CN112424390A - Optical functional film, sputtering target, and method for producing sputtering target - Google Patents

Optical functional film, sputtering target, and method for producing sputtering target Download PDF

Info

Publication number
CN112424390A
CN112424390A CN201980046706.2A CN201980046706A CN112424390A CN 112424390 A CN112424390 A CN 112424390A CN 201980046706 A CN201980046706 A CN 201980046706A CN 112424390 A CN112424390 A CN 112424390A
Authority
CN
China
Prior art keywords
component
powder
sputtering target
film
optical functional
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.)
Pending
Application number
CN201980046706.2A
Other languages
Chinese (zh)
Inventor
梅本启太
白井孝典
杉内幸也
大友健志
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Materials Corp
Original Assignee
Mitsubishi Materials Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Mitsubishi Materials Corp filed Critical Mitsubishi Materials Corp
Priority claimed from PCT/JP2019/035342 external-priority patent/WO2020050421A1/en
Publication of CN112424390A publication Critical patent/CN112424390A/en
Pending legal-status Critical Current

Links

Images

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
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • 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
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
    • 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
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • 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
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5463—Particle size distributions

Abstract

Optical function of the inventionThe film contains a first component comprising at least one element selected from the group consisting of TiC, NbC, VC, TiN, NbN and VN and an element selected from the group consisting of In2O3、Y2O3、Nb2O5、V2O5、Al2O3ZnO and SiO2The film thickness d of the optical functional film is 30nm to 100nm, the refractive index n in the visible light region is 1.5 to 2.7, and the extinction coefficient k in the visible light region is 0.3 to 1.5.

Description

Optical functional film, sputtering target, and method for producing sputtering target
Technical Field
The present invention relates to an optical functional film laminated on a metal thin film or the like and reducing reflection of light from the metal thin film or the like, a sputtering target for forming the optical functional film, and a method for producing the sputtering target.
The present application claims priority based on patent application No. 2018-167996, which was filed in japan on 7.9.2018, and patent application No. 2019-163288, which was filed in japan on 6.9.2019, and the contents of which are incorporated herein by reference.
Background
In recent years, a projection type capacitance touch panel has been used as an input means of a mobile terminal device or the like. In the touch panel of this aspect, a sensing electrode is formed to detect a touched position. The sensing electrodes are generally formed by patterning, and X electrodes extending in the X direction and Y electrodes extending in the Y direction orthogonal to the X direction are provided on one surface of a transparent substrate, and these electrodes are arranged in a grid pattern.
When a metal film is used for the electrodes of the touch panel, the pattern of the electrodes can be visually recognized from the outside because the metal film has metallic luster. Therefore, it is considered that visibility of the electrode is reduced by forming a low-reflectance film having a low reflectance of visible light on the metal thin film.
A color filter for the purpose of color display is used in flat panel displays represented by liquid crystal display devices and plasma displays. In the color filter, a black member called a black matrix is formed for the purpose of improving contrast and color purity and improving visibility.
The low-reflectance film can also be used as the black matrix (hereinafter referred to as "BM").
In the solar cell panel, when sunlight is incident through a glass substrate or the like, a back electrode of the solar cell is formed on the opposite side. As the back electrode, a metal film of molybdenum (Mo), silver (Ag), or the like is used. When the solar cell panel of this type is viewed from the back surface side, the metal film serving as the back electrode is visually recognized.
Therefore, it is considered that the visibility of the back electrode is reduced by forming the low-reflectance film on the back electrode.
As the low-reflectance film, for example, patent document 1 discloses a black film having a black pigment composed of carbon black or titanium nitride, a resin, a polymerization initiator, and an oxide for refractive index adjustment.
Patent documents 2 and 3 propose a sputtering target containing a carbide and an oxide as a sputtering target for forming an optical thin film.
Patent document 1: japanese patent laid-open publication No. 2017-211826
Patent document 2: japanese laid-open patent publication No. 2005-068507
Patent document 3: japanese patent laid-open publication No. 2003-321771
In the low reflection film described in patent document 1, the resin containing the black pigment composed of carbon black or titanium nitride is formed into a film shape, and the resin is a main component, so that the durability is not sufficient.
In the sputtering targets described in patent documents 2 and 3, although carbide is contained, the carbide has a high melting point and is inferior in sinterability, and therefore it is difficult to sufficiently increase the density of the sintered body. In a sputtering target having a low density, abnormal discharge may often occur during sputtering, and stable deposition may not be possible.
Further, in the sputtering targets described in patent documents 2 and 3, since the conductivity is insufficient, the deposition by DC sputtering cannot be stably performed and the deposition by RF sputtering is performed. Since RF sputtering has a low film formation efficiency compared to DC sputtering, an optical functional film cannot be efficiently formed.
The optical functional film is required to have durability so that optical characteristics do not significantly change during production and use. For example, when a heating step is performed after film formation, heat resistance is required. Further, when a wiring pattern is formed by etching, alkali resistance is required because alkali is used when the resist film is peeled. Further, water resistance is required because of contact with water every time of cleaning after etching and after alkali treatment.
Disclosure of Invention
The present invention has been made in view of the above circumstances, and an object thereof is to provide an optical functional film having durability and capable of sufficiently suppressing reflection of light from a metal thin film or the like, a sputtering target capable of efficiently and stably forming the optical functional film, and a method for producing the sputtering target.
In order to solve the above problem, an optical functional film according to an aspect of the present invention includes: the first component is composed of one or more than two of TiC, NbC, VC, TiN, NbN and VN; and a second component selected from In2O3、Y2O3、Nb2O5、V2O5、Al2O3ZnO and SiO2The film thickness d of the optical functional film is set to be in the range of 30nm to 100nm, the refractive index n in the visible light region is set to be in the range of 1.5 to 2.7, and the extinction coefficient k in the visible light region is set to be in the range of 0.3 to 1.5.
According to the optical functional film having such a structure, the first component composed of one or more selected from TiC, NbC, VC, TiN, NbN, and VN can improve the durability of the film and ensure the conductivity of the film.
And, by containing a compound selected from In2O3、Y2O3、Nb2O5、V2O5、Al2O3ZnO and SiO2One or two or more of the second components can adjust the optical characteristics of the film so as to further reduce the reflectance when the film is laminated on the metal wiring film. The first component and the second component are not limited to the stoichiometric ratio, and similar effects can be obtained even if some of carbon, nitrogen, and oxygen are absent.
In the optical functional film according to one aspect of the present invention, the film thickness d is set to be in the range of 30nm to 100nm, the refractive index n in the visible light region is set to be in the range of 1.5 to 2.7, and the extinction coefficient k in the visible light region is set to be in the range of 0.3 to 1.5, so that the reflectance can be suppressed to be low, and the reflection of metal can be suppressed.
In the optical functional film according to one embodiment of the present invention, the resistivity is preferably 5 Ω · cm or less.
In this case, the electrical conductivity is secured with the resistivity of 5 Ω · cm or less, and the electrical conduction can be performed through the optical functional film.
In the optical functional film according to one embodiment of the present invention, the atomic ratio α/β of the total content α of C, N to the content β of O is preferably in the range of 0.01 to 5.
In this case, the atomic ratio α/β of the total content α of C, N to the content β of O is set to 0.01 or more, and therefore, the durability of the film can be improved. On the other hand, the optical characteristics can be maintained because the atomic ratio α/β of the total content α of C, N to the content β of O is 5 or less.
A sputtering target according to an aspect of the present invention includes: a first component consisting of one or more selected from TiC, NbC, VC, TiN, NbN and VN; and a second component selected from In2O3、Y2O3、Nb2O5、V2O5、Al2O3ZnO and SiO2One or more than two of them.
The sputtering target having such a structure comprises a material selected from the group consisting ofA first component consisting of one or more of TiC, NbC, VC, TiN, NbN and VN and In2O3、Y2O3、Nb2O5、V2O5、Al2O3ZnO and SiO2One or two or more of the second components, and thus the optical functional film can be formed. The first component and the second component are not limited to the stoichiometric ratio, and similar effects can be obtained even if some of carbon, nitrogen, and oxygen are absent.
In the sputtering target according to one embodiment of the present invention, the density ratio is preferably 90% or more, and the specific resistance is preferably 0.1 Ω · cm or less.
In this case, since the density ratio is set to 90% or more, it is possible to suppress the occurrence of abnormal discharge during sputtering and to stably perform film formation. Further, since the resistivity is set to 0.1 Ω · cm or less, the film can be stably formed by DC sputtering, and the optical functional film can be efficiently formed.
In the sputtering target according to one embodiment of the present invention, the molar ratio a/B between the content a of the first component and the content B of the second component is preferably in the range of 0.1 to 20.
In this case, since the molar ratio a/B of the content a of the first component to the content B of the second component is set to 0.1 or more and 20 or less, a film having an optical constant suitable for suppressing the reflectance of the base metal can be obtained as the optical functional film.
A method for manufacturing a sputtering target according to an aspect of the present invention is a method for manufacturing a sputtering target, including: a powder mixing step of mixing a first component powder consisting of one or more selected from TiC, NbC, VC, TiN, NbN and VN with In2O3、Y2O3、Nb2O5、V2O5、Al2O3ZnO and SiO2Mixing one or more second component powders; and a sintering step of sintering a mixed powder in which the first component powder is mixed so that the particle diameter thereof is 10 [ mu ] m or lessThe above powder is in the range of 3 vol% to 50 vol%, and the powder having a particle diameter of 10 μm or less in the second component powder is 70 vol% or more.
The method for manufacturing a sputtering target having this configuration includes: a powder mixing step of mixing a first component powder consisting of one or more selected from TiC, NbC, VC, TiN, NbN and VN with In2O3、Y2O3、Nb2O5、V2O5、Al2O3ZnO and SiO2Mixing one or more second component powders; and a sintering step of sintering the mixed powder, thereby producing the sputtering target.
In the first component powder, the first component particles having a particle diameter of 10 μm or more are bonded to each other in the sintered body, and therefore, the conductivity of the sputtering target can be sufficiently ensured, because the powder having a particle diameter of 10 μm or more is 3 vol% or more.
Since the first component powder having a particle size of 10 μm or more is 50 vol% or less and the second component powder having a particle size of 10 μm or less is 70 vol% or more, the density of the sintered body can be sufficiently increased.
According to the present invention, it is possible to provide an optical functional film having durability and capable of sufficiently suppressing reflection of light from a metal thin film or the like, a sputtering target capable of efficiently and stably forming the optical functional film, and a method for producing the sputtering target.
Drawings
Fig. 1 is a cross-sectional explanatory view of a laminated film including an optical functional film according to an embodiment of the present invention.
Fig. 2 is a flowchart illustrating a method for manufacturing a sputtering target according to an embodiment of the present invention.
FIG. 3 shows the structure of a sputtering target of example 8 of the present invention.
FIG. 4 shows the structure of the sputtering target of example 29 of the present invention.
Detailed Description
Hereinafter, an optical functional film, a sputtering target, and a method for manufacturing a sputtering target according to embodiments of the present invention will be described with reference to the drawings.
As shown in fig. 1, the optical functional film 12 according to the present embodiment is formed to be laminated on the metal wiring film 11 formed on the surface of the substrate 1.
The metal wiring film 11 is made of aluminum, an aluminum alloy, copper, a copper alloy, or the like, which is a metal having excellent conductivity. The metal wiring film 11 has a metallic luster, and thus reflects visible light and is visually recognized from the outside.
The optical functional film 12 of the present embodiment is provided to suppress reflection of visible light in the metal wiring film 11 to be stacked.
The optically functional film 12 of the present embodiment contains a first component consisting of one or more selected from TiC, NbC, VC, TiN, NbN and VN and a second component consisting of In2O3、Y2O3、Nb2O5、V2O5、Al2O3ZnO and SiO2One or two or more of the above-mentioned second components.
The first component composed of one or more selected from TiC, NbC, VC, TiN, NbN, and VN has conductivity, and the conductivity of the optical functional film 12 is ensured by the first component. Further, the durability of the optical functional film 12 is improved by the first component.
From In2O3、Y2O3、Nb2O5、V2O5、Al2O3ZnO and SiO2The optical characteristics of the optical functional film 12 can be adjusted by mixing the first component with one or two or more kinds of second components.
The content ratio of the first component and the second component is appropriately set according to the optical characteristics of the optical functional film 12, but the atomic ratio α/β of the total content α of C, N derived from the first component to the content β of O derived from the second component is preferably in the range of 0.01 to 5. C. If the atomic ratio α/β of the total content α of N and the content β of O is 0.01 or more, the durability of the film can be ensured. On the other hand, if the atomic ratio α/β of the total content α of C, N to the content β of O is 5 or less, the reflectance increase and the like can be suppressed while maintaining the optical characteristics. Further, any element or compound may be added as the third component within the range of achieving the present function.
In the optical functional film 12 of the present embodiment, the film thickness d is set to be in the range of 30nm to 100nm, the refractive index n in the visible light region is set to be in the range of 1.5 to 2.7, and the extinction coefficient k in the visible light region is set to be in the range of 0.3 to 1.5. The visible light described herein has a wavelength in the range of 380nm to 780 nm.
In the optical functional film 12, reflection of the metal wiring film 11 is suppressed by absorption of visible light (extinction coefficient k) and disturbance (film thickness d and refractive index n). The extinction coefficient k is adjusted to suppress reflection of the total wavelength of visible light, and the film thickness d and the refractive index n are adjusted to suppress the waveform and peak of reflected light.
In the present embodiment, the lower limit of the film thickness d of the optical functional film 12 is preferably 35nm or more, and more preferably 40nm or more. The upper limit of the film thickness d of the optical functional film 12 is preferably 85nm or less, and more preferably 70nm or less.
The lower limit of the refractive index n in the visible light region is preferably 1.8 or more, and more preferably 2.0 or more. The upper limit of the refractive index n in the visible light region is preferably 2.6 or less, and more preferably 2.5 or less.
The lower limit of the extinction coefficient k in the visible light region is preferably 0.4 or more, and more preferably 0.5 or more. The upper limit of the extinction coefficient k in the visible light region is preferably 1.4 or less, and more preferably 1.3 or less.
In the optical functional film 12 of the present embodiment, the product d × n × k of the film thickness d, the refractive index n in the visible light region (wavelength 550nm), and the extinction coefficient k in the visible light region (wavelength 550nm) is preferably in the range of 30 to 150. By setting d × n × k within the above range, reflection in the visible light region can be more reliably suppressed by absorption and interference of visible light.
The lower limit of d × n × k is preferably 40 or more, and more preferably 50 or more. The upper limit of d × n × k is preferably 130 or less, and more preferably 110 or less.
The electrical resistivity of the optical functional film 12 of the present embodiment is preferably 5 Ω · cm or less. This allows the metal wiring film 11 to be electrically connected to an external wiring via the optical functional film 12. When the resistivity is higher than 5 Ω · cm, the low reflection film or the substrate is provided with a hole to conduct electricity to the external wiring in order to conduct the metal wiring to the outside.
The resistivity is preferably 1 Ω · cm or less, and more preferably 0.1 Ω · cm or less.
Next, the sputtering target of the present embodiment will be explained. The sputtering target of the present embodiment is used for forming the optical functional film 12.
The sputtering target of the present embodiment contains a first component consisting of one or more selected from TiC, NbC, VC, TiN, NbN and VN and a second component consisting of In2O3、Y2O3、Nb2O5、V2O5、Al2O3ZnO and SiO2One or two or more of the above-mentioned second components.
The first component composed of one or two or more selected from TiC, NbC, VC, TiN, NbN, and VN has conductivity, and the conductivity of the sputtering target of the present embodiment is ensured by the first component.
Selected from In as compared with the first component2O3、Y2O3、Nb2O5、V2O5、Al2O3ZnO and SiO2One or two or more of the second components are more excellent in sinterability, and therefore the density of the sputtering target of the present embodiment is improved.
The content ratio of the first component to the second component is appropriately set according to the optical characteristics of the optical functional film 12 to be formed, and for example, the molar ratio a/B of the content a of the first component to the content B of the second component is preferably in the range of 0.1 to 20, and more preferably 0.1 to 10.
The structure of the sputtering target of the present embodiment changes depending on the content ratio of the first component to the second component, but in the present embodiment, the structure is as follows: in the presence of a catalyst selected from In2O3、Y2O3、Nb2O5、V2O5、Al2O3ZnO and SiO2One or more second components selected from TiC, NbC, VC, TiN, NbN and VN, and a first component composed of one or more first components dispersed therein.
In the sputtering target of the present embodiment, the density ratio is 90% or more. By setting the density ratio to 90% or more, abnormal discharge can be suppressed from occurring during sputtering.
In the sputtering target of the present embodiment, the density ratio is preferably 92% or more, and more preferably 93% or more.
In the sputtering target of the present embodiment, the resistivity is 0.1 Ω · cm or less. By setting the resistivity to 0.1 Ω · cm or less, film formation by DC sputtering can be performed.
In the sputtering target of the present embodiment, the resistivity is preferably set to 5 × 10-2Omega cm, more preferably to 1 x 10-2Omega cm or less.
Next, a method for manufacturing a sputtering target according to the present embodiment will be described with reference to fig. 2.
As shown in fig. 2, the present embodiment includes: a powder mixing step S01 of mixing a first component powder consisting of one or more selected from TiC, NbC, VC, TiN, NbN and VN with In2O3、Y2O3、Nb2O5、V2O5、Al2O3ZnO and SiO2Mixing one or more second component powders; a sintering step S02 of sintering the obtained mixed powder; and a machining step S03 of machining the obtained sintered body.
(powder mixing step S01)
In the powder mixing step S01, the content of the first component powder composed of one or more selected from TiC, NbC, VC, TiN, NbN and VN is set to be in the range of 3 vol% to 50 vol% in terms of the powder having a particle size of 10 μm or more. And, with respect to the compounds selected from In2O3、Y2O3、Nb2O5、V2O5、Al2O3ZnO and SiO2Wherein the content of the powder having a particle size of 10 μm or less is 70 vol% or more.
When the content of the powder having a particle size of 10 μm or more is less than 3 vol%, the first component may not sufficiently secure conductivity. On the other hand, when the content of the powder having a particle size of 10 μm or more is more than 50 vol%, the sinterability may be insufficient and the density may not be sufficiently increased.
Therefore, in the present embodiment, the content of the powder having a particle size of 10 μm or more is set to be in the range of 3 vol% or more and 50 vol% or less with respect to the first component powder.
The lower limit of the content of the powder having a particle size of 10 μm or more is preferably 10 vol% or more, and more preferably 20 vol% or more with respect to the first component powder. On the other hand, the upper limit of the content of the powder having a particle size of 10 μm or more is preferably 45 vol% or less, and more preferably 40 vol% or less.
When the content of the second component powder having a particle size of 10 μm or less is less than 70 vol%, sinterability may not be secured and the density may not be sufficiently increased.
Therefore, in the present embodiment, the content of the powder having a particle size of 10 μm or less is 70 vol% or more with respect to the second component powder.
The lower limit of the second component powder having a particle size of 10 μm or less is preferably 75% by volume or more, and more preferably 80% by volume or more.
These first component powders and second component powders are mixed to obtain a sintering raw material powder.
(sintering step S02)
The sintering raw material powder is heated while being pressurized, and is sintered to obtain a sintered body. In the present embodiment, sintering is performed using a hot press apparatus or a hot isostatic pressing apparatus (HIP).
The sintering temperature in the sintering step S02 is set to be in the range of 800 ℃ to 1800 ℃, the holding time at the sintering temperature is set to be in the range of 1 hour to 15 hours, and the pressing pressure is set to be in the range of 10MPa to 200 MPa.
(machining operation S03)
The obtained sintered body was machined to a prescribed size. Thus, the sputtering target of the present embodiment is manufactured.
According to the optical functional film 12 of the present embodiment configured as described above, the first component composed of one or two or more selected from TiC, NbC, VC, TiN, NbN, and VN can improve the durability of the film and can ensure the electrical conductivity of the film.
And, by containing a compound selected from In2O3、Y2O3、Nb2O5、V2O5、Al2O3ZnO and SiO2One or two or more of the second components can adjust the optical properties of the film.
In the optical functional film 12 of the present embodiment, the film thickness d is set to be in the range of 30nm to 100nm, the refractive index n in the visible light region is set to be in the range of 1.5 to 2.7, and the extinction coefficient k in the visible light region is set to be in the range of 0.3 to 1.5, so that the reflectance can be reduced, the metal reflection of the metal wiring film 11 can be suppressed, and the metal wiring film 11 can be suppressed from being visually recognized from the outside.
Since the resistivity is set to 5 Ω · cm or less, the conductivity is secured, and the electric current can be passed through the optical functional film 12.
The sputtering target according to the present embodiment comprises a material selected from the group consisting of TiC, NbC, VC, TiN, NbN and VNAnd a first component consisting of one or more kinds selected from In2O3、Y2O3、Nb2O5、V2O5、Al2O3ZnO and SiO2One or two or more of the second components, and thus the optical functional film 12 can be formed.
Further, since the density ratio is set to 90% or more, it is possible to suppress the occurrence of abnormal discharge during sputtering and to stably form a film.
Since the resistivity is set to 0.1 Ω · cm or less, the film can be stably formed by DC sputtering, and the optical functional film 12 can be efficiently formed.
According to the method of manufacturing a sputtering target of the present embodiment, the sputtering target can be manufactured by including the step of mixing the powder of the first component powder consisting of one or two or more selected from TiC, NbC, VC, TiN, NbN and VN with the powder of the first component powder selected from In at the powder mixing step S012O3、Y2O3、Nb2O5、V2O5、Al2O3ZnO and SiO2Mixing one or more second component powders; and a sintering step S02 for sintering the mixed powder.
Since the first component powder has a particle size of 10 μm or more of 3 vol% or more, the first component particles having conductivity in the sintered body are connected to each other, and the conductivity of the sputtering target can be sufficiently ensured.
Since the first component powder having a particle size of 10 μm or more is 50 vol% or less and the second component powder having a particle size of 10 μm or less is 70 vol% or more, the density of the sintered body can be sufficiently increased.
The embodiments of the present invention have been described above, but the present invention is not limited to these embodiments, and can be modified as appropriate within a scope not departing from the technical spirit of the present invention.
For example, in the present embodiment, the laminated film having the structure shown in fig. 1 is exemplified, but the present invention is not limited to this, and a laminated film having a structure of a glass substrate, an optical functional film, and a metal wiring may be used. In this case, light from the glass substrate is reflected. In addition, the optical functional film does not need to be conductive as long as it has this structure.
Examples
The results of an evaluation test for evaluating the operational effects of the optically functional film, sputtering target and sputtering target production method according to the present invention will be described below.
First component powders (TiC powder, NbC powder, VC powder, TiN powder, NbN powder, and VN powder) and second component powders (In powder) having a particle size described In tables 1 to 3 and a purity of 99 mass% or more were prepared for producing sputtering targets2O3Powder, Y2O3Powder, Nb2O5Powder, V2O5Powder, Al2O3Powder, ZnO powder and SiO2Powder) of 2kg each of the powders weighed so as to be a desired target composition ratio was charged into a 10L pot, and 6kg of the powder was charged
Figure BDA0002893799650000091
The balls were then mixed by a ball mill.
The molar ratio a/B of the content a of the first component to the content B of the second component is shown in tables 1 to 3. Comparative examples 1 to 3, which do not contain the second component, are represented by "-", and comparative example 4, which does not contain the first component but contains only the second component, is represented by "0".
The mixed powder was sintered under the conditions shown in tables 4 to 6 to obtain sintered bodies.
As for the hot pressing example, the mixed powder was filled into a carbon heating press mold
Figure BDA0002893799650000092
In the examples, hot pressing was performed in vacuum at the temperatures and pressures described in the examples for 3 hours to prepare a sintered body.
As to the embodiment of HIP, first, the mixture is mixedPowder is filled into
Figure BDA0002893799650000093
The rubber mold of (3) was further subjected to pressure molding at 150MPa for 5 minutes by a Cold Isostatic Pressing (CIP) apparatus to prepare a molded article. Then, the molded body was mounted on an SPCC (rolled steel material) can, and after welding the SPCC, the vacuum was sucked to 0.001Pa or less, and then the can was sealed, and sintering was performed at the temperature and pressure described in the examples for 2 hours to prepare a sintered body.
Machining these sintered bodies to diameter: 125mm, thickness: after 5mm, a sputtering target was produced by In bonding to a Cu backing plate. In addition, when the impurity element is to be reduced, it is preferable to use a raw material powder having a higher purity. And, In2O3Since the powder and the ZnO powder are reduced at the time of hot pressing and HIP to precipitate In and Zn, respectively, boron nitride is preferably sufficiently applied to the carbon mold so as not to react with In2O3The powder and ZnO powder are in direct contact.
The particle diameters of the first component powder and the second component powder were measured as follows.
100mL of a 0.2 vol% aqueous solution of sodium hexametaphosphate was prepared, 10mg of each raw material powder was added to the aqueous solution, and the particle size distribution (volume basis) was measured by a laser diffraction/scattering method (measuring apparatus: NikkisO Co., Ltd., Microtrac MT3000, manufactured by Ltd.).
From the obtained particle size distribution (volume basis), the first component powder obtained a proportion of the powder volume of 10 μm or more, and the second component powder obtained a proportion of the powder volume of 10 μm or less.
As described above, the following items were evaluated with respect to the obtained sputtering target and the optical functional film formed using the sputtering target.
(Density ratio of sputtering target)
The volume of the sputtering target is calculated from the obtained size of the finished sputtering target, and the measured weight value is divided by the volume to calculate the size density of the sputtering target. The ratio obtained by dividing the dimensional density by the calculated density is shown in the table as "density ratio". Further, the calculated density was calculated according to the following formula. The evaluation results are shown in tables 4 to 6.
Calculated Density (g/cm)3) 100/{ first component loading (mass%)/first component density (g/cm)3) + second component loading (mass%)/second component density (g/cm)3)}
(Structure of sputtering target)
An observation sample was collected from the obtained sputtering target, embedded in an epoxy resin, and subjected to a polishing treatment, and then elemental mapping was performed on a range of 36 μm × 28 μm at a magnification of 3000 times using an Electron Probe Microanalyzer (EPMA) apparatus.
The structural structure of the first component and the second component is observed from the mapping image of the metal contained in the first component and the mapping image of the metal contained in the second component.
When an arbitrary line segment crossing the obtained image is drawn, if the region of the first component and the region of the second component are crossed at the same time, it is determined that the first component is uniformly dispersed in the matrix of the second component, and this is referred to as "Y". The structure of the single component in the comparative example is "-". The evaluation results are shown in tables 4 to 6.
Fig. 3 shows the observation result of invention example 8, and fig. 4 shows the observation result of invention example 29.
(resistivity of sputtering target)
The values measured by the four-probe method using a low resistance meter (Loresta-GP) manufactured by Mitsubishi Chemical Corporation are shown in the table for the central portion of the sputtering surface of the obtained sputtering target. The measurement was carried out at a temperature of 23. + -. 5 ℃ and a humidity of 50. + -. 20%. In addition, an ASP probe was used as a probe for measurement. When no measurement is measured, it is recorded as O.R (overRange). The evaluation results are shown in tables 4 to 6.
(measurement of abnormal discharge)
The number of abnormal discharges when the obtained sputtering target was used and sputtering was performed for 1 hour under the following conditions is shown in the table. The sputtering target without discharge was judged to be incapable of DC sputtering. The evaluation results are shown in tables 4 to 6.
Power supply: DC power supply (RPG-50 made by MKS Instruments)
Electric power: 615W
Air pressure: 0.67Pa
Gas flow rate: ar 50sccm
(evaluation of Single film)
Among the sputtering targets obtained, the sputtering target subjected to DC sputtering with stability was formed into a 50nm film on a 20mm square Si substrate. The sputtering target that was not stably DC sputtered was judged to be incapable of film formation. The film thickness at this time was controlled as follows: the film was formed within a film formation time corresponding to a target film thickness (50nm) using the film adhesion rate calculated in advance at the time of film formation. The obtained film was subjected to the following evaluations (1) to (3).
(1) Analysis of Membrane composition
The quantitative analysis by the EPMA apparatus was performed to quantify each metal component and C, O, N component. From the obtained results, the ratio of each component when the total value of the detected metal component and C, O, N component was defined as 100% was calculated and is shown in tables 7 to 9. In this case, the O component is described as the remainder.
From the depth profile of the XPS apparatus, it was confirmed that peaks recognized as TiC, NbC, VC, TiN, NbN, and VN, respectively, were obtained from the profile of the metal components of TiC, NbC, VC, TiN, NbN, and VN added as the first components. And In added as a second component2O3、Y2O3、Nb2O5、V2O5、Al2O3ZnO and SiO2In (2), it was confirmed that In was confirmed from the analysis of the metal component2O3、Y2O3、Nb2O5、V2O5、Al2O3ZnO and SiO2Peak of (2).
(2) Refractive index/extinction coefficient determination
The refractive index and extinction coefficient were calculated using a UVISEL-HR320(HORIBA, Ltd. component spectroscopic polarimetry). From the obtained refractive index and extinction coefficient, the values at a wavelength of 550nm are shown in tables 7 to 9. The values calculated for the product (n × k × d) of the refractive index and the extinction coefficient and the film thickness of the optical functional film at the time of black film formation (at the time of laminated film formation) are also shown in tables 7 to 9. The film thickness of the optical functional film when the black film was formed (when the laminated film was formed) was determined by the reflectance measurement described later, and the film thicknesses d described in tables 7 to 9 were used.
(3) Resistivity measurement
The values measured by the four-probe method using Loresta-GP (manufactured by Mitsubishi chemical Analyticech Co., Ltd.) are shown in tables 7 to 9. The measurement was carried out at a temperature of 23. + -. 5 ℃ and a humidity of 50. + -. 20%. In addition, a PSP probe was used as a probe for measurement.
(measurement of reflectance)
On the glass substrate, a Cu film having a thickness of 200nm was formed. Further, a Mo film having a thickness of 20nm, an Al film having a thickness of 100nm, and a Mo film having a thickness of 20nm (MAM film) were formed on the glass substrate.
Then, the optical functional films were formed on the Cu film and the MAM film to have the film thicknesses d shown in tables 7 to 9, respectively, to produce laminated films. Next, the reflectance of the laminated film formed on the glass substrate as described above was measured. In this measurement, a spectrophotometer (U4100, Ltd.) was used to measure the wavelength of 380 to 780nm from the side of the formed film. The average values of the obtained data values of the reflectance are shown in tables 10 to 12.
(Heat resistance test)
The laminated film produced in the reflectance measurement was subjected to a heat treatment at 400 ℃ under a nitrogen atmosphere for 30 minutes. The reflectance after the treatment was measured in the same manner as immediately after the film formation. The evaluation results are shown in tables 10 to 12.
(alkali resistance test)
The laminated film produced in the reflectance measurement was immersed in a 3 mass% NaOH aqueous solution at room temperature for 30 minutes. The reflectance after the treatment was measured in the same manner as immediately after the film formation. The evaluation results are shown in tables 10 to 12.
(immersion test)
The laminated film prepared in the reflectance measurement was immersed in pure water at 40 ℃ for 30 minutes. The reflectance after the treatment was measured in the same manner as immediately after the film formation. The evaluation results are shown in tables 10 to 12.
[ Table 1]
Figure BDA0002893799650000121
[ Table 2]
Figure BDA0002893799650000131
[ Table 3]
Figure BDA0002893799650000141
[ Table 4]
Figure BDA0002893799650000151
[ Table 5]
Figure BDA0002893799650000161
[ Table 6]
Figure BDA0002893799650000162
[ Table 7]
Figure BDA0002893799650000171
[ Table 8]
Figure BDA0002893799650000181
[ Table 9]
Figure BDA0002893799650000191
[ Table 10]
Figure BDA0002893799650000201
[ Table 11]
Figure BDA0002893799650000211
[ Table 12]
Figure BDA0002893799650000221
In comparative example 1, which was composed of copper oxide without containing the first component and the second component, the density ratio of the sputtering target was reduced to 88.2%, and the number of abnormal discharges was relatively large, 11. In addition, in the film formed by the sputtering target, the reflectance was greatly changed after the alkali resistance test, and the alkali resistance was poor.
In comparative example 2, which contained NbC as the first component but did not contain the second component, the density ratio of the sputtering target was reduced to 49.1%. In addition, the film formed by the sputtering target has a high reflectance.
In comparative example 3, which contained VC as the first component but did not contain the second component, the density ratio of the sputtering target was reduced to 78.2%. In addition, the film formed by the sputtering target has a high reflectance.
In the presence of Y as a second component2O3But does not contain the first componentIn comparative example 4, the resistivity was too high to be measured. Therefore, film formation by DC sputtering cannot be performed.
On the other hand, in the present invention example containing the first component and the second component, in which the content of the powder of 10 μm or more in the first component powder is 5% by volume or more and 50% by volume or less, and the content of the powder of 10 μm or less in the second component powder is 70% by volume or more, the density ratio is as high as 90% or more, and the resistivity is 0.1 Ω · cm or less. Therefore, the generation of abnormal discharge is suppressed, and the film is stably formed by DC sputtering. Further, structural observation of the sputtering target was performed, and it was confirmed that the structure was a structure in which the first component was uniformly dispersed in the second component.
The formed optical functional film has a resistivity of 5 Ω · cm or less. And is excellent in conductivity. Further, the reflectance after film formation is low, and the reflection of the metal wiring film is suppressed. Further, the reflectance did not change much even after the heat resistance test, alkali resistance test, and water immersion test, and the durability was excellent.
Therefore, it has been confirmed that the present invention can provide an optical functional film having durability and conductivity and capable of sufficiently suppressing reflection of light from a metal thin film or the like, a sputtering target capable of efficiently and stably forming the optical functional film, and a method for producing the sputtering target.
Industrial applicability
According to the present invention, it is possible to provide an optical functional film having durability and conductivity and capable of sufficiently suppressing reflection of light from a metal thin film or the like, a sputtering target capable of efficiently and stably forming the optical functional film, and a method for producing the sputtering target.
Description of the symbols
12-optical functional film.

Claims (7)

1. An optical functional film, comprising: a first component consisting of one or more selected from TiC, NbC, VC, TiN, NbN and VN; and a second component selected from In2O3、Y2O3、Nb2O5、V2O5、Al2O3ZnO and SiO2One or more of the components (A) and (B),
the film thickness d of the optical functional film is more than 30nm and less than 100nm, the refractive index n in a visible light region is more than 1.5 and less than 2.7, and the extinction coefficient k in the visible light region is more than 0.3 and less than 1.5.
2. The optical functional film according to claim 1,
the electrical resistivity of the optical functional film is 5 omega cm or less.
3. The optical functional film according to claim 1 or 2,
C. the atomic ratio alpha/beta of the total content alpha of N to the content beta of O is 0.01 to 5.
4. A sputtering target, comprising: a first component consisting of one or more selected from TiC, NbC, VC, TiN, NbN and VN; and a second component selected from In2O3、Y2O3、Nb2O5、V2O5、Al2O3ZnO and SiO2More than one of them.
5. The sputtering target according to claim 4,
the sputtering target has a density ratio of 90% or more and a resistivity of 0.1 Ω · cm or less.
6. The sputtering target according to claim 4 or 5,
the molar ratio A/B between the content A of the first component and the content B of the second component is 0.1 to 20.
7. A method for manufacturing a sputtering target, comprising:
a powder mixing step of mixing a powder of a material selected from the group consisting of TiC. A first component powder composed of at least one of NbC, VC, TiN, NbN and VN and a second component powder composed of In2O3、Y2O3、Nb2O5、V2O5、Al2O3ZnO and SiO2Mixing the second component powder of one or more kinds of components to obtain mixed powder; and
a sintering step of sintering the mixed powder,
in the powder mixing step, the content of the powder having a particle diameter of 10 [ mu ] m or more in the first component powder is 3 to 50 vol%,
the content of the second component powder is 70% or more, wherein the second component powder has a particle size of 10 μm or less.
CN201980046706.2A 2018-09-07 2019-09-09 Optical functional film, sputtering target, and method for producing sputtering target Pending CN112424390A (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP2018167996 2018-09-07
JP2018-167996 2018-09-07
JP2019163288A JP2020041217A (en) 2018-09-07 2019-09-06 Optical functional film, sputtering target, and method for manufacturing sputtering target
JP2019-163288 2019-09-06
PCT/JP2019/035342 WO2020050421A1 (en) 2018-09-07 2019-09-09 Optical functional film, sputtering target, and method for manufacturing sputtering target

Publications (1)

Publication Number Publication Date
CN112424390A true CN112424390A (en) 2021-02-26

Family

ID=69797738

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201980046706.2A Pending CN112424390A (en) 2018-09-07 2019-09-09 Optical functional film, sputtering target, and method for producing sputtering target

Country Status (4)

Country Link
JP (1) JP2020041217A (en)
KR (1) KR20210055669A (en)
CN (1) CN112424390A (en)
TW (1) TW202018111A (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW202200816A (en) * 2020-05-28 2022-01-01 日商三菱綜合材料股份有限公司 Sputtering target and optical functional film

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1441082A (en) * 2002-02-28 2003-09-10 东曹株式会社 Sputtering target and its producing method
CN1700322A (en) * 2004-05-17 2005-11-23 株式会社理光 Optical recording medium and manufacturing method of the same
US20060269717A1 (en) * 2003-11-10 2006-11-30 Hiroshi Miura Optical recording medium and process for producing the same, sputtering target, using process of optical recording medium, and optical recording apparatus
JP2015067867A (en) * 2013-09-30 2015-04-13 Tdk株式会社 Sputtering target
CN106132901A (en) * 2014-03-14 2016-11-16 住友金属矿山株式会社 Oxidate sintered body, sputtering target and the oxide semiconductor thin-film obtained with it

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003321771A (en) 2002-02-28 2003-11-14 Tosoh Corp Sputtering target and production method thereof
JP4519431B2 (en) 2003-08-26 2010-08-04 株式会社東芝 Sputtering target for forming oxide film and manufacturing method of oxide film using the same
JP6717053B2 (en) 2016-05-25 2020-07-01 凸版印刷株式会社 Wiring board, touch panel, color filter board, and display device

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1441082A (en) * 2002-02-28 2003-09-10 东曹株式会社 Sputtering target and its producing method
US20060269717A1 (en) * 2003-11-10 2006-11-30 Hiroshi Miura Optical recording medium and process for producing the same, sputtering target, using process of optical recording medium, and optical recording apparatus
CN1700322A (en) * 2004-05-17 2005-11-23 株式会社理光 Optical recording medium and manufacturing method of the same
JP2015067867A (en) * 2013-09-30 2015-04-13 Tdk株式会社 Sputtering target
CN106132901A (en) * 2014-03-14 2016-11-16 住友金属矿山株式会社 Oxidate sintered body, sputtering target and the oxide semiconductor thin-film obtained with it

Also Published As

Publication number Publication date
TW202018111A (en) 2020-05-16
KR20210055669A (en) 2021-05-17
JP2020041217A (en) 2020-03-19

Similar Documents

Publication Publication Date Title
JP6109323B2 (en) Layer system for absorbing light, its production and sputter target suitable therefor
JP4552950B2 (en) Oxide sintered body for target, manufacturing method thereof, manufacturing method of transparent conductive film using the same, and transparent conductive film obtained
JP5884549B2 (en) Transparent oxide film and method for producing the same
TWI700382B (en) Oxide thin film and oxide sintered body for sputtering target for manufacturing the thin film
JP5170009B2 (en) Indium oxide sputtering target and method for producing the same
JP2016522317A (en) LIGHT ABSORBING LAYER, LAYER SYSTEM HAVING THIS LAYER, LAYER SYSTEM MANUFACTURING METHOD, AND SPUTTER TARGET MATERIAL
KR20070088246A (en) Sintered body target for transparent conductive film fabrication, transparent conductive film fabricated by using the same, and transparent conductive base material comprising this conductive film formed thereon
JP2016132609A (en) Oxide sintered body, sputtering target and oxide thin film
JP6705526B2 (en) Shield layer, method for manufacturing shield layer, and oxide sputtering target
WO2019208240A1 (en) Shield layer, method for producing shield layer, and oxide sputtering target
JP2007314812A (en) Sputtering target and film-forming method
CN112424390A (en) Optical functional film, sputtering target, and method for producing sputtering target
JP5167575B2 (en) Oxide sintered body, sputtering target, and transparent conductive film
WO2020050421A1 (en) Optical functional film, sputtering target, and method for manufacturing sputtering target
WO2021241687A1 (en) Sputtering target and optical functional film
TW201412542A (en) Light-absorbing layered structure
JP2023057730A (en) Oxide sputtering target and oxide film
JP2021188133A (en) Sputtering target and optical function film
WO2021090662A1 (en) Sputtering target, optical function film, and method for manufacturing sputtering target
JP2012173799A (en) Transparent conductive substrate and electronic device and touch panel using the same
WO2022097635A1 (en) Sputtering target, method for producing sputtering target, and optical functional film
WO2021251094A1 (en) Sputtering target, method for producing sputtering target and optical functional film
KR20220097377A (en) high-resistance transparent film
JP2022143917A (en) Sputtering target, method for manufacturing the same, and optical function film
JP2022075552A (en) Sputtering target, manufacturing method of sputtering target, and optical film

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
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20210226