WO2019208240A1 - Couche de protection, procédé de production de couche de protection, et cible de pulvérisation d'oxyde - Google Patents

Couche de protection, procédé de production de couche de protection, et cible de pulvérisation d'oxyde Download PDF

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Publication number
WO2019208240A1
WO2019208240A1 PCT/JP2019/015779 JP2019015779W WO2019208240A1 WO 2019208240 A1 WO2019208240 A1 WO 2019208240A1 JP 2019015779 W JP2019015779 W JP 2019015779W WO 2019208240 A1 WO2019208240 A1 WO 2019208240A1
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Prior art keywords
shield layer
atomic
transmittance
range
oxide
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PCT/JP2019/015779
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English (en)
Japanese (ja)
Inventor
理恵 森
山口　剛
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三菱マテリアル株式会社
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Priority claimed from JP2019068393A external-priority patent/JP6705526B2/ja
Application filed by 三菱マテリアル株式会社 filed Critical 三菱マテリアル株式会社
Priority to KR1020207025509A priority Critical patent/KR102234874B1/ko
Priority to CN201980019072.1A priority patent/CN111902561B/zh
Publication of WO2019208240A1 publication Critical patent/WO2019208240A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133512—Light shielding layers, e.g. black matrix
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • 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
    • 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
    • G02B1/16—Optical coatings produced by application to, or surface treatment of, optical elements having an anti-static effect, e.g. electrically conducting coatings
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073—Shielding materials
    • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
    • H05K9/0083—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising electro-conductive non-fibrous particles embedded in an electrically insulating supporting structure, e.g. powder, flakes, whiskers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3286—Gallium oxides, gallates, indium oxides, indates, thallium oxides, thallates or oxide forming salts thereof, e.g. zinc gallate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
    • G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
    • G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices

Definitions

  • the present invention relates to a shield layer disposed for preventing charging in a display panel, a method for producing the shield layer, and an oxide sputtering target used in the method for producing the shield layer.
  • a shield layer is provided in order to prevent malfunction due to charging of a liquid crystal element, an organic EL element, or the like.
  • the above-described shield layer is also required to have an effect of causing the touch signal to reach the sensor portion inside the panel while eliminating external noise.
  • this shield layer is also required to have high visible light permeability in order to ensure the visibility of the display panel.
  • Patent Document 1 an ITO film and an IZO film are cited as the above-described shield layer.
  • a polarizing film is disposed on the surface of a glass substrate disposed on a liquid crystal element, and the above-described shield layer is laminated on the polarizing film.
  • Patent Document 2 proposes a transparent conductive film containing indium tin oxide (ITO) containing 7.2 to 11.2 at% silicon (Si).
  • Patent Document 1 when an ITO film and an IZO film are used as a shield layer, the visible light transmittance is low, so that it appears to be yellowish. There was a risk that the visibility would deteriorate.
  • the transparent conductive film described in Patent Document 2 has a high resistance value and excellent light transmittance, but has insufficient environmental resistance. There was a possibility that permeability might deteriorate.
  • the shield layer even when used in a high temperature and high humidity environment, depending on the usage status of the display panel, excellent environmental resistance (heat resistance, Moisture resistance) is required.
  • excellent environmental resistance heat resistance, Moisture resistance
  • the ITO film and the IZO film described above are likely to be crystalline, corrosive substances such as moisture are likely to enter the film and the resistance value and transmittance change when used in a high temperature and high humidity environment. There was a risk of doing so.
  • the present invention has been made in view of the above-described circumstances, has a high visible light transmittance, a sufficiently high resistance value, and has excellent environmental resistance (heat resistance, moisture resistance). It aims at providing a shield layer, a manufacturing method of a shield layer, and an oxide sputtering target.
  • the shield layer of the present invention is a shield layer disposed in a display panel, wherein the total of metal components is 100 atomic%, and In is in the range of 60 atomic% to 80 atomic%. And the remainder is made of an oxide made of Si and inevitable impurity metal elements.
  • the total of the metal components is 100 atomic%, In is included in the range of 60 atomic% or more and 80 atomic% or less, and the balance is composed of Si and an oxide with inevitable impurity metal elements. Therefore, it has excellent visible light transmittance and a sufficiently high resistance value. Furthermore, since the shield layer of the present invention tends to be amorphous, corrosive substances such as moisture are less likely to enter the film, and the resistance value and transmittance greatly change even when used in a high temperature and high humidity environment. Without having excellent environmental resistance (heat resistance, moisture resistance). Further, since the shield layer of the present invention has resistance to water and alcohol, the transmittance and the resistance value do not change greatly even when the shield layer is cleaned with water and alcohol.
  • the total of the metal components may be 100 atomic%, and Zr may be further included in the range of 1 atomic% to 32 atomic%.
  • the Zr content is 1 atomic% or more, the durability of the shield layer is further improved.
  • the hardness is increased and it is strong against scratches and the like.
  • the Zr content is limited to 32 atomic% or less, it is possible to suppress an increase in the refractive index, to suppress unnecessary reflection, and to reduce the visible light transmittance. Can be suppressed.
  • the thickness is preferably in the range of 7 nm to 25 nm. In this case, since the thickness of the shield layer is 7 nm or more, the durability can be sufficiently improved. On the other hand, since the thickness of the shield layer is 25 nm or less, it is possible to sufficiently ensure the transmittance and the resistance value.
  • the transmittance at a wavelength of 550 nm is preferably 95% or more.
  • the transmittance for visible light is excellent. For this reason, it becomes possible to comprise the display panel excellent in visibility.
  • the sheet resistance is preferably in the range of 1E + 7 ⁇ / ⁇ to 5E + 10 ⁇ / ⁇ .
  • the sheet resistance is in the range of 1E + 7 ⁇ / ⁇ or more and 5E + 10 ⁇ / ⁇ , static electricity and noise can be effectively removed, and the touch sensor inside the display can detect the touch signal accurately.
  • the numerical value A ⁇ 10 B is expressed as AE + B (when B is a positive number) based on JIS X 0210-1986. .
  • the method for producing a shield layer according to the present invention is a method for producing a shield layer for producing the above-mentioned shield layer, wherein the total of the metal components is 100 atomic% and includes In in the range of 60 atomic% to 80 atomic%.
  • oxygen is introduced into the sputtering apparatus to perform sputtering film formation.
  • the flow rate ratio of oxygen / argon is 0.03 or less.
  • the manufacturing method of the shield layer of this configuration using an oxide sputtering target composed of an oxide containing In in a range of 60 atomic% to 80 atomic% and the balance being Si and inevitable impurity metal elements, Since sputtering is performed by introducing oxygen into the sputtering apparatus, a shield layer having a high visible light transmittance and a sufficiently high resistance can be formed. Moreover, since the flow rate ratio of oxygen / argon is set to 0.03 or less for the amount of oxygen to be introduced, it is possible to suppress the resistance value of the formed shield layer from becoming too high.
  • the oxide sputtering target may contain Zr in the range of 1 atomic% to 32 atomic%, with the total of the metal components being 100 atomic%. Good.
  • the oxide sputtering target further contains Zr in the range of 1 atomic% to 32 atomic%, the shield has high hardness and excellent durability while ensuring visible light transmittance. A layer can be formed.
  • the sheet resistance of the said shield layer into the range of 1E + 7 ohm / square or more and 5E + 10 ohm / square or less.
  • the sheet resistance of the shield layer by setting the sheet resistance of the shield layer within the range of 1E + 7 ⁇ / ⁇ or more and 5E + 10 ⁇ / ⁇ , static electricity and noise can be effectively removed and the touch sensor inside the display can detect the touch signal accurately. It is possible to manufacture a shield layer that can be used.
  • the oxide sputtering target of the present invention is used in the above-described method for producing a shield layer.
  • the above-described shield layer can be formed by introducing oxygen into the sputtering apparatus with an oxygen / argon flow ratio of 0.03 or less and performing sputtering. .
  • a shield layer having a high visible light transmittance and a sufficiently high resistance value, and further having excellent environmental resistance (heat resistance, moisture resistance), a method for manufacturing the shield layer, and An oxide sputtering target can be provided.
  • the shield layer which is one Embodiment of this invention, and the manufacturing method of a shield layer are demonstrated with reference to attached drawing.
  • the shield layer according to the present embodiment is disposed for preventing charging in a display panel such as a liquid crystal display panel, an organic EL display panel, and a touch panel.
  • a display panel such as a liquid crystal display panel, an organic EL display panel, and a touch panel.
  • description will be made assuming that the liquid crystal display panel is disposed.
  • the liquid crystal display panel 10 provided with the shield layer 20 according to the present embodiment will be described with reference to FIG.
  • the liquid crystal display panel 10 includes a first glass substrate 11, a second glass substrate 12, and a liquid crystal layer disposed between the first glass substrate 11 and the second glass substrate 12. 13.
  • the first glass substrate 11 and the second glass substrate 12 are made of non-alkali glass and do not contain Na.
  • the 1st glass substrate 11 and the 2nd glass substrate 12 with a non-alkali glass, it can suppress that an alkali component mixes in a liquid crystal layer or TFT, and can avoid display performance degradation.
  • a shield layer 20 according to the present embodiment is disposed on the second glass substrate 12.
  • a polarizing film 15 is disposed on the shield layer 20, and a protective film 16 is formed on the polarizing film 15.
  • the shield layer 20 is formed, if the shield layer 20 surface is contaminated for some reason before proceeding to the next step, the surface of the shield layer 20 may be washed with water, alcohol, or the like. . For this reason, the above-described shield layer 20 also needs resistance to water and alcohol.
  • the total of the metal components is 100 atomic%, In is included in the range of 60 atomic% to 80 atomic%, and the balance is Si and inevitable impurity metal elements. Made of oxide.
  • the total of the metal components may be 100 atomic%, and in addition to In described above, Zr may be further included in the range of 1 atomic% to 32 atomic%. .
  • the thickness t is in the range of 7 nm or more and 25 nm or less. Furthermore, in the shield layer 20 which is this embodiment, the transmittance
  • the shield layer 20 made of an oxide of In and Si
  • the conductivity necessary for the shield layer 20 may not be ensured. is there.
  • the content of In exceeds 80 atomic%, the short wavelength transmittance is lowered, and the visibility may be lowered. From the above, in this embodiment, the total of the metal components is 100 atomic%, and the In content is in the range of 60 atomic% to 80 atomic%.
  • the total of the metal components is 100 atomic%, and the lower limit of the In content is 62 atomic% or more, and 64 atomic% or more. Is more preferable.
  • the upper limit of the In content is preferably set to 78 atomic% or less.
  • the shield layer 20 according to the present embodiment may contain Zr as a metal component in addition to In and Si.
  • Zr as a metal component in addition to In and Si.
  • the durability of the shield layer 20 can be improved, the hardness becomes hard, and it is resistant to scratches. Become.
  • the Zr content to 32 atomic% or less, an increase in the refractive index can be suppressed and generation of unnecessary reflection can be suppressed, so that a decrease in visible light transmittance can be suppressed.
  • the total of the metal components is 100 atomic% and the Zr content is in the range of 1 atomic% to 32 atomic%.
  • the content thereof may be less than 1 atomic%.
  • the total of the metal components is 100 atomic%, and the lower limit of the Zr content is 2 atomic% or more, preferably 3 atomic% or more. Is more preferable.
  • the upper limit of the Zr content is preferably 28 atomic% or less, and preferably 25 atomic% or less. Is more preferable.
  • the thickness t of the shield layer 20 when the thickness t is 7 nm or more, the durability of the shield layer 20 can be sufficiently ensured. On the other hand, when the thickness t of the shield layer 20 is 25 nm or less, it is possible to sufficiently ensure the transmittance of visible light and the resistance value. From the above, in the present embodiment, it is preferable that the thickness t of the shield layer 20 is in the range of 7 nm to 25 nm.
  • the lower limit of the thickness t of the shield layer 20 is preferably 8 nm or more, and more preferably 10 nm or more.
  • the upper limit of the thickness t of the shield layer 20 is preferably 20 nm or less, and more preferably 18 nm or less.
  • the transmittance at a wavelength of 550 nm when the transmittance at a wavelength of 550 nm is 95% or more, a sufficient transmittance can be ensured, and the liquid crystal display panel 10 having excellent visibility is configured. It becomes possible. From the above, in the shield layer 20 of the present embodiment, the transmittance at a wavelength of 550 nm is preferably 95% or more. In addition, in order to constitute the liquid crystal display panel 10 with further excellent visibility, the transmittance of the shield layer 20 according to the present embodiment at a wavelength of 550 nm is preferably 97% or more, and preferably 98% or more. Further preferred.
  • the resistance value of the shield layer 20 is in the range of 1E + 7 ⁇ / ⁇ or more and 5E + 10 ⁇ / ⁇ or less.
  • the lower limit of the resistance value in the shield layer 20 is preferably 3E + 7 ⁇ / ⁇ or more, and 5E + 7 ⁇ / ⁇ or more. More preferably.
  • the upper limit of the resistance value is preferably 9E + 9 ⁇ / ⁇ or less, and more preferably 5E + 9 ⁇ / ⁇ or less.
  • the manufacturing method of the shield layer which manufactures the shield layer 20 which is this embodiment mentioned above is demonstrated.
  • the oxide sputtering target of the composition corresponding to the above-mentioned shield layer 20 is used.
  • This oxide sputtering target is made of an oxide sintered body containing 100 atomic% of total metal components, containing In in the range of 60 atomic% to 80 atomic%, and the balance being Si and inevitable impurity metal elements. Become. Note that the total of the metal components may be 100 atomic%, and Zr may be further included in the range of 1 atomic% to 32 atomic%. When Zr is included as an inevitable impurity metal element, the content thereof may be less than 1 atomic%.
  • this oxide sputtering target is manufactured as follows.
  • the In 2 O 3 powder preferably has a purity of 99.9% by mass or more and an average particle size of 0.1 ⁇ m or more and 10 ⁇ m or less.
  • the SiO 2 powder preferably has a purity of 99.8% by mass or more and an average particle size of 0.2 ⁇ m or more and 20 ⁇ m or less.
  • the ZrO 2 powder preferably has a purity of 99.9% by mass or more and an average particle size of 0.2 ⁇ m or more and 20 ⁇ m or less.
  • the purity of the ZrO 2 powder is calculated by measuring the contents of Fe 2 O 3 , SiO 2 , TiO 2 , and Na 2 O and the balance being ZrO 2 .
  • the ZrO 2 powder of this embodiment may contain HfO 2 at a maximum of 2.5 mass%.
  • the mixed raw material powder preferably has a specific surface area (BET specific surface area) in the range of 11.5 m 2 / g to 13.5 m 2 / g.
  • BET specific surface area specific surface area
  • the compact is placed in an electric furnace and heated to sinter.
  • the holding temperature is preferably in the range of 1300 ° C. to 1600 ° C., and the holding time is preferably in the range of 2 hours to 10 hours.
  • the obtained sintered body is machined to produce an oxide sputtering target of a predetermined size.
  • the shield layer 20 is formed on the surface of the second glass substrate 12 using this oxide sputtering target.
  • the above-mentioned oxide sputtering target is bonded to a backing material and mounted in a sputtering apparatus.
  • Ar gas and oxygen gas are introduced to adjust the sputtering gas pressure, and sputtering film formation is performed.
  • the flow rate ratio of oxygen / argon is preferably 0.03 or less, and more preferably 0.02 or less.
  • the lower limit of the oxygen / argon flow ratio is not particularly limited, but is preferably 0.002 or more. By introducing oxygen within this range, a shield layer having a more preferable resistance value can be formed.
  • the total of the metal components is 100 atomic%, In is included in the range of 60 atomic% to 80 atomic%, and the balance is Si and inevitable. Since it is composed of an oxide made of an impurity metal element, it has excellent visible light transmittance, has a sufficiently high resistance value, and functions sufficiently as the shield layer 20 in the liquid crystal display panel 10. become.
  • the shield layer 20 according to the present embodiment is likely to be amorphous, corrosive substances such as moisture are difficult to enter the film, and even when used in a high temperature and high humidity environment, the resistance value and the transmittance. Does not change significantly and has excellent environmental resistance (heat resistance, moisture resistance). In addition, even when it comes into contact with water and alcohol, the transmittance and the resistance value do not change greatly. Therefore, after the shield layer 20 is formed, the surface of the shield layer 20 is caused for some reason before proceeding to the next step. Even if the contaminated shield layer 20 is washed with water and alcohol, the shield layer 20 does not deteriorate.
  • the shield layer 20 when the total of the metal components is 100 atomic% and Zr is included in the range of 1 atomic% to 32 atomic%, the durability of the shield layer 20 Can be further improved. In addition, the hardness of the shield layer 20 increases, and it becomes strong against scratches and the like. Moreover, since it can suppress that a refractive index increases and generation
  • the thickness of the shield layer 20 when the thickness of the shield layer 20 is 7 nm or more, the durability of the shield layer 20 can be sufficiently improved. On the other hand, when the thickness of the shield layer 20 is 25 nm or less, the visible light transmittance and resistance value of the shield layer 20 can be sufficiently ensured. Therefore, it is particularly suitable as the shield layer 20 in the liquid crystal display panel 10.
  • the shield layer 20 when the transmittance at a wavelength of 550 nm is 95% or more, the transmittance of visible light is excellent and the visibility of the liquid crystal display panel 10 is ensured. Can do.
  • the shield layer 20 when the resistance value is 1E + 7 ⁇ / ⁇ or more and 5E + 10 ⁇ / ⁇ or less, static electricity and noise can be effectively removed, and the touch sensor inside the display detects the touch signal. Does not prevent you from doing.
  • oxygen is introduced into the sputtering apparatus using an oxide sputtering target made of an oxide containing In in a range of 60 atomic% to 80 atomic%. Since the sputtering film formation is performed, the shield layer 20 having a high visible light transmittance and a sufficiently high resistance value can be stably formed. Moreover, since the flow rate ratio of oxygen / argon is 0.03 or less with respect to the amount of oxygen to be introduced, it is possible to suppress the resistance value of the formed shield layer 20 from becoming too high.
  • the shield layer 20 which is this embodiment, when the said oxide sputtering target contains the total of a metal component as 100 atomic%, and also contains Zr in 1 atomic% or more and 32 atomic% or less. Makes it possible to form the shield layer 20 having a high hardness and excellent durability while ensuring the transmittance of visible light.
  • the shield layer 20 provided in the liquid crystal display panel 10 illustrated in FIG. 1 has been described as an example.
  • the present invention is not limited thereto, and the shield layer 20 is provided in a liquid crystal display panel having another structure. It may be provided, or may be provided on another display panel such as an organic EL display and a touch panel.
  • the film was formed using the oxide sputtering target manufactured as described above, but the present invention is not limited to this, and the sputtering target manufactured by another manufacturing method. You may form into a film using.
  • ⁇ Oxide sputtering target As raw material powder, indium oxide powder (In 2 O 3 powder: purity 99.9% by mass or more, average particle size 1 ⁇ m) and silicon oxide powder (SiO 2 powder: purity 99.8% by mass or more, average particle size 2 ⁇ m) And zirconium oxide powder (ZrO 2 powder: purity 99.9% by mass or more, average particle diameter 2 ⁇ m) was prepared as needed. And these were weighed so that it might become a compounding ratio shown in Table 1.
  • indium oxide powder In 2 O 3 powder: purity 99.9% by mass or more, average particle size 1 ⁇ m
  • silicon oxide powder SiO 2 powder: purity 99.8% by mass or more, average particle size 2 ⁇ m
  • zirconium oxide powder ZrO 2 powder: purity 99.9% by mass or more, average particle diameter 2 ⁇ m
  • the purity of the zirconium oxide powder was calculated by measuring the content of Fe 2 O 3 , SiO 2 , TiO 2 , and Na 2 O and the balance being ZrO 2 , and HfO 2 may be contained at a maximum of 2.5 mass%.
  • Each of the weighed raw material powders was put into a bead mill apparatus together with zirconia balls having a diameter of 0.5 mm and a solvent (Solmix A-11 manufactured by Nippon Alcohol Sales Co., Ltd.) as a grinding medium, and pulverized and mixed.
  • the grinding / mixing time was 1 hour.
  • zirconia balls were separated and recovered to obtain a slurry containing raw material powder and solvent.
  • the obtained slurry was heated and the solvent was removed to obtain a mixed powder.
  • the obtained mixed powder was filled in a mold having an inner diameter of 200 mm and pressed at a pressure of 150 kg / cm 2 to produce a disk-shaped molded body having a diameter of 200 mm and a thickness of 10 mm.
  • the obtained molded body was charged into an electric furnace (furnace volume 27000 cm 3 ), fired by holding at a firing temperature of 1400 ° C. for 7 hours while introducing oxygen gas at a flow rate of 4 L / min, and sintered.
  • the body was manufactured. After firing, the furnace was cooled to 600 ° C. at a cooling rate of 130 ° C./hour in an electric furnace while continuously introducing oxygen gas. Thereafter, the introduction of oxygen gas was stopped, the furnace was cooled to room temperature, and the sintered body was taken out of the electric furnace.
  • the obtained sintered body was machined to produce a disk-shaped oxide sputtering target having a diameter of 152.4 mm and a thickness of 6 mm.
  • the oxide sputtering target was soldered to an oxygen-free copper backing plate and mounted in a magnetron type sputtering apparatus (Showa Vacuum SPH-2307).
  • a magnetron type sputtering apparatus Showa Vacuum SPH-2307
  • the flow rate ratio of oxygen / argon described in the column of “amount of oxygen during sputtering” in Table 1 is obtained.
  • Ar gas and oxygen gas were introduced, the sputtering gas pressure was adjusted to 0.67 Pa, and pre-sputtering for 1 hour was performed to remove the processed layer on the target surface.
  • the flow rate with the oxygen gas at this time was the conditions described in Table 1, and the power was DC615W.
  • the flow rate ratio of oxygen / argon was the ratio of oxygen flow rate (sccm) and argon flow rate (sccm).
  • sputtering film formation was performed under the same conditions as the above pre-sputtering, on a 50 mm square non-alkali glass substrate, A shield layer (oxide film) having a thickness described in Table 1 was formed. The distance between the substrate and the target at this time was 60 mm.
  • composition, transmittance, resistance value, refractive index, hardness, transmittance and resistance value after the constant temperature and humidity test of the obtained shield layer (oxide film) were evaluated as follows. Further, the crystallinity of the oxide film was confirmed.
  • composition of oxide film The solution obtained by dissolving the above oxide film with an acid was analyzed with an induction plasma emission spectroscopy (ICP-OES) apparatus (Agilent 5100) manufactured by Agilent Technologies, Inc., and the In concentration, Zr concentration and The Si concentration was measured. Table 1 shows the composition of the film in which the total of the metal components is 100 atomic%.
  • ICP-OES induction plasma emission spectroscopy
  • the refractive index of the oxide film was measured using a spectroscopic ellipsometer at an incident angle of 75 ° and a measurement wavelength of 550 nm.
  • Example 11 The oxide film formed to a thickness of 30 nm under the conditions of Invention Example 11 and Conventional Example 1 was subjected to XRD analysis to confirm the crystallinity of the oxide film. As a result, in Conventional Example 1, it was confirmed that the oxide film was crystalline. In contrast, in Example 11 of the present invention, the oxide film was amorphous.
  • Example 1 in which an ITO film was formed as the shield layer, the initial transmittance at a wavelength of 550 nm, the relative value of the transmittance at a wavelength of 350 nm with respect to the transmittance at a wavelength of 550 nm, and the resistance value were insufficient. Moreover, after the constant temperature / humidity test 1 and the constant temperature / humidity test 2, the fluctuation
  • Example 2 in which an IZO film was formed as a shield layer, the initial transmittance at a wavelength of 550 nm, the relative value of the transmittance at a wavelength of 350 nm with respect to the transmittance at a wavelength of 550 nm, and the resistance value were insufficient. Moreover, after the constant temperature / humidity test 1 and the constant temperature / humidity test 2, the fluctuation
  • Comparative Example 1 In Comparative Example 1 in which the In content of the shield layer (oxide film) is less than the range of the present invention, the resistance value was too high, and the conductivity required for the shield layer could not be ensured.
  • Comparative Example 2 where the In content of the shield layer (oxide film) is larger than the range of the present invention, the short wavelength transmittance was lowered. Moreover, the fluctuation
  • Comparative Example 3 in which the Zr content of the shield layer (oxide film) is larger than the range of the present invention, the refractive index was increased.
  • the transmittance is sufficiently high and the resistance value is within an appropriate range. It was confirmed that it is particularly suitable as a shield layer. Further, even after the constant temperature and humidity test 1 and the constant temperature and humidity test 2, the transmittance and the resistance value did not vary greatly. Further, it was confirmed that the inventive examples 1-4 and 6-17 containing Zr were improved in hardness as compared with the inventive example 5 containing no Zr.
  • the relative value of the transmittance at a wavelength of 350 nm with respect to the transmittance at a wavelength of 550 nm was 0.85 or more, and high transmittance even at a short wavelength. It was confirmed that it has a rate.
  • a shield layer having a high visible light transmittance and a sufficiently high resistance value, and further having excellent environmental resistance (heat resistance, moisture resistance), a method for manufacturing the shield layer, and An oxide sputtering target can be provided.

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Abstract

L'invention concerne une couche de protection (20) disposée sur un panneau d'affichage à cristaux liquides (10) et caractérisée en ce qu'elle comprend un oxyde qui contient, en utilisant 100 % d'atomes pour le total des constituants métalliques, du In dans la plage de 60 à 80 % d'atomes, le reste étant constitué de Si et d'éléments métalliques constituant des impuretés inévitables. La couche de protection (20) peut aussi contenir du Zr dans la plage de 1 à 32 % d'atomes en utilisant 100 % d'atomes pour le total des constituants métalliques.
PCT/JP2019/015779 2018-04-26 2019-04-11 Couche de protection, procédé de production de couche de protection, et cible de pulvérisation d'oxyde WO2019208240A1 (fr)

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CN201980019072.1A CN111902561B (zh) 2018-04-26 2019-04-11 屏蔽层、屏蔽层的制造方法及氧化物溅射靶

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