CN108028094B - Substrate with transparent conductive layer and liquid crystal panel - Google Patents

Substrate with transparent conductive layer and liquid crystal panel Download PDF

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Publication number
CN108028094B
CN108028094B CN201780002944.4A CN201780002944A CN108028094B CN 108028094 B CN108028094 B CN 108028094B CN 201780002944 A CN201780002944 A CN 201780002944A CN 108028094 B CN108028094 B CN 108028094B
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conductive layer
transparent conductive
substrate
liquid crystal
oxide
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CN108028094A (en
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须田具和
高桥明久
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Ulvac Inc
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Ulvac Inc
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • 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
    • 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
    • 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
    • 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
    • G02F1/1343—Electrodes
    • 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
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
    • 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

Abstract

The invention provides a substrate with a transparent conductive layer with little change of resistance along with time, a liquid crystal panel and a manufacturing method of the substrate with the transparent conductive layer. The substrate with a transparent conductive layer according to one embodiment of the present invention includes a substrate and a transparent conductive layer. The substrate with the transparent conductive layer is provided with the transparent conductive layer provided on the substrate, and contains tin oxide and at least one of niobium oxide, tantalum oxide, and antimony oxide. This reduces the change in resistance with time in the substrate with the transparent conductive layer.

Description

Substrate with transparent conductive layer and liquid crystal panel
Technical Field
The present invention relates to a substrate with a transparent conductive layer, a liquid crystal panel, and a method for manufacturing a substrate with a transparent conductive layer.
Background
An In-cell type liquid crystal panel of a so-called lateral electric Field driving method (IPS (In-Plane Switching) method or FFS (Fringe Field Switching) method) In which an electric Field having a horizontal component is generated In a liquid crystal panel substrate to drive a liquid crystal has the following structure. For example, this structure has a color filter substrate, a counter substrate having a liquid crystal driving electronic circuit for driving the liquid crystal and a sensor electrode for sensing a finger touch, and the liquid crystal provided between these substrates.
In such a liquid crystal panel, no electrode is formed on the color filter substrate, and the color filter is charged to cause a malfunction of a display operation. In order to prevent such electrification, there are the following techniques: a transparent conductive layer containing silicon and indium tin oxide having a high resistance as a main material is provided on a surface of a color filter substrate on which a color filter is not formed (see, for example, patent document 1).
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 5855948.
Disclosure of Invention
Problems to be solved by the invention
However, the transparent conductive layer containing indium tin oxide as a main component and silicon has indium tin oxide exposed on the surface thereof. Therefore, the transparent conductive layer is poor in weather resistance and chemical resistance, and the resistance thereof is likely to change with time.
In view of the above, an object of the present invention is to provide a substrate with a transparent conductive layer, a liquid crystal panel, and a method for manufacturing a substrate with a transparent conductive layer, in which a change in resistance with time is small.
Means for solving the problems
In order to achieve the above object, a substrate with a transparent conductive layer according to one embodiment of the present invention includes a substrate and a transparent conductive layer.
The transparent conductive layer is provided on the substrate, and contains tin oxide and at least one of niobium oxide, tantalum oxide, and antimony oxide.
This reduces the change in resistance with time in the substrate with the transparent conductive layer.
In the substrate with a transparent conductive layer, a content of at least one of the niobium oxide, the tantalum oxide, and the antimony oxide may be 5 wt% or more and 15 wt% or less in the transparent conductive layer.
Thus, in the substrate with the transparent conductive layer, the oxide is hardly reduced, and the high resistance state of the transparent conductive layer is maintained.
In the substrate with a transparent conductive layer, the sheet resistance of the transparent conductive layer may be 1 × 107(omega/sq.) or more and 1X 1010(omega/sq.) below.
The transmittance of the transparent conductive layer may be 98.5% or more at a wavelength of 550 nm.
By using such a substrate with a transparent conductive layer having high light transmittance for an In-cell type liquid crystal panel, electrification of the color filter is suppressed, and the light transmittance of the liquid crystal panel is not significantly reduced.
In the substrate with a transparent conductive layer, the thickness of the transparent conductive layer may be 5nm or more and 15nm or less.
In this way, in the substrate with a transparent conductive layer, a transparent conductive layer having appropriate resistance and transmittance is provided on the substrate.
In the substrate with a transparent conductive layer, the transparent conductive layer may contain nitrogen.
Thus, in the substrate with the transparent conductive layer, the resistance of the transparent conductive layer is adjusted by the amount of nitrogen added.
In the substrate with a transparent conductive layer described above, the substrate may have a transparent substrate and a color filter.
The transparent substrate may be disposed between the transparent conductive layer and the color filter.
Thereby, the transparent conductive layer suppresses charging of the color filter.
A liquid crystal panel according to an embodiment of the present invention includes a substrate with a transparent conductive layer, a counter substrate, and a liquid crystal.
The substrate with the transparent conducting layer is provided with a first transparent substrate, the transparent conducting layer and a color filter, wherein the first transparent substrate is provided with a first surface and a second surface. The transparent conductive layer is provided on the first surface, and contains tin oxide and at least one of niobium oxide, tantalum oxide, and antimony oxide. The color filter is arranged on the second surface.
The counter substrate has a second transparent substrate, and a sensor electrode and a liquid crystal driving electronic circuit provided on the second transparent substrate.
The liquid crystal is provided between the substrate with the transparent conductive layer and the counter substrate, and is driven and controlled by the liquid crystal driving electronic circuit.
In this way, in the liquid crystal panel, the transparent conductive layer prevents the color filter from being charged. In addition, in the transparent conductive layer, the change in resistance with time is small. As a result, the touch sensing function of the liquid crystal panel is less likely to change with time, and the reliability is further improved.
In the above-described liquid crystal panel, a content of at least one of the niobium oxide, the tantalum oxide, and the antimony oxide may be 5 wt% or more and 15 wt% or less in the transparent conductive layer.
Thus, in the substrate with the transparent conductive layer of the liquid crystal panel, the oxide is hardly reduced, and the high resistance state of the transparent conductive layer is maintained.
In the above liquid crystal panel, the sheet resistance of the transparent conductive layer may be 1 × 107(omega/sq.) or more and 1X 1010(omega/sq.) below.
The transmittance of the transparent conductive layer may be 98.5% or more at a wavelength of 550 nm.
By using such a substrate with a transparent conductive layer having high light transmittance for an In-cell type liquid crystal panel, electrification of the color filter is suppressed, and the light transmittance of the liquid crystal panel is not significantly reduced.
In the above-described liquid crystal panel, the thickness of the transparent conductive layer may be 5nm or more and 15nm or less.
In this way, in the liquid crystal panel, a transparent conductive layer having appropriate resistance and transmittance is provided on the transparent substrate.
In the above liquid crystal panel, the transparent conductive layer may contain nitrogen.
Thus, in the liquid crystal panel, the resistance of the transparent conductive layer is adjusted by the amount of nitrogen added.
In addition, in the method for manufacturing a substrate with a transparent conductive layer according to one embodiment of the present invention, a target containing tin oxide and at least one of niobium oxide, tantalum oxide, and antimony oxide is used, and the content of at least one of niobium oxide, tantalum oxide, and antimony oxide in the target is 5 wt% or more and 15 wt% or less. A transparent conductive layer containing tin oxide and at least one of niobium oxide, tantalum oxide, and antimony oxide is formed on a substrate in a mixed gas atmosphere of argon and oxygen having an oxygen partial pressure of 0.005Pa to 0.05 Pa.
By forming a transparent conductive layer in such a mixed gas atmosphere, a transparent conductive layer having a desired high resistance can be obtained. Further, reduction of the oxide in the transparent conductive layer is suppressed, and a transparent conductive layer with little change in resistance with time can be obtained.
In the above-described method for manufacturing a substrate with a transparent conductive layer, the mixed gas may contain nitrogen, and the transparent conductive layer may be formed when the partial pressure of nitrogen is 0.025Pa or more and 0.1Pa or less.
Thus, in the substrate with the transparent conductive layer, the resistance of the transparent conductive layer is adjusted by the amount of nitrogen added.
Effects of the invention
As described above, the present invention provides a substrate with a transparent conductive layer, a liquid crystal panel, and a method for manufacturing a substrate with a transparent conductive layer, in which a change in resistance with time is small.
Drawings
Fig. 1 is a schematic cross-sectional view showing a liquid crystal panel according to the present embodiment.
Fig. 2 is a schematic graph showing the relationship between the oxygen flow rate and the sheet resistance of the transparent conductive layer in the case where a target containing tin oxide and niobium oxide is used.
Fig. 3 is a schematic graph showing the relationship between the oxygen flow rate and the sheet resistance of the ITO layer in the case where a target made of ITO was used as a comparative example.
Fig. 4 is a schematic graph showing a relationship between a nitrogen flow rate and a sheet resistance of the transparent conductive layer in a case where nitrogen is added to a mixed gas of argon and oxygen.
Fig. 5 is a schematic graph showing the light transmittance of the transparent conductive layer.
Fig. 6 is a schematic diagram (1) showing a change in the sheet resistance of the transparent conductive layer with time.
Fig. 7 is a schematic diagram (2) showing a change in the sheet resistance of the transparent conductive layer with time.
Fig. 8 is a schematic diagram showing the corrosion resistance of the transparent conductive layer.
Detailed Description
Hereinafter, embodiments of the present invention will be described with reference to the drawings. In each drawing, XYZ-axis coordinates are sometimes introduced. The numerical values, graphs, and diagrams shown below are examples, and are not limited to the examples.
In the present embodiment, an In-cell type liquid crystal panel with a touch panel function using an FFS method is exemplified, but the present invention is not limited thereto. For example, the liquid crystal panel according to the present embodiment can be applied to an IPS liquid crystal panel, and can be applied to the following configuration: an electronic circuit for driving a liquid crystal and an electrode for a sensor are provided on one of a pair of substrates constituting a liquid crystal panel, and a color filter is formed on the other substrate without forming an electrode.
[ liquid Crystal Panel ]
Fig. 1 is a schematic cross-sectional view showing a liquid crystal panel according to the present embodiment.
The liquid crystal panel 1 shown in fig. 1 has both a function of displaying an image and a touch panel function. The liquid crystal panel 1 includes a substrate 10 with a transparent conductive layer, a counter substrate 20, a liquid crystal 40, a polarizing plate 50, a glass cover 60, and a polarizing plate 51. In the example of fig. 1, a polarizing plate 51, a counter substrate 20, a liquid crystal 40, a substrate 10 with a transparent conductive layer, a polarizing plate 50, and a glass cover plate 60 are laminated in this order in the Z-axis direction. Spacers 41 are provided in the liquid crystal 40.
In the liquid crystal panel 1, a backlight is incident on the polarizing plate 51. Further, an image is viewed through the glass cover 60 in the liquid crystal panel 1. In addition, in the liquid crystal panel 1, the touch operation can be performed by touching the glass cover 60 with a finger 70 or the like. The structure of each member of the liquid crystal panel 1 will be described in detail below.
The substrate 10 with a transparent conductive layer has a transparent conductive layer 12 and a color filter substrate 14. The color filter substrate 14 includes a transparent substrate 11 (first transparent substrate) and a color filter 15. The transparent substrate 11 is disposed between the transparent conductive layer 12 and the color filter 15. The transparent substrate 11 is, for example, a glass substrate. The transparent conductive layer 12 functions as an antistatic layer in the liquid crystal panel 1, for example.
The transparent conductive layer 12 is provided on the surface 11a (first surface) of the transparent substrate 11. Transparent conductive layer 12 contains niobium oxide (Nb)2O3Or Nb2O5) Tantalum oxide (Ta)2O3Or Ta2O5) And antimony oxide (Sb)2O3Or Sb2O5) At least any one of (1) and tin oxide (SnO)2)。
For example, the transparent conductive layer 12 is composed of tin oxide as a main component and at least one of niobium oxide, tantalum oxide, and antimony oxide as a sub-component. Here, the transparent conductive layer 12 may contain a trace amount of an element such as aluminum (Al) or zirconium (Zr) introduced in the process of manufacturing the target. Substantially the same effect can be obtained in the present embodiment with or without containing a trace element (Al, Zr, or the like) in the transparent conductive layer 12. In addition, the subcomponent may be an oxide of any element of group iii elements in addition to the above-described oxides.
In the transparent conductive layer 12, the content of at least one of niobium oxide, tantalum oxide, and antimony oxide is 5 wt% or more and 15 wt% or less. When the content of at least one of niobium oxide, tantalum oxide, and antimony oxide is less than 5 wt%, the resistance of the transparent conductive layer 12 is undesirably low, for example. On the other hand, when the content of at least one of niobium oxide, tantalum oxide, and antimony oxide is more than 15 wt%, for example, a target material used in film formation is liable to be broken, which is not preferable.
The sheet resistance of the transparent conductive layer 12 made of such an oxide is, for example, 1 × 107(omega/sq.) or more and 1X 1010(omega/sq.) below. When the square resistance of the transparent conductive layer 12 is less than 1 × 107(Ω/sq.) it is not preferable that a touch signal during a touch operation, for example, is shielded by the transparent conductive layer 12. On the other hand, when the sheet resistance of the transparent conductive layer 12 is larger than 1X 1010(Ω/sq.) is not preferable because, for example, the static eliminating function of the transparent conductive layer 12 is lowered.
The sheet resistance of the transparent conductive layer 12 can be adjusted by changing the content of at least one of niobium oxide, tantalum oxide, and antimony oxide contained in the transparent conductive layer 12. Alternatively, the sheet resistance can be adjusted by changing the amount of oxygen introduced into the transparent conductive layer 12 during film formation, for example. The transparent conductive layer 12 having such a sheet resistance has a transmittance of 98.5% or more at a wavelength of 550 nm.
In the liquid crystal panel 1 provided with the transparent conductive layer 12, the transparent conductive layer 12 is excellent in weather resistance and chemical resistance, and the oxide contained in the transparent conductive layer 12 is hardly reduced. Thus, the resistance of the transparent conductive layer 12 is in a high resistance state (1 × 10)7(omega/sq.) or more and 1X 1010(omega/sq.) or less) can be maintained for a long period of time. As a result, in the liquid crystal panel 1, the touch sensing during the touch operation is stable, and the electrification of the color filter 15 is suppressed. In the liquid crystal panel 1, the light transmittance of the transparent conductive layer 12 is high, and the image of the liquid crystal panel 1 can be more clearly viewed without significantly decreasing the light transmittance of the liquid crystal panel. That is, the operational reliability of the liquid crystal panel 1 is further improved.
The thickness of the transparent conductive layer 12 is 5nm to 15 nm. When the thickness of the transparent conductive layer 12 is less than 5nm, for example, the sheet resistance of the transparent conductive layer 12 becomes higher than the above range, and the antistatic function of the transparent conductive layer 12 is lowered, which is not preferable. When the thickness of the transparent conductive layer 12 is more than 15nm, it is not preferable because, for example, the transmittance of the transparent conductive layer 12 is lowered.
Further, nitrogen (N) may be contained in the transparent conductive layer 12. Nitrogen is contained as an impurity element in the transparent conductive layer 12, for example. The sheet resistance of the transparent conductive layer 12 can be adjusted by changing the amount of nitrogen added, for example. For example, when forming the transparent conductive layer 12, the sheet resistance of the transparent conductive layer 12 can be adjusted by adjusting the proportion of oxygen introduced during film formation to such an extent that the transparent conductive layer 12 is not reduced and controlling the proportion of nitrogen introduced during film formation independently of the proportion of oxygen.
When the transparent conductive layer is formed of an ITO (Indium Tin Oxide) layer alone, the sheet resistance of the ITO layer decreases with time because the ITO layer has low weather resistance and chemical resistance. Thus, in the liquid crystal panel composed of the ITO layer alone, the touch sensing function gradually deteriorates with time. The reason for this is considered to be that oxygen contained in the ITO layer is desorbed with time (so-called oxygen escape), and the sheet resistance thereof decreases with time. Further, for this reason, when ITO is formed on the bonded substrate, annealing treatment cannot be sufficiently performed, and an ITO layer having high crystallinity cannot be formed. In addition, in the monomer layer in which Si is added to the ITO layer, ITO is exposed on the surface of the monomer layer, and therefore, the same phenomenon occurs.
In order to prevent the phenomenon that oxygen contained in the ITO layer is released with time, a method of providing a capping layer for suppressing the release of oxygen on the ITO layer is considered. However, the number of layers of the laminate in which the coating layer is provided on the ITO layer is increased as compared with the single layer, and the light transmittance of the laminate itself is lowered. As a method for increasing the light transmittance of the laminate, there is a method in which the cover layer functions as an antireflection layer. However, the antireflection layer needs to be formed relatively thick, and this method increases the manufacturing cost.
In this manner, the transparent conductive layer 12 is preferably used for a liquid crystal panel.
The color filter 15 is formed on the surface 11b (second surface) of the transparent substrate 11. The color filter 15 includes a black matrix formed in a lattice shape using a black resin or the like, and a red color layer, a green color layer, and a blue color layer formed in a stripe shape, for example, so as to fill the opening of the black matrix. An alignment film, not shown, is formed on the color filter 15.
The openings formed by the lattice-shaped black matrix correspond to the sub-pixels, and one pixel is composed of three sub-pixels, namely a red sub-pixel, a green sub-pixel, and a blue sub-pixel.
The counter substrate 20 includes a transparent substrate 21 (second transparent substrate) and a functional layer 22, and the functional layer 22 includes a sensor electrode and a liquid crystal driving electronic circuit. The transparent substrate 21 is, for example, a glass substrate.
The transparent substrate 21 has a surface 21a and a surface 21 b. The functional layer 22 is provided on the surface 21b of the transparent substrate 21. An alignment film, not shown, is formed on the functional layer 22.
The liquid crystal driving electronic circuit is a component for driving the liquid crystal 40. The sensing sensor electrode constitutes a part of the sensing sensor, and is a member for sensing a touch operation on the surface of the glass cover plate 60.
The functional layer 22 includes a pixel electrode, a TFT (Thin Film Transistor), a gate line, a signal line, a common electrode driving line, a sensing sensor driving line, and a sensing sensor detecting line.
The liquid crystal driving electronic circuit includes a pixel electrode, a TFT, a gate line, a signal line, a common electrode, and a common electrode driving line. These liquid crystal driving electronic circuits are driven and controlled by a drive control circuit provided on a drive circuit board, not shown, electrically connected to the liquid crystal panel.
The sensing sensor electrode is composed of a sensing sensor drive line, a sensing sensor detection line, and a common electrode. The sensor includes these sensor electrodes and a touch position detection control circuit provided on a drive circuit board, not shown, electrically connected to the liquid crystal panel. By providing the sensing sensor, the liquid crystal panel has a touch panel function. The common electrode used for liquid crystal driving also functions as an electrode for a sensor.
In this manner, the counter substrate 20 is provided with a liquid crystal driving electronic circuit that generates an image to be displayed on the display screen of the liquid crystal panel 1, and a part of a sensor that senses a touch by a tool such as a finger 70 or a stylus pen on the surface of the liquid crystal panel 1.
When the horizontal surface of the transparent substrate 21 is an XY plane, gate lines and signal lines are provided in the X-axis direction and the Y-axis direction, respectively, with an interlayer insulating film interposed therebetween, and TFTs and pixel electrodes in the shape of comb teeth are provided at each intersection thereof. A gate electrode constituting the TFT is electrically connected to the gate line, and a source and a drain constituting the TFT are electrically connected to the signal line and the pixel electrode, respectively.
The common electrode is formed in a plurality of island shapes corresponding to each pixel. The TFT, the common electrode, and the pixel electrode are each a structure in which the TFT, the interlayer insulating film, the common electrode, the interlayer insulating film, and the pixel electrode are stacked in this order from the transparent substrate 21 side.
The common driving line is electrically connected to the common electrode and formed in the same layer as the signal line, the source, and the drain.
A plurality of driving lines for sensing sensors are formed in the X-axis direction on the same layer as the gate electrodes and the gate lines. The drive line for the sensing sensor is electrically connected to a part of the common electrode, and the common electrode connected to the drive electrode for the sensing sensor functions as a drive electrode for the sensing sensor. The drive electrode for the sensor is connected to a touch position detection control circuit, not shown, which outputs a drive signal for touch position detection.
A plurality of sense sensor detection lines are formed in the Y-axis direction on the same layer as the source and signal lines. The sensing lines for the sensing sensors are electrically connected to other common electrodes that are not electrically connected to the driving lines for the sensing sensors, and the common electrodes connected to the sensing lines for the sensing sensors function as the sensing electrodes of the sensing sensors. The sensing sensor drive lines are connected to a touch position detection control circuit, not shown, which receives detection signals sent from the sensing sensor detection lines. And, the coordinates of the touch position are calculated by analyzing the received detection signal.
In the liquid crystal panel 1, in the display stage, a lateral electric field is formed by the liquid crystal driving electronic circuit to drive the liquid crystal 40, and an image is displayed on the liquid crystal panel 1. In the touch phase, since the capacitance between the driving electrode and the detecting electrode of the sensing sensor is reduced by the approach of the finger to the display surface, the touch position of the finger is determined by detecting the change in the capacitance by the sensing sensor.
The liquid crystal 40 is provided between the color filter 15 and the counter substrate 20 of the substrate 10 with a transparent conductive layer. The gap between the color filter 15 and the counter substrate 20 is maintained by the spacer 41. The surface 11b of the transparent substrate 11 on which the color filter 15 is formed faces the surface 21b of the transparent substrate 21 on which the functional layer 22 is provided of the counter substrate 20. The driving of the liquid crystal 40 is controlled by an electronic circuit for driving the liquid crystal. The glass cover 60 is fixed to the polarizing plate 50 by an adhesive layer not shown.
[ method for producing transparent conductive layer ]
A method for manufacturing a substrate 10 with a transparent conductive layer, which is a component of the liquid crystal panel 1, will be described with reference to fig. 1.
For example, a color filter substrate 14 is prepared in which a color filter 15 including a black matrix, a red colored layer, a green colored layer, and a blue colored layer is formed on the surface 11b of the transparent substrate 11.
Next, the transparent conductive layer 12 is formed on the surface 11a of the transparent substrate 11 on which the color filter 15 is not formed. The transparent conductive layer 12 is formed using, for example, a DC sputtering method. The DC sputtering method may be a magnetron DC sputtering method. Alternatively, the transparent conductive layer 12 may be formed using, for example, an AC sputtering method. As the AC sputtering method, a magnetron AC sputtering method may be used. According to the AC sputtering method, when the transparent conductive layer 12 in a high resistance state is formed using a conductive target (reactive sputtering), an anode can be secured, and productivity is excellent.
As the target, a target containing tin oxide and at least one of niobium oxide, tantalum oxide, and antimony oxide is used. For example, the target is composed of tin oxide as a main component and at least one of niobium oxide, tantalum oxide, and antimony oxide as a sub-component. Here, trace elements such as aluminum (Al) and zirconium (Zr) may be introduced into the target material during the production of the target material. The target material may or may not contain trace elements (Al, Zr, etc.), and substantially the same effects can be obtained in the present embodiment.
The content of at least one of niobium oxide, tantalum oxide, and antimony oxide in the target material is 5 wt% or more and 15 wt% or less. Hereinafter, a case of using a target material containing niobium oxide among niobium oxide, tantalum oxide, and antimony oxide will be exemplified. Here, the content of niobium oxide in the target material is, for example, 10 wt%.
For example, a target containing tin oxide and niobium oxide is used to form transparent conductive layer 12 on surface 11a of transparent substrate 11 in a DC sputtering apparatus. The thickness of the transparent conductive layer 12 is, for example, 10 nm. The film formation conditions are as follows.
Target material: tin oxide/niobium oxide (10 wt%)
Discharge gas: argon (Ar)/oxygen (O)2)
Total gas pressure: 0.1Pa or more and 1.0Pa or less
Argon partial pressure: 0.2Pa (flow rate 40sccm)
Oxygen partial pressure: 0.005Pa (flow rate of 1.0sccm) or more and 0.05Pa (10sccm) or less, preferably 0.005Pa (flow rate of 1.0sccm) or more and 0.013Pa (flow rate of 2.5sccm) or less
Substrate temperature: setting 25 deg.C
When an ITO layer alone having a high resistance is formed as a transparent conductive layer, it is necessary to increase the partial pressure of oxygen in the mixed gas during film formation to introduce a large amount of oxygen into the ITO layer. However, in this method, a large amount of oxygen is introduced into the ITO layer, and oxygen is released with time, and the sheet resistance thereof decreases with time.
In contrast, in the present embodiment, a target material is used which can obtain a transparent conductive layer 12 in a high resistance state without increasing the oxygen partial pressure in the mixed gas. The reason for this will be described with reference to fig. 2 below.
Fig. 2 is a schematic graph showing the relationship between the oxygen flow rate and the sheet resistance of the transparent conductive layer in the case where a target containing tin oxide and niobium oxide is used.
In fig. 2, the horizontal axis represents the flow rate of oxygen (sccm) during film formation, and the vertical axis represents the sheet resistance (Ω/sq.) of the transparent conductive layer 12. Fig. 2 shows the results of the case where the transparent conductive layer 12 is left to stand in an atmospheric environment at room temperature, and the case where the transparent conductive layer 12 is left to stand in an atmospheric environment at 120 ℃ for 60 minutes. The meaning of arrow a here is the desired high resistance state (1 × 10)7(omega/sq.) or more to 1X 1010(Ω/sq.)). This range is an example, and the high resistance state is not limited to the range shown by arrow a.
As shown in FIG. 2, when the transparent conductive layer 12 is left to stand in the atmospheric environment at room temperature (△), the sheet resistance of the transparent conductive layer 12 becomes extremely small when the oxygen flow rate is 1.5sccm or less in the range of 1.0sccm to 2.5sccm, and the minimum value (1X 10)8(Ω/sq.)) is in the range of desired high resistance states.
When the transparent conductive layer 12 is left to stand in an atmospheric environment at 120 ℃ for 60 minutes (○), the sheet resistance of the transparent conductive layer 12 becomes extremely small when the oxygen flow rate is 2.5sccm in the range of 1.0sccm to 2.5sccm, and the minimum value (1 × 10 ℃)7(Ω/sq.)) is in the range of desired high resistance states. The relationship between the oxygen flow rate and the sheet resistance of the ITO layer in the case where a target made of ITO is used for comparison will be described below.
Fig. 3 is a schematic graph showing the relationship between the oxygen flow rate and the sheet resistance of the ITO layer in the case where a target made of ITO was used as a comparative example.
As shown in fig. 3, when a target made of ITO is used, in order to obtain an ITO layer in a desired high resistance state, it is necessary to increase the flow rate of oxygen (oxygen partial pressure) as compared with the case of using a target containing tin oxide and niobium oxide. For example, 4.5sccm or more of oxygen was introduced into the ITO layer. However, in such an ITO layer, oxygen may be released with time.
In contrast, when a target material containing tin oxide and niobium oxide is used, the transparent conductive layer 12 in a desired high resistance state can be obtained without increasing the flow rate (oxygen partial pressure) in the mixed gas. That is, if a target containing tin oxide and niobium oxide is used, the transparent conductive layer 12 in a desired high resistance state is formed without introducing oxygen excessively into the transparent conductive layer 12. In other words, if a target containing tin oxide and niobium oxide is used, the transparent conductive layer 12 in a high resistance state can be obtained by introducing a smaller amount of oxygen into the transparent conductive layer 12 than in the case of forming an ITO layer.
Thus, in the transparent conductive layer 12, reduction of the oxide is suppressed for a long time, and a high-resistance state is maintained for a long time. As a result, the liquid crystal panel 1 is a liquid crystal panel having high operation reliability, in which touch sensitivity is not deteriorated and malfunction due to charging is reduced. When a target material containing tin oxide and niobium oxide is used, it is not preferable that the flow rate of oxygen be less than 1sccm (partial pressure of 0.005Pa), because the light transmittance of the transparent conductive layer 12 is increased, for example. When a target material containing tin oxide and niobium oxide is used, if the flow rate of oxygen is greater than 10sccm (partial pressure of 0.05Pa), for example, a large amount of oxygen is introduced into the transparent conductive layer 12, and oxygen is likely to be released from the transparent conductive layer 12 with time, which is not preferable.
In addition, the mixed gas (Ar/O) may be used2) Further contains nitrogen (N)2) And the transparent conductive layer 12 is formed. In this case, for example, nitrogen (N) is introduced as an impurity element into the transparent conductive layer 12. The film formation conditions are as follows.
Target material: tin oxide/niobium oxide (10 wt%)
Discharge gas: argon (Ar)/oxygen (O)2) Nitrogen (N)2)
Total gas pressure: 0.1Pa or more and 1.0Pa or less
Argon partial pressure: 0.2Pa (flow rate 40sccm)
Oxygen partial pressure: 0.005Pa (flow rate of 1.0sccm) or more and 0.05Pa (10sccm) or less, preferably 0.005Pa (flow rate of 1.0sccm) or more and 0.013Pa (flow rate of 2.5sccm) or less
Nitrogen partial pressure: 0.025Pa (flow rate of 5.0sccm) or more and 0.1Pa (flow rate of 20sccm) or less
Substrate temperature: setting 25 deg.C
Fig. 4 is a schematic graph showing a relationship between a nitrogen flow rate and a sheet resistance of the transparent conductive layer in a case where nitrogen is added to a mixed gas of argon and oxygen.
In fig. 4, the horizontal axis represents the flow rate of nitrogen (sccm) during film formation, and the vertical axis represents the sheet resistance (Ω/sq.) of the transparent conductive layer 12. Fig. 4 shows the result of the case where the transparent conductive layer 12 is left to stand at 120 ℃ for 60 minutes in an atmospheric environment.
As shown in fig. 4, when mixed gas (Ar/O) is added2) When the flow rate of the added nitrogen is changed, the sheet resistance of the transparent conductive layer 12 is changed within a range of a desired high resistance state. For example, when the flow rate of nitrogen is increased in a range of 5sccm or more and 20sccm or less, the sheet resistance of the transparent conductive layer 12 increases in accordance with the increase in the flow rate of nitrogen. That is, the sheet resistance of the transparent conductive layer 12 can be controlled by adjusting the flow rate of nitrogen.
For example, in the present embodiment, a mixed gas (Ar/O) is used in forming the transparent conductive layer 122) The proportion of oxygen in the transparent conductive layer 12 is adjusted to such an extent that the transparent conductive layer 12 is difficult to be reduced, thereby forming the transparent conductive layer 12. As an example, in the case where the transparent conductive layer 12 is left to stand in an atmospheric environment at 120 ℃ for 60 minutes, the oxygen flow rate is adjusted to 2.5 sccm. In addition, during the film formation, the sheet resistance of the transparent conductive layer 12 can be controlled to a predetermined resistance by adjusting the ratio of nitrogen independently of the ratio of oxygen.
This reliably suppresses the reduction of the oxide over a long period of time, and provides the transparent conductive layer 12 adjusted to a desired sheet resistance according to the amount of nitrogen added.
In addition, in an example of the film forming method, the transparent conductive layer 12 is formed on the color filter substrate 14. In the present embodiment, the color filter substrate 14 and the counter substrate 20 may be opposed to each other in advance, the liquid crystal 40 may be injected between the color filter substrate 14 and the counter substrate 20, and then the transparent conductive layer 12 may be formed on the color filter substrate 14. In this case, the same conditions are applied to the formation of the transparent conductive layer 12.
[ evaluation of transparent conductive layer ]
Fig. 5 is a schematic graph showing the light transmittance of the transparent conductive layer.
In fig. 5, the horizontal axis represents wavelength (nm) and the vertical axis represents light transmittance (%).
Further, fig. 5 shows the result of the case where the transparent conductive layer 12 is left to stand at 120 ℃ for 60 minutes in an atmospheric environment. The film formation conditions in fig. 5 are as follows.
Target material: tin oxide/niobium oxide (10 wt%)
Discharge gas: argon (Ar)/oxygen (O)2) Nitrogen (N)2)
Total gas pressure: 0.1Pa or more and 1.0Pa or less
Argon partial pressure: 0.2Pa (flow rate 40sccm)
Oxygen partial pressure: 0.013Pa (flow 2.5sccm)
Nitrogen partial pressure: 0Pa (flow rate 0sccm) or more and 0.1Pa (flow rate 20sccm) or less
Substrate temperature: setting 25 deg.C
As shown in fig. 5, in the above-described film formation conditions in which the nitrogen partial pressure is changed in the range of 0Pa (flow rate 0sccm) or more and 0.1Pa (flow rate 20sccm) or less, the light transmittance spectrum of the transparent conductive layer 12 is substantially the same line under any film formation conditions. For example, under the above-described film formation conditions in which the nitrogen partial pressure is changed within a range of 0Pa (flow rate 0sccm) or more and 0.1Pa (flow rate 20sccm) or less, the transmittance of the transparent conductive layer 12 is 94.0% or more at a wavelength of 400nm, 98.5% or more at a wavelength of 550nm, and 99.4% or more at a wavelength of 700 nm. As described above, in the present embodiment, the transparent conductive layer 12 having high light transmittance can be obtained.
Fig. 6 and 7 are schematic graphs showing changes in the sheet resistance of the transparent conductive layer with time.
In fig. 6 and 7, the horizontal axis represents time (h) and the vertical axis represents the square resistance (Ω/sq.).
Fig. 6 shows the result of the case where the transparent conductive layer 12 is placed at room temperature in an atmospheric environment.
Fig. 7 shows the results of the case where the transparent conductive layer 12 was placed at 60 ℃ and 90 RH% of water vapor. The film formation conditions in fig. 6 and 7 are as follows.
Target material: tin oxide/niobium oxide (10 wt%)
Discharge gas: argon (Ar)/oxygen (O)2) Nitrogen (N)2)
Total gas pressure: 0.1Pa or more and 1.0Pa or less
Argon partial pressure: 0.2Pa (flow rate 40sccm)
Oxygen partial pressure: 0.013Pa (flow 2.5sccm)
Nitrogen partial pressure: 0Pa (flow rate 0sccm) or more and 0.05Pa (flow rate 10sccm) or less
Substrate temperature: setting 25 deg.C
As shown in fig. 6 and 7, even when the transparent conductive layer 12 is placed in an atmospheric environment or under a constant temperature and humidity condition, the sheet resistance of the transparent conductive layer 12 is maintained in a desired high resistance state for 200 hours or more. As described above, according to the present embodiment, the transparent conductive layer 12 which is an antistatic layer and is less deteriorated with time can be obtained.
Fig. 8 is a schematic diagram showing the corrosion resistance of the transparent conductive layer.
In fig. 8, the abscissa represents the time (minutes) for which the transparent conductive layer 12 and the ITO layer were immersed in a phosphoric acid-nitric acid-acetic acid mixed acid (リン nitric acid), and the ordinate represents the sheet resistance (Ω/sq.).
The film formation conditions are as follows. The partial pressure of oxygen during film formation is controlled so that the sheet resistance of the transparent conductive layer 12 and the ITO layer is 1X 108(omega/sq.) or more and 1X 1010(Ω/sq.) was adjusted in the following manner.
Film formation conditions of transparent conductive layer 12:
target material: tin oxide/niobium oxide (10 wt%)
Discharge gas: argon (Ar)/oxygen (O)2)
Total gas pressure: 0.21Pa
Argon partial pressure: 0.2Pa (flow rate 40sccm)
Film thickness: 10nm
Substrate temperature: setting 25 deg.C
Film formation conditions of the ITO layer:
target material: indium oxide/tin oxide (10 wt%)
Discharge gas: argon (Ar)/oxygen (O)2)
Total gas pressure: 0.23Pa
Argon partial pressure: 0.2Pa (flow rate 40sccm)
Film thickness: 10nm
Substrate temperature: setting 25 deg.C
As shown in FIG. 8, the sheet resistance of the ITO layer immediately after film formation was 2.1X 109(Ω/sq.). Thereafter, when the ITO layer was immersed in a phosphoric acid-nitric acid-acetic acid mixed acid for 10 minutes, the film thickness of the ITO layer decreased, and the sheet resistance increased to 2.5X 1014(Ω/sq.)。
In contrast, in the transparent conductive layer 12, the sheet resistance immediately after film formation was 2.0 × 108(Ω/sq.). After that, the transparent conductive layer 12 is immersed in a phosphoric acid-nitric acid-acetic acid mixed acid, but the decrease in film thickness is suppressed as compared with the ITO layer. For example, the sheet resistance of the transparent conductive layer 12 after being immersed in a phosphoric acid-nitric acid-acetic acid mixed acid for 5 minutes becomes 2.8 × 108(Ω/sq.), the square resistance after 10 minutes of immersion became 3.1X 108(Ω/sq.) and the square resistance after 20 minutes of immersion was 2.3X 108(Ω/sq.). As described above, in the transparent conductive layer 12, the sheet resistance does not increase to the extent of the ITO layer even when immersed in a phosphoric acid-nitric acid-acetic acid mixed acid. That is, the transparent conductive layer 12 has higher corrosion resistance to acid than the ITO layer.
In addition, the transparent conductive layer 12 and the ITO layer are generally amorphous layers under film formation conditions at a film formation temperature of 25 ℃. Here, it is known that the ITO layer is subjected to a high-temperature annealing treatment, whereby crystallinity is improved and corrosion resistance is increased. However, the liquid crystal panel becomes thin by the thinning process, and may be broken by air expansion in the liquid crystal when heated. Therefore, an ITO layer having good crystallinity cannot be provided on the liquid crystal panel.
In contrast, in the present embodiment, the transparent conductive layer 12 can be formed on the color filter substrate 14 at room temperature. Even if the transparent conductive layer 12 is amorphous, the corrosion resistance is high, and thus a highly reliable liquid crystal panel is realized. In addition, in the liquid crystal panel 1, high-temperature annealing treatment for the transparent conductive layer 12 is not required, and the manufacturing process is further simplified.
Further, table 1 shows a comparison of the hardness of the transparent conductive layers.
[ Table 1]
Figure BDA0001583864550000171
In Table 1, the conditions of the annealing treatment were 240 ℃ for 40 minutes in an atmospheric environment. Further, "HM" is mahalanobis hardness. "HIT" is nanoindentation hardness. "HV" is Vickers hardness. The film thickness was 1000 nm.
As shown in table 1, the mahalanobis hardness, nanoindentation hardness, and vickers hardness of the transparent conductive layer 12 are increased as compared with the corresponding hardness of the ITO layer. This further improves the durability of the liquid crystal panel 1 having the transparent conductive layer 12.
For example, the transparent conductive layer 12 has higher scratch resistance than the case of using an ITO layer due to an increase in vickers Hardness (HV).
In addition, zinc oxide and titanium oxide are used as transparent conductive materials. However, it is known that the zinc oxide layer has inferior resistance to a phosphoric acid-nitric acid-acetic acid mixed acid to the transparent conductive layer 12. On the other hand, the refractive index of the titanium oxide layer is higher than that of the transparent conductive layer 12, and light reflection is more likely to occur at the interface between the titanium oxide layer and the layer in contact with the titanium oxide layer.
As described above, according to the present embodiment, the substrate 10 with a transparent conductive layer and the liquid crystal panel 1 having stable operation characteristics over a long period of time can be obtained. It should be understood that the present invention is not limited to the above-described embodiments, and various changes can be made.
Description of the reference numerals
1a liquid crystal panel;
10 a substrate with a transparent conductive layer;
11a transparent substrate;
11a, 11b surfaces;
12 a transparent conductive layer;
14 a color filter substrate;
15 a color filter;
20 a counter substrate;
21a transparent substrate;
21a, 21b surface;
22 a functional layer;
40 liquid crystal;
41 a spacer;
50. a 51 polarizing plate;
60 glass cover plates;
70 fingers.

Claims (8)

1. A substrate with a transparent conductive layer, comprising:
a substrate having a transparent substrate as a glass substrate and a color filter; and
an amorphous transparent conductive layer provided on the substrate, the amorphous transparent conductive layer containing tin oxide as a main component and at least one of niobium oxide, tantalum oxide, and antimony oxide as a subcomponent, wherein the content of at least one of niobium oxide, tantalum oxide, and antimony oxide is 5 wt% or more and 15 wt% or less, and the sheet resistance is 1 × 107Omega/sq. or more and 1X 1010A high resistance state of not more than Ω/sq, the transparent conductive layer functioning as an antistatic layer of the color filter,
the transparent substrate is arranged between the transparent conductive layer and the color filter.
2. The substrate with a transparent conductive layer according to claim 1,
the transmittance of the transparent conductive layer is 98.5% or more at a wavelength of 550 nm.
3. The substrate with a transparent conductive layer according to claim 1 or 2,
the thickness of the transparent conductive layer is 5nm to 15 nm.
4. The substrate with a transparent conductive layer according to claim 1 or 2,
the transparent conductive layer contains nitrogen.
5. A liquid crystal panel has:
a substrate with a transparent conductive layer, comprising a first transparent substrate as a glass substrate, an amorphous transparent conductive layer, and a color filter, wherein the first transparent substrate has a first surface and a second surface, the transparent conductive layer is provided on the first surface, the color filter is provided on the second surface, the transparent conductive layer contains tin oxide as a main component and at least one of niobium oxide, tantalum oxide, and antimony oxide as a subcomponent, the content of at least one of niobium oxide, tantalum oxide, and antimony oxide is 5 wt% or more and 15 wt% or less, and the sheet resistance is 1 x 107Omega/sq. or more and 1X 1010A high resistance state of not more than Ω/sq, in which the transparent conductive layer functions as an antistatic layer of the color filter;
a counter substrate having a second transparent substrate, and a sensor electrode and a liquid crystal driving electronic circuit provided on the second transparent substrate; and
and a liquid crystal provided between the substrate with the transparent conductive layer and the counter substrate, and driven and controlled by the liquid crystal driving electronic circuit.
6. The liquid crystal panel of claim 5,
the transmittance of the transparent conductive layer is 98.5% or more at a wavelength of 550 nm.
7. The liquid crystal panel of claim 5 or 6,
the thickness of the transparent conductive layer is 5nm to 15 nm.
8. The liquid crystal panel of claim 5 or 6,
the transparent conductive layer contains nitrogen.
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