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WO2021090829A1 - Film transparent à haute resistance - Google Patents

Film transparent à haute resistance Download PDF

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Publication number
WO2021090829A1
WO2021090829A1 PCT/JP2020/041181 JP2020041181W WO2021090829A1 WO 2021090829 A1 WO2021090829 A1 WO 2021090829A1 JP 2020041181 W JP2020041181 W JP 2020041181W WO 2021090829 A1 WO2021090829 A1 WO 2021090829A1
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WO
WIPO (PCT)
Prior art keywords
transparent film
resistance transparent
film
resistance
atomic
Prior art date
Application number
PCT/JP2020/041181
Other languages
English (en)
Japanese (ja)
Inventor
栞里 河村
理恵 森
佑一 近藤
山口　剛
Original Assignee
三菱マテリアル株式会社
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
Priority claimed from JP2020183906A external-priority patent/JP2021075788A/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 KR1020227002340A priority Critical patent/KR20220097377A/ko
Publication of WO2021090829A1 publication Critical patent/WO2021090829A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • 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
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • 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
    • G02F1/133308—Support structures for LCD panels, e.g. frames or bezels
    • G02F1/133334—Electromagnetic shields
    • 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
    • G02F2202/00—Materials and properties
    • G02F2202/22—Antistatic materials or arrangements
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F1/00—Details not covered by groups G06F3/00 - G06F13/00 and G06F21/00
    • G06F1/16—Constructional details or arrangements
    • G06F1/18—Packaging or power distribution
    • G06F1/181—Enclosures
    • G06F1/182—Enclosures with special features, e.g. for use in industrial environments; grounding or shielding against radio frequency interference [RFI] or electromagnetical interference [EMI]
    • 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

Definitions

  • the present invention relates to a high resistance transparent film.
  • This application claims priority based on Japanese Patent Application No. 2019-20894 filed in Japan on November 5, 2019 and Japanese Patent Application No. 2020-18396 filed in Japan on November 2, 2020. Is used here.
  • a shield layer (high resistance transparent film) is provided inside to prevent malfunctions due to charging of liquid crystal elements, organic EL elements, and the like.
  • the shield layer used for the in-cell type touch panel is also required to have an action of allowing the touch signal to reach the sensor portion inside the panel while eliminating noise from the outside.
  • the shield layer is also required to have high transparency of visible light in order to ensure the visibility of the display panel.
  • Patent Document 1 an ITO film and an IZO film are mentioned as the above-mentioned shield layer.
  • a polarizing film is disposed on the surface of a glass substrate arranged on a liquid crystal element, and the above-mentioned shield layer is laminated on the polarizing film.
  • Patent Document 2 discloses a Si—In—M1-O-based material (at least one element selected from M1: Zr and Hf) used for the interface layer of an information recording medium.
  • Patent Document 1 when an ITO film and an IZO film are used as the shield layer, the transmittance in visible light is low, so that the film looks yellowish and is visible. There was a risk of deterioration of sex. Further, since the ITO film and the IZO film used for the shield layer in Patent Document 1 tend to be crystalline, corrosive substances such as moisture easily invade the inside of the film when used in a high temperature and high humidity environment. There was a risk that the resistance value and transmittance would change.
  • a layer containing In and Zr / Hf metal element components having a high visible light transmittance is formed when forming a film on a glass substrate, it is used as a shield layer (high resistance transparent film). The transmittance was not sufficient.
  • the present invention has been made in view of the above-mentioned circumstances, has a high visible light transmittance, a sufficiently high resistance value, and has excellent environmental resistance (heat resistance, moisture resistance). It is an object of the present invention to provide a high resistance transparent film.
  • the present invention includes the following aspects.
  • the high-resistance transparent film according to one aspect of the present invention is formed on a transparent substrate and is composed of an oxide containing In, Zr, and Si as metal components, and is said to be highly resistant and transparent in X-ray photoelectron spectroscopic analysis.
  • a peak shift layer having a peak position of the binding energy of In3d 5/2 on the energy side higher than the peak position of the binding energy of In3d 5/2 on the surface layer of the film by 0.5 eV or more is provided on the transparent substrate side.
  • the peak shift layer is characterized in that the SiO 2 equivalent film thickness is 6.5 nm or less.
  • a glass substrate can be used as the transparent substrate.
  • the high resistance transparent film tends to be amorphous, corrosive substances such as moisture do not easily enter the inside of the film, and the high resistance transparent film is arranged in a high temperature and high humidity environment. Even when a display panel is used, the resistance value and transmittance do not change significantly, and it has excellent environmental resistance (heat resistance, moisture resistance). Further, since the high resistance transparent film of the aspect (1) above has resistance to water and alcohol, the transmittance and the resistance value greatly change even when cleaned with water, alcohol or the like. None. Then, according to the aspect (1) above, since the SiO 2 equivalent film thickness of the peak shift layer is 6.5 nm or less, the peak shift layer having a high visible light absorption rate becomes thin and the transmittance becomes high.
  • the high-resistance transparent film according to (1) above is an oxide composed of a metal component and oxygen, and the metal component has an In of 60 atomic% or more and 90, with the total of the metal components being 100 atomic%. It may be contained in the range of atomic% or less, Zr may be contained in the range of 1 atomic% or more and 32 atomic% or less, and the balance may be Si and unavoidable impurities. According to this aspect, the high resistance transparent film contains In in the range of 60 atomic% or more and 90 atomic% or less, Zr in the range of 1 atomic% or more and 32 atomic% or less, and the balance is Si and unavoidable impurities. Since it is composed of an oxide composed of an oxide, the high-resistance transparent film tends to be amorphous, has excellent visible light transmittance, and has a sufficiently high resistance value.
  • the high-resistance transparent film according to (1) or (2) above may have a film thickness of 7 nm or more and 25 nm or less. According to this aspect, the durability of the high resistance transparent film can be sufficiently improved, and the transparency and resistance value of the high resistance transparent film can be sufficiently ensured.
  • the high-resistance transparent film according to any one of (1) to (3) above may have a transmittance of 97% or more at a wavelength of 550 nm. According to this aspect, a sufficient transmittance can be secured, and a display panel having excellent visibility can be configured.
  • a high resistance transparent film having a high visible light transmittance, a sufficiently high resistance value, and excellent environmental resistance (heat resistance, moisture resistance).
  • the high-resistance transparent film 20 according to the embodiment of the present invention will be described below with reference to the attached drawings.
  • the high-resistance transparent film 20 according to the present embodiment is arranged in a liquid crystal display panel, an organic EL display panel, a display panel such as a touch panel, for antistatic purposes.
  • the high resistance transparent film 20 according to the present embodiment will be described as being arranged on the liquid crystal display panel 10.
  • FIG. 1 is a cross-sectional view of a liquid crystal display panel 10 provided with a high-resistance transparent film 20 according to an embodiment of the present invention.
  • the liquid crystal display panel 10 has a liquid crystal layer 13 arranged between the first glass substrate 11, the second glass substrate 12, and the first glass substrate 11 and the second glass substrate 12. And have.
  • the high-resistance transparent film 20, the polarizing film 15, and the protective film 16 of the present embodiment are formed in this order on the second glass substrate 12 used as the transparent substrate to form the liquid crystal display panel 10.
  • Non-alkali glass that does not contain an alkaline component such as Na can be used for the first glass substrate 11 and the second glass substrate 12 (transparent substrate).
  • an alkaline component such as Na
  • the first glass substrate 11 and the second glass substrate 12 transparent substrate.
  • the high-resistance transparent film 20 of the present embodiment is formed on the second glass substrate 12 and is made of an oxide containing In, Zr, and Si as metal components. Since the high-resistance transparent film 20 of the present embodiment tends to be amorphous, corrosive substances such as moisture do not easily enter the inside of the film, and a liquid crystal display panel on which the high-resistance transparent film 20 is arranged in a high-temperature and high-humidity environment. Even when 10 is used, the resistance value and the transmittance do not change significantly, and it has excellent environmental resistance (heat resistance, moisture resistance). Further, since the high resistance transparent film 20 of the present embodiment has resistance to water and alcohol, the transmittance and resistance value may change significantly even when cleaned with water, alcohol or the like. Absent.
  • the high-resistance transparent film 20 of the present embodiment is composed of an oxide composed of a metal component and oxygen and an unavoidable impurity, and the metal component contains 60 atomic% or more and 90 atomic% of In, where the total of the metal components is 100 atomic%. It is preferable that it is contained within the following range, Zr is contained in the range of 1 atomic% or more and 32 atomic% or less, and the balance is Si and an unavoidable metal.
  • the unavoidable impurities are elements other than oxygen and metal components.
  • the unavoidable metal is an element whose content is specified and a metal element other than Si.
  • the metal component includes a metalloid such as Si. Therefore, the unavoidable metal includes a metalloid.
  • the high-resistance transparent film 20 of the present embodiment is composed of an oxide composed of a metal component and oxygen and an unavoidable impurity, and the metal component contains In in a range of 60 atomic% or more and 90 atomic% or less.
  • Zr is contained in the range of 1 atomic% or more and 32 atomic% or less, and the balance is Si and unavoidable metal. Therefore, the transmittance of visible light is excellent, and the resistance value is sufficiently high. If the In content is less than 60 atomic%, the conductivity required for the high-resistance transparent film 20 may not be secured. On the other hand, when the In content exceeds 90 atomic%, the transmittance of short wavelengths may decrease and the visibility may decrease.
  • the lower limit of the In content is preferably 62 atomic% or more, and more preferably 64 atomic% or more.
  • the upper limit of the In content of the high-resistance transparent film 20 is 89 atomic%. It is more preferably 78 atomic% or less.
  • the high-resistance transparent film 20 of the present embodiment has a Zr content of 1 atomic% or more, the durability of the high-resistance transparent film 20 can be improved. Further, according to this configuration, the hardness of the high-resistance transparent film 20 is increased, so that the high-resistance transparent film 20 is resistant to scratches and the like. Since the high-resistance transparent film 20 of the present embodiment has a Zr content of 32 atomic% or less, it is possible to suppress an increase in the refractive index in the high-resistance transparent film 20 and suppress the occurrence of unnecessary reflection. It becomes. Further, according to this configuration, it is possible to suppress a decrease in the transmittance of visible light passing through the high resistance transparent film 20.
  • the lower limit of the Zr content is more preferably 2 atomic% or more, and further preferably 3 atomic% or more.
  • the upper limit of the Zr content is more preferably 28 atomic% or less, and further preferably 25 atomic% or less. preferable.
  • the high-resistance transparent film 20 of the present embodiment preferably has a film thickness t of 7 nm or more and 25 nm or less.
  • the durability of the high resistance transparent film 20 can be sufficiently improved.
  • the upper limit value of the film thickness t of the high resistance transparent film 20 is more preferably 8 nm or more, and further preferably 10 nm or more.
  • the upper limit of the film thickness t of the high resistance transparent film 20 is more preferably 20 nm or less, and further preferably 18 nm or less.
  • the high-resistance transparent film 20 of the present embodiment preferably has a transmittance of 97% or more at a wavelength of 550 nm. According to this configuration, a sufficient transmittance can be secured, and the liquid crystal display panel 10 having excellent visibility can be configured (realized). Further, in order to configure (realize) the liquid crystal display panel 10 having excellent visibility, the transmittance of the high resistance transparent film 20 of the present embodiment at a wavelength of 550 nm is more preferably 97.5% or more, 98 It is more preferably% or more.
  • the high-resistance transparent film 20 of the present embodiment has a peak shift layer 21 on the second glass substrate 12 side.
  • the high resistance transparent film 20 is formed on the second glass substrate 12, and the high resistance transparent film 20 has a peak shift layer 21 and a surface layer 22.
  • the peak shift layer 21 is located on the second glass substrate 12 side, and the surface layer 22 is located on the peak shift layer 21.
  • the peak shift layer 21 is defined as In3d 5 on the energy side of the surface layer 22 of the high resistance transparent film 20 by 0.5 eV or more higher than the peak position of the binding energy of In3d 5/2 in X-ray photoelectron spectroscopy.
  • an intermediate layer (not shown) is located between the peak shift layer 21 and the surface layer 22. That is, the high resistance transparent film 20 also has an intermediate layer.
  • the intermediate layer is a value of more than 0 eV and less than 0.5 eV than the peak position of the binding energy of In3d 5/2 of the surface layer 22 in X-ray photoelectron spectroscopy, and the peak position of the binding energy of In3d 5/2 on the high energy side. Refers to the layer having. Since the intermediate layer is minute, it is not shown in FIG. Further, in FIG. 2, the intermediate layer is included in the region of the surface layer 22.
  • the surface layer 22 is a layer in which the peak position of the binding energy of In3d 5/2 is not shifted and is constant, and the peak position of the binding energy of In3d 5/2 of the surface layer 22 is constant.
  • the peak shift layer 21 is defined as described above with reference to.
  • FIG. 2 shows the results of X-ray photoelectron spectroscopy (data of Example 2) for explaining the peak shift layer 21 according to the embodiment of the present invention.
  • the Y1 axis (vertical axis on the right side) indicates the processing time (spatter time) (unit: min) by the Ar beam
  • the Y2 axis (vertical axis on the left side) is the photoelectron intensity (unit: c).
  • / S) is shown
  • the horizontal axis shows the binding energy (unit: eV).
  • FIG. 2 is a depth profile of the photoelectron spectrum obtained by depth analysis described later, and FIG. 2 shows the photoelectron spectrum of the surface of the sample sputtered at each processing time.
  • two peaks can be confirmed, but the peak having a binding energy smaller (weaker) than the binding energy of 448 eV shows In3d 5/2.
  • a peak with a binding energy greater (stronger) than the binding energy of 448 eV indicates In3d 3/2.
  • the layer having the peak position on the vertical broken line indicating “shift: 0 eV” is the surface layer 22 of the high resistance transparent film 20.
  • the layer having the peak position of the binding energy of In3d 5/2 which is 0.5 eV or more larger than the “shift: 0 eV” indicated by the vertical broken line, is referred to as the peak shift layer 21.
  • the peak position of the binding energy of In3d 5/2 of the peak shift layer 21 is "shift: 0 eV" shown by the vertical broken line in FIG. 2, that is, In3d of the surface layer 22 of the high resistance transparent film 20. It shall be 0.5 eV or more higher than the peak position of the binding energy of 5/2.
  • the SiO 2 equivalent film thickness of the peak shift layer 21 related to the high resistance transparent film 20 is 6.5 nm or less.
  • the SiO 2 equivalent film thickness of the peak shift layer 21 is calculated by the following method. First, a commercially available Si wafer having a SiO 2 film (thermal oxide film) having a known thickness of about 100 nm is prepared. The SiO 2 film is sputtered with an Ar beam having a constant output by an X-ray photoelectron spectroscopy (XPS) apparatus, and etched in the thickness direction of the film (sputtering). The surface sputtered is analyzed by X-ray photoelectron spectroscopy (XPS). Sputtering and surface analysis are repeated alternately.
  • XPS X-ray photoelectron spectroscopy
  • the surface of the sample is sputtered with an Ar beam under the same conditions (acceleration voltage, irradiation range, etc.) as the sputtering process applied to the SiO 2 film described above.
  • the surface of the sputtered surface is analyzed by X-ray photoelectron spectroscopy (XPS) at regular intervals of the sputtering process. That is, the sputtering process for a certain period of time and the surface analysis are alternately repeated. This gives a depth profile of the photoelectron spectrum (the peak of the binding energy of In3d 5/2). This is called depth analysis.
  • the value obtained by multiplying the time required for sputtering from the appearance of the portion corresponding to the peak shift layer 21 to the disappearance by the above-mentioned sputtering rate is defined as the SiO 2 equivalent film thickness of the peak shift layer 21.
  • the time when the peak shift layer 21 disappears is determined as follows. For example, in FIG. 2, the time when the peak of the binding energy of In3d 5/2 cannot be confirmed is determined to be the time when the peak shift layer 21 disappears. More quantitatively, the peak intensity of the binding energy of In3d 5/2 is, a time point when 10% or less of the maximum peak intensity of the binding energy of In3d 5/2 in peak shift layer 21, the peak shift layer 21 disappears Judge as the time when it was done. For example, in FIG.
  • the SiO 2 equivalent film thickness of the peak shift layer 21 is 4.8 nm. According to this configuration, since the SiO 2 equivalent film thickness of the peak shift layer 21 is 6.5 nm or less, sufficient transmittance can be secured and a display panel having excellent visibility can be configured. It becomes.
  • the SiO 2 equivalent film thickness of the peak shift layer 21 is preferably 6.0 nm or less, and more preferably 5.5 nm or less.
  • an oxide sputtering target having a composition corresponding to the above-mentioned high-resistance transparent film 20 is used.
  • This oxide sputtering target is a sintered body composed of an oxide composed of a metal component and oxygen and an unavoidable impurity, and the metal component has an In of 60 atomic% or more and 90 atoms, where the total of the metal components is 100 atomic%. It is contained in the range of% or less, Zr is contained in the range of 1 atomic% or more and 32 atomic% or less, and the balance is Si and unavoidable metal.
  • this oxide sputtering target is manufactured as follows.
  • In 2 O 3 powder, ZrO 2 powder, and SiO 2 powder are prepared as raw material powders.
  • the In 2 O 3 powder preferably has a purity of 99.9 mass% or more and an average particle size of 0.1 ⁇ m or more and 10 ⁇ m or less.
  • the ZrO 2 powder preferably has a purity of 99.9 mass% or more and an average particle size of 0.2 ⁇ m or more and 20 ⁇ m or less.
  • the SiO 2 powder preferably has a purity of 99.8 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 as follows.
  • each metal component of Fe 2 O 3 , SiO 2 , TiO 2 and Na 2 O is measured and calculated by converting it into the amount of oxide.
  • the purity of the ZrO 2 powder is calculated assuming that the balance other than these oxides is ZrO 2.
  • These oxide powders are weighed so as to have a predetermined composition ratio and mixed using a pulverizing and mixing device to prepare a mixed raw material powder.
  • the specific surface area (BET specific surface area) of the mixed raw material powder is within the range of 11.5 m 2 / g or more and 13.5 m 2 / g or less.
  • the obtained mixed raw material powder is filled in a molding die and pressed to obtain a molded product having a predetermined shape.
  • This molded product is placed in an electric furnace, heated and sintered.
  • the holding temperature is in the range of 1300 ° C. or higher and 1600 ° C. or lower, and the holding time is in the range of 2 hours or more and 10 hours or less.
  • oxygen it is preferable to introduce oxygen into the electric furnace. Then, it is cooled to 600 ° C. in an electric furnace at a cooling rate of 200 ° C./hour or less, then cooled to room temperature, and the sintered body is taken out from the electric furnace. The obtained sintered body is machined to produce an oxide sputtering target of a predetermined size.
  • the above-mentioned oxide sputtering target is bonded to the backing material and mounted in the sputtering apparatus. Then, the inside of the sputtering apparatus is made into a vacuum atmosphere. Next, Ar gas and oxygen gas are introduced to adjust the sputter gas pressure, and sputter film formation is carried out. At this time, regarding the amount of oxygen to be introduced into the sputtering apparatus, 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 rate ratio is not particularly limited, but is preferably 0.005 or more. By introducing oxygen in this range, it is possible to form a high-resistance transparent film 20 having a more preferable resistance value and a high visible light transmittance.
  • the high resistance transparent film 20 having the thicker peak shift layer 21 is formed.
  • the high resistance transparent film 20 having the thinner peak shift layer 21 is formed. That is, as the amount of oxygen introduced into the sputtering apparatus during sputtering film formation increases, the peak shift layer 21 having a high visible light absorption rate becomes thinner, so that a highly transparent high-resistance transparent film 20 can be obtained. ..
  • the transmittance of visible light is excellent and the resistance value is sufficiently high, and the high resistance in the liquid crystal display panel 10 is obtained. It will fully function as the transparent film 20.
  • the high resistance transparent film 20 of the present embodiment tends to be amorphous, corrosive substances such as moisture do not easily enter the inside of the film, and even when used in a high temperature and high humidity environment, the resistance value and the resistance value and The transmittance does not change significantly, and it has excellent environmental resistance (heat resistance, moisture resistance). Further, since the transmittance and the resistance value do not change significantly even when they come into contact with water and alcohol, the high resistance transparent film 20 is formed and the high resistance transparent film 20 is formed before proceeding to the next step. Even if the high resistance transparent film 20 whose surface is contaminated is washed with water and alcohol, the high resistance transparent film 20 does not deteriorate.
  • the sputtering film formation is performed by controlling the amount of oxygen introduced into the sputtering apparatus, the transmittance of visible light is high and the resistance value is high.
  • a sufficiently high resistance transparent film 20 can be stably formed.
  • the flow rate ratio of oxygen / argon is set to 0.03 or less with respect to the amount of oxygen to be introduced, it is possible to prevent the resistance value of the formed high-resistance transparent film 20 from becoming too high.
  • the present invention is not limited to this, and can be appropriately modified without departing from the technical requirements of the invention.
  • the high-resistance transparent film 20 provided on the liquid crystal display panel 10 shown in FIG. 1 has been described as an example, but the present invention is not limited to this, and a liquid crystal display panel having another structure can be used. It may be provided, or it may be provided on an organic EL display and another display panel such as a touch panel.
  • the film formation is performed 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 is used. May be used to form a film.
  • Indium oxide powder In 2 O 3 powder: purity 99.9 mass% or more, average particle size 1 ⁇ m
  • zirconium oxide powder ZrO 2 powder: purity 99.9 mass% or more, average particle size 2 ⁇ m
  • Silicon oxide powder SiO 2 powder: purity 99.8 mass% or more, average particle size 2 ⁇ m
  • the purity of the zirconium oxide powder was calculated by measuring the contents of Fe 2 O 3 , SiO 2 , TiO 2 and Na 2 O, and assuming that the balance other than these oxides was ZrO 2.
  • Each of the weighed raw material powders was put into a bead mill device together with a zirconia ball having a diameter of 0.5 mm and a solvent (Solmix A-11 manufactured by Japan Alcohol Trading Co., Ltd.) as a pulverizing medium, and pulverized and mixed.
  • the crushing / mixing time was 1 hour.
  • the zirconia balls were separated and recovered to obtain a slurry containing the raw material powder and the solvent.
  • the obtained slurry was heated to remove the solvent to obtain a mixed powder.
  • the obtained mixed powder was filled in a mold of 220 mm ⁇ 275 mm and pressed at a pressure of 150 kg / cm 2 to prepare a flat plate-shaped molded product.
  • the obtained molded product is charged into an electric furnace (internal volume 27,000 cm 3 ), and while introducing oxygen gas at a flow rate of 4 L / min, it is calcined and sintered by holding it at a calcining temperature of 1400 ° C. for 7 hours. Manufactured the body. After firing, the mixture was cooled in an electric furnace at a cooling rate of 130 ° C./hour up to 600 ° C. while continuously introducing oxygen gas. Then, the introduction of oxygen gas was stopped, the mixture was cooled to room temperature in the furnace, and the sintered body was taken out from the electric furnace. The obtained sintered body was machined to produce a flat plate-shaped oxide sputtering target having a size of 126 mm ⁇ 178 mm ⁇ 6 mm.
  • the oxide sputtering target was soldered to a backing plate made of oxygen-free copper, and this was mounted in a magnetron type sputtering device (Showa Vacuum SPH-2307). Further, a 50 mm square non-alkali glass substrate was placed in the sputtering apparatus. Next, the inside of the sputtering apparatus was evacuated to 7 ⁇ 10 -4 Pa or less by the vacuum exhaust apparatus. Next, Ar gas and oxygen gas were introduced so as to have the oxygen / argon flow rate ratio described in the column of "Oxygen amount at the time of sputtering" in Table 1.
  • the sputter gas pressure was adjusted to 0.67 Pa, and pre-sputtering was carried out for 1 hour to remove the processed layer on the target surface.
  • the flow rates of Ar gas and oxygen gas at this time were the conditions shown in Table 1 as described above, and a pulse DC power supply was used as the electric power.
  • the input power was p-DC450W.
  • the oxygen / argon flow rate ratio was the ratio of the oxygen flow rate (sccm) and the argon flow rate (sccm).
  • the inside of the sputtering apparatus was exhausted to 7 ⁇ 10 -4 Pa or less by the vacuum exhaust apparatus.
  • a sputtering film was formed under the same conditions as the above pre-sputtering, and a high-resistance transparent film having the film thickness shown in Table 1 was formed on a 50 mm square non-alkali glass substrate. The distance between the substrate and the target at this time was set to 60 mm.
  • composition, film thickness, thickness of the peak shift layer, transmittance, and resistance value of the obtained high resistance transparent film were evaluated as follows.
  • crystallinity of the high-resistance transparent film was confirmed.
  • composition of high resistance transparent film The above-mentioned high-resistance transparent film was analyzed by an X-ray photoelectron spectroscopy (XPS) apparatus (manufactured by ULVACPHI Corporation), and the In concentration, Zr concentration and Si concentration of each high-resistance transparent film were measured. Table 1 shows the composition of the film in which the total of the metal components is 100 atomic%.
  • the above-mentioned high-resistance transparent film was analyzed by a stylus type surface shape measuring instrument (manufactured by Bruker Japan Co., Ltd.), and the film thickness of each high-resistance transparent film was measured.
  • the surface of the sputtered surface is analyzed every time the above-mentioned high-resistance transparent film is sputtered by an X-ray photoelectron spectroscopy (XPS) device (manufactured by ULVACPHI Co., Ltd.) with Ar sputtering (acceleration voltage 500V) for 1 minute. It was. As a result, for example, a depth analysis for 50 minutes was performed. The analysis time may be changed according to the film thickness. From the obtained analysis results, the SiO 2 equivalent film thickness of the peak shift layer was calculated by the following method.
  • XPS X-ray photoelectron spectroscopy
  • the Ar beam used for processing was used to sputter a SiO 2 film having a known thickness under the same conditions as for sputtering, and the sputter rate was calculated from the required time.
  • the depth analysis of the sample for measurement was carried out, and the time required for the part corresponding to the peak shift layer to be processed by sputtering (from the appearance of the part corresponding to the peak shift layer to the disappearance of the part corresponding to the peak shift layer required for the sputtering process). Time) was measured. The time required for this sputtering process was multiplied by the calculated sputtering rate, and the obtained value was obtained as the SiO 2 equivalent film thickness of the peak shift layer.
  • Comparative Examples 1 and 2 the amount of oxygen during sputtering was smaller than the amount of oxygen during sputtering in the examples of the present application. As a result, the transmittance was 97% or less, and a sufficient transmittance could not be obtained. It can be considered that the reason is that the thickness of the peak shift layer in Comparative Example 1 was 8.1 nm in Comparative Example 1 and 7.0 nm in Comparative Example 2.
  • the thickness of the peak shift layer was formed thinner than in Comparative Examples 1 and 2, and the resistance value and the transmittance were also high.
  • the transmittance of visible light is high, the resistance value is sufficiently high, and the environmental resistance (heat resistance, moisture resistance) is excellent. It was confirmed that it is possible to provide a high resistance transparent film having.
  • the high-resistance transparent film of the present embodiment can be suitably applied as a shield layer of a display panel such as a liquid crystal display, an organic EL display, and a touch panel.
  • a display panel such as a liquid crystal display, an organic EL display, and a touch panel.
  • Liquid crystal display panel 11 1st glass substrate 12 2nd glass substrate (transparent substrate) 13 Liquid crystal layer 15 Polarizing film 16 Protective film 20 High resistance transparent film 21 Peak shift layer 22 Surface layer

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Abstract

La présente invention concerne un film transparent à haute résistance (20) comprenant un oxyde qui est formé sur un substrat transparent (12) et qui contient, en tant que composants métalliques, de l'In, du Zr et du Si. Une couche de décalage de pic (21), pour laquelle la position de pic de l'énergie de liaison In3d5/2 est d'au moins 0,5 eV plus loin vers le côté haute énergie que la position de pic de l'énergie de liaison In3d 5/2 dans une couche de surface (22) du film transparent à haute résistance (20), en spectrométrie photoélectronique à rayons X, est disposée sur le côté du substrat transparent (12) du film transparent à haute résistance (20) et l'épaisseur de film de la couche de décalage de pic (21) en termes de SiO2 est de 6,5 nm ou moins.
PCT/JP2020/041181 2019-11-05 2020-11-04 Film transparent à haute resistance WO2021090829A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019114808A (ja) * 2012-11-08 2019-07-11 株式会社半導体エネルギー研究所 トランジスタ
WO2019208240A1 (fr) * 2018-04-26 2019-10-31 三菱マテリアル株式会社 Couche de protection, procédé de production de couche de protection, et cible de pulvérisation d'oxyde

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8075973B2 (en) 2005-12-02 2011-12-13 Panasonic Corporation Information recording medium and method for manufacturing the same
US9001280B2 (en) 2012-06-08 2015-04-07 Apple Inc. Devices and methods for shielding displays from electrostatic discharge

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019114808A (ja) * 2012-11-08 2019-07-11 株式会社半導体エネルギー研究所 トランジスタ
WO2019208240A1 (fr) * 2018-04-26 2019-10-31 三菱マテリアル株式会社 Couche de protection, procédé de production de couche de protection, et cible de pulvérisation d'oxyde

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