is computed, in Fig. 1 visuals field (60 60 μm of μ m), the result of copper phase area ratio is 0.48.On the other hand, in comparative example 1
Situation, as oxygen content is larger, therefore think target entirety by the insulant that constituted with oxide phase.Also, in comparative example 2
Situation, is the low state of crystallinity, and copper phase is distinguished as indefinite structural state with oxide phase.It is therefore contemplated that volume is electric
Resistance also becomes very high person.Furthermore, in the situation of comparative example 3, become the tissue that can hardly confirm copper alloy phase, therefore,
Think to become the state person for being close to insulant.
Also, in Fig. 2, representing the result of the section of the sputtered target material of observation embodiment 4.The part for showing black in Fig. 2 is
The alloy phase (copper system metal phase) of copper and nickel, remainder are oxide phase.From EDS spectrum and the result of EBSD patterns, it is known that
Also contain nickel oxide phase.Jing understands the nikel powder as raw material, and a part forms copper system metal phase, and remainder forms copper alloy oxygen
Compound phase.Also, identical with the situation of Fig. 1, the copper system metal phase in embodiment 4 connects to network state.Furthermore, calculate Fig. 2
In the visual field (60 60 μm of μ m), the result of the area ratio of copper system metal phase is 0.70.
The mean diameter of embodiment 1, copper system metal phase (copper phase) is 4.8 μm, oxide is mutually 3.9 μm.Thus, it is known that compared with
Mean diameter (the D of the copper powder used with raw material50=3.0 μm) somewhat carry out grain growth.Also, also it is unconfirmed go out oxide phase
Cohesion.In the situation of comparative example 2, do not know, whether because sintering is insufficient, not being specifically detected Kikuchi pattern in EBSD devices, and
Fail to calculate the mean diameter of copper phase.
Then, illustrate the result about blackening layer is formed using made sputtered target material.The evaluation of blackening layer, be
Copper is formed with copper on glass substrate and matches somebody with somebody exhausted layer, and be made in the evaluation sample that its layers of copper surface is formed with blackening layer.
Although the thickness of blackening layer is not particularly limited, but can be set to 5nm to 100nm.Sputter also only can be implemented with argon, but
The just purpose of the optical characteristics of the formed blackening layer of adjustment, can also add oxygen or nitrogen, or both as sputter gas.Here
The ratio (gas flow/argon flow amount for being added) preferably less than 20% of situation, the gas flow for being added and argon flow amount is planted,
More preferably less than 15%.If the excessive oxygen of addition or nitrogen or both, have and cause the rate of film build to reduce or discharge instability
Tendency.
In this evaluation sample, although form the layers of copper using fine copper, but the copper wiring constituted in colorimetric sensor films etc.
When, require it is to use fine copper for low-resistance, it is considered to during cohesive with base material, can also use copper alloy.Also, for really and base
The purpose of the adherence of material, also can form the adhesive layer such as titanium or molybdenum in the substrate of copper wiring.Although the thickness of copper wiring is without especially
Limit, but can also be set to such as 50nm to 10000nm.
The manufacturing condition for evaluating sample is as follows.First, made each sputtered target material and gripper shoe phase made of copper are made
Fit and become sputter target.By this sputter target and distribution fine copper sputter target, it is installed in and possesses the sputtering unit for having DC source
And carry out film forming.Membrance casting condition is as follows.
<Membrance casting condition>
Laminated film is constituted：Blackening layer/copper wiring film/glass substrate
Blackening layer thickness：20nm
Copper wiring layer thickness：200nm
Glass substrate：40mm×40mm×0.7mmt
Reach pressure：5×10-6Below Torr
Oxygen flow：0.0 to 10.0sccm (interval 2.5sccm)
The ratio of oxygen flow/argon flow amount：0.0 to 20.4%
Apply electric power：100W to 300W (1.3W/cm2To 3.7W/cm2)
For made evaluation sample, the brightness (L*) on its surface is determined.L*'s is determined as using spectral photometric colour measuring meter
(CM-2500d/Konica Minolta (stock) systems), and with L*a*b* color specification systems, the laminated film surface of evaluation of measuring sample
L*.In order to compare, also make using commercially available tough copper metallurgy (tough-pitch copper) (C110, target oxygen content 0.04at%
Below), and the person's (comparative example 4) that forms blackening layer.In table 2, represent gained each evaluation sample laminated film it is most preferred
Oxygen flow, and with the L* of the laminated film of its condition institute film forming.Most preferred oxygen flow alleged by here, be when 0.0 to
When the scope of 10.0sccm (interval 2.5sccm) forms laminated film, the oxygen flow of the situation of minimum L* is represented.
[table 2]
| Oxygen flow sccm | Brightness L* | |
| Embodiment 1 | 2.5 | 21.8 |
| Embodiment 2 | 2.5 | 29.8 |
| Embodiment 3 | 5.0 | 27.4 |
| Embodiment 4 | 2.5 | 36.0 |
| Embodiment 5 | 2.5 | 24.8 |
| Comparative example 4 | 10.0 | 49.7 |
In the blackening layer of embodiment 1 to 5, the contrast reduction to suppressing display device as the value of the brightness L* of target is
Less than 40 scope person.Also, if oxygen content in understanding sputtered target material increases, even if few oxygen flow, the value of brightness L*
Diminish.On the other hand, in the situation of comparative example 4, although oxygen flow is set to the 10sccm of maximum and is formed blackening layer, but still
So fail to make brightness L* form less than 40.
[industrial applicability]
If using the present invention, a kind of sputter process for being capable of achieving and being discharged with DC source can be efficiently manufactured, and
The contrast of display device is not reduced, and possesses the contact panel colorimetric sensor films of blackening layer.
Claims (18)
1. a kind of sputtered target material, the line and staff control with copper system metal phase with oxide phase,
Oxide is mutually copper oxide phase or copper alloy oxide phase,
The oxygen content of the sputtered target material is the 5 atom % of atom % to 30, and relative density is more than 85%, and volumetric resistivity value is
1.0×10-2Below Ω cm.
2. sputtered target material according to claim 1, it is characterised in that copper system metal phase be copper phase or containing in nickel, titanium extremely
A kind of few copper alloy phase.
3. sputtered target material according to claim 1, it is characterised in that copper system metal phase is that copper-nickel alloy phase or copper-titanium are closed
Metallographic.
4. sputtered target material according to claim 1, it is characterised in that copper alloy oxide is mutually containing in nickel, titanium at least
Kind.
5. sputtered target material according to claim 1, it is characterised in that copper alloy oxide is mutually copper-nickel alloy oxide
Phase or copper-titanium alloy oxide phase.
6. the sputtered target material according to any one of claim 2 to 5, it is characterised in that nickel content is below 61.0 atom %,
Ti content is below 7.50 atom %.
7. the sputtered target material according to any one of claim 1 to 5, it is characterised in that the mean diameter of copper system metal phase is
0.5 μm to 10.0 μm, the mean diameter of oxide phase is 0.05 μm to 7.0 μm.
8. the sputtered target material according to any one of claim 1 to 5, it is characterised in that during the section of observation sputtered target material,
In 60 μ m, 60 μ m, the area ratio of copper system metal phase is more than 0.32.
9. the sputtered target material according to any one of claim 1 to 5, which is used for the electric discharge carried out with DC source.
10. the sputtered target material according to any one of claim 1 to 5, which is used to form blackening layer.
A kind of 11. methods of manufacture sputtered target material, are the sides of the manufacture sputtered target material according to any one of claim 1 to 5
Method, comprises the steps of：
By copper powder and/or copper alloy powder or to form the metal powder beyond the copper of copper powder and copper alloy, carry out with oxidate powder
The step of mixing, and
Under vacuum atmosphere, the sintering temperature within the temperature range of 450 DEG C to 200 DEG C low compared with the fusing point of copper or copper alloy is carried out
The step of sintering.
The methods of 12. manufacture sputtered target materials according to claim 11, it is characterised in that copper alloy powder contains nickel, titanium
It is at least one.
The method of 13. manufacture sputtered target materials according to claim 11, copper alloy powder are that copper-nickel alloy powder or copper-titanium are closed
Bronze.
The methods of 14. manufacture sputtered target materials according to claim 11, it is characterised in that to form the copper of copper alloy with
Outer metal powder contains at least one of nikel powder, titanium valve.
15. it is according to claim 11 manufacture sputtered target materials methods, it is characterised in that oxidate powder be cupric oxide powder,
Or copper alloy oxidate powder.
The method of 16. manufacture sputtered target materials according to claim 11, it is characterised in that oxidate powder is containing nickel, titanium
At least one of copper alloy oxidate powder.
The method of 17. manufacture sputtered target materials according to claim 11, it is characterised in that oxidate powder is copper-nickel alloy
Oxide or copper-titanium alloy oxidate powder.
The method of 18. manufacture sputtered target materials according to claim 11, it is characterised in that sintering is entered by electric sintering process
OK.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014096515 | 2014-05-08 | ||
| JP2014-096515 | 2014-05-08 | ||
| PCT/JP2015/060441 WO2015170534A1 (en) | 2014-05-08 | 2015-04-02 | Sputtering target material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105358734A CN105358734A (en) | 2016-02-24 |
| CN105358734B true CN105358734B (en) | 2017-03-29 |
Family
ID=54392387
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580001209.2A Active CN105358734B (en) | 2014-05-08 | 2015-04-02 | Sputtered target material |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5808513B1 (en) |
| KR (1) | KR20160017101A (en) |
| CN (1) | CN105358734B (en) |
| TW (1) | TWI525208B (en) |
| WO (1) | WO2015170534A1 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6876268B2 (en) * | 2016-03-22 | 2021-05-26 | 三菱マテリアル株式会社 | Sputtering target |
| WO2017164168A1 (en) * | 2016-03-22 | 2017-09-28 | 三菱マテリアル株式会社 | Sputtering target |
| JP6932908B2 (en) * | 2016-09-26 | 2021-09-08 | 住友金属鉱山株式会社 | Laminated board, conductive board, method of manufacturing laminated board, method of manufacturing conductive board |
| WO2018159753A1 (en) * | 2017-03-01 | 2018-09-07 | 三菱マテリアル株式会社 | Sputtering target and method for manufacturing sputtering target |
| JP6447761B2 (en) * | 2017-03-01 | 2019-01-09 | 三菱マテリアル株式会社 | Sputtering target and manufacturing method of sputtering target |
| JP6533805B2 (en) * | 2017-03-31 | 2019-06-19 | Ｊｘ金属株式会社 | Sputtering target, method of manufacturing sputtering target, amorphous film, method of manufacturing amorphous film, method of manufacturing crystalline film and crystalline film |
| WO2019167564A1 (en) * | 2018-03-01 | 2019-09-06 | 三菱マテリアル株式会社 | Cu-Ni ALLOY SPUTTERING TARGET |
| JP6627993B2 (en) * | 2018-03-01 | 2020-01-08 | 三菱マテリアル株式会社 | Cu-Ni alloy sputtering target |
| JP6853440B2 (en) * | 2019-03-11 | 2021-03-31 | 三菱マテリアル株式会社 | Method for producing metallic copper and copper oxide-containing powder, metallic copper and copper oxide-containing powder, and method for producing sputtering target material and sputtering target material. |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3779856B2 (en) * | 2000-04-10 | 2006-05-31 | 株式会社日鉱マテリアルズ | Sputtering target for optical disk protective film formation |
| JP2010030824A (en) * | 2008-07-28 | 2010-02-12 | Idemitsu Kosan Co Ltd | Metal phase-containing indium oxide sintered compact and method for producing the same |
| JP2010077530A (en) * | 2008-08-26 | 2010-04-08 | Hitachi Metals Ltd | Method for producing sputtering target and sputtering target |
| JP2011084754A (en) * | 2009-10-13 | 2011-04-28 | Hitachi Metals Ltd | Method for manufacturing sputtering target |
| JP5641402B2 (en) * | 2010-02-01 | 2014-12-17 | 学校法人 龍谷大学 | Oxide film and method for producing the same, and method for producing target and oxide sintered body |
-
2015
- 2015-04-02 CN CN201580001209.2A patent/CN105358734B/en active Active
- 2015-04-02 JP JP2015533359A patent/JP5808513B1/en active Active
- 2015-04-02 WO PCT/JP2015/060441 patent/WO2015170534A1/en active Application Filing
- 2015-04-02 KR KR1020167001775A patent/KR20160017101A/en not_active Application Discontinuation
- 2015-04-30 TW TW104113853A patent/TWI525208B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| WO2015170534A1 (en) | 2015-11-12 |
| JP5808513B1 (en) | 2015-11-10 |
| TW201542849A (en) | 2015-11-16 |
| JPWO2015170534A1 (en) | 2017-04-20 |
| KR20160017101A (en) | 2016-02-15 |
| CN105358734A (en) | 2016-02-24 |
| TWI525208B (en) | 2016-03-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105358734B (en) | Sputtered target material | |
| TWI338720B (en) | ||
| CN105143931B (en) | Light absorbing layer and containing system, layer system manufacturing method and the applicable sputter target layer by layer | |
| KR101155358B1 (en) | Composite oxide sinter, process for producing amorphous composite oxide film, amorphous composite oxide film, process for producing crystalline composite oxide film, and crystalline composite oxide film | |
| KR100957733B1 (en) | Gallium oxide-zinc oxide sputtering target, method of forming transparent conductive film and transparent conductive film | |
| JP4098345B2 (en) | Gallium oxide-zinc oxide sputtering target, method for forming transparent conductive film, and transparent conductive film | |
| CN105439541B (en) | The manufacturing method of indium oxide sintered body, indium oxide transparent conductive film and the transparent conductive film | |
| JP4761868B2 (en) | Sputtering target, manufacturing method thereof and transparent conductive film | |
| TW200535283A (en) | Indium oxide-zinc oxide-magnesium oxide based sputtering target and transparent conductive film | |
| TWI603938B (en) | Niobium oxide sputtering target, method of producing the same, and niobium oxide film | |
| KR20130029365A (en) | Transparent conductive films | |
| KR20100012040A (en) | Amorphous composite oxide film,crystalline composite oxide film,process for producing amorphous composite oxide film,process for producing crystalline composite oxide film,and composite oxide sinter | |
| CN100513353C (en) | Target for transparent conductive film, transparent conductive material, transparent conductive glass, and transparent conductive film | |
| JP6533805B2 (en) | Sputtering target, method of manufacturing sputtering target, amorphous film, method of manufacturing amorphous film, method of manufacturing crystalline film and crystalline film | |
| CN103849842B (en) | Sputtering target and conductive metal oxide film | |
| CN109695020A (en) | Mn-W-Cu-O base sputtering target and preparation method thereof | |
| JP2015124145A (en) | Indium oxide-based oxide sintered compact and production method of the same | |
| JP5913523B2 (en) | Oxide sintered body, oxide sputtering target, high refractive index conductive oxide thin film, and method for producing oxide sintered body | |
| JPH0316954A (en) | Oxide sintered product and preparation and use thereof | |
| TWI422701B (en) | Galliu oxide-zinc oxide series sputtering target | |
| JP2014047400A (en) | Ag ALLOY MEMBRANE FOR SEMI-TRANSMISSIVE ELECTRODE OF FLAT PANEL DISPLAY, AND SEMI-TRANSMISSIVE ELECTRODE FOR FLAT PANEL DISPLAY | |
| TW202018111A (en) | Optical functional film, sputtering target and method of manufacturing sputtering target | |
| CN104120336A (en) | Thin-film resistor, sputtering target material, metal foil with resistor and preparation method of thin-film resistor | |
| JP7141276B2 (en) | sputtering target | |
| Eufinger et al. | The dc magnetron sputtering behavior of TiO2− x targets with added Fe2O3 or Nd2O3 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |