Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
  • H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
  • H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
  • H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
  • H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
  • H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
  • H01L27/124—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition, shape or layout of the wiring layers specially adapted to the circuit arrangement, e.g. scanning lines in LCD pixel circuits
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/02104—Forming layers
  • H01L21/02365—Forming inorganic semiconducting materials on a substrate
  • H01L21/02518—Deposited layers
  • H01L21/02521—Materials
  • H01L21/02565—Oxide semiconducting materials not being Group 12/16 materials, e.g. ternary compounds
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
  • H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
  • H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
  • H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
  • H01L27/1222—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition, shape or crystalline structure of the active layer
  • H01L27/1225—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition, shape or crystalline structure of the active layer with semiconductor materials not belonging to the group IV of the periodic table, e.g. InGaZnO
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
  • H10K59/10—OLED displays
  • H10K59/12—Active-matrix OLED [AMOLED] displays
  • H10K59/123—Connection of the pixel electrodes to the thin film transistors [TFT]
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
  • H10K59/80—Constructional details
  • H10K59/805—Electrodes
  • H10K59/8051—Anodes

Definitions

• the first group of the present invention relates to a substrate provided with an A1 metal wiring and a transparent conductive film, and more particularly to a transparent conductive film laminated substrate having an A1 metal wiring of a thin film transistor, that is, a TFT substrate.
• the present invention also relates to a method for manufacturing the TFT substrate.
• a TFT substrate is known as one of typical examples of a transparent conductive film laminated substrate provided with A1 metal wiring.
• a so-called TFT thin film transistor
• ⁇ -SiTFT amorphous silicon thin-film transistor
• p-SiTFT polysilicon thin-film transistor
• TFT substrates are widely used.
• the present invention relates to the TFT substrate and a manufacturing method thereof.
• a TFT substrate is often called a TFT array substrate because a plurality of TFTs are generally provided on the substrate.
• the present invention relates to the contact resistance between the pixel electrode pattern and the A1 source / drain wiring, and the A1 gate wiring extracting portion, the A1 wiring of the A1 source ′ drain electrode extracting portion, and the transparent electrode.
• the present invention relates to a liquid crystal display device and a TFT substrate for organic EL, which can reduce the resistance even when in direct contact, and a manufacturing method thereof.
• the second group of the present invention relates to a substrate provided with A1 wiring and a transparent conductive film, that is, a transparent conductive film laminated substrate provided with A1 wiring, as described above. It also relates to this manufacturing method.
• the present invention relates to a substrate on which A1 and a transparent conductive film are laminated, and a method of manufacturing the same, in which excessive contact resistance does not occur even when A1 wiring metal and a transparent electrode are in direct contact.
• This multilayer substrate can be used as a substrate for a liquid crystal display device or an organic EL.
• the third group of the present invention relates to a laminated circuit board in which A1 wiring and a transparent conductive film are laminated so as to be directly connected, and a method for manufacturing the same. More specifically, Ni A transparent conductive film laminated circuit board in which the Al metal wiring contained and the transparent electrode are directly connected! /, which is used as a substrate for liquid crystal display devices and a substrate for organic EL.
• the present invention relates to a circuit board and a manufacturing method thereof. Such a laminated circuit board is laminated so that the A1 metal wiring and the transparent conductive film are directly connected.
• a fourth group of the present invention relates to a laminated circuit board in which A1 wiring and a transparent conductive film are laminated so as to be directly connected and a method for manufacturing the same, as described above. More specifically, a transparent conductive film laminated circuit board in which a metal wiring made of A1 or an A1 alloy and a transparent electrode are directly connected!
• the present invention relates to a transparent conductive film laminated circuit board used as a manufacturing substrate and a manufacturing method thereof. Such a laminated circuit board is laminated so that the A1 metal wiring and the transparent conductive film are directly connected.
• Liquid crystal display devices and organic EL display devices are promising among thin displays because they have features such as low power consumption and easy full colorization.
• development relating to the enlargement of the display screen of these devices has been active.
• an active matrix system in which at-SiTFT or p-SiTFT is arranged in a matrix as a switching element for each pixel to drive each pixel is widely used, and development is also active.
• An active matrix liquid crystal flat display using this method for a liquid crystal display device is attracting attention as a high-performance color display without degradation of the contrast ratio even when the resolution is increased to 800 x 600 pixels or higher. .
• a transparent electrode such as ITO (Indium Tin Oxide) is used as a pixel electrode, and an A1 alloy thin film is used as a source electrode of a transistor (FET).
• FET transistor
• FIG. 1 is a cross-sectional view showing a state in the middle of producing a transparent conductive film laminated substrate provided with A1 metal wiring.
• FIG. 1 itself is a diagram of the present invention as well as a diagram of the prior art.
• FIG. 1 shows a cross section in the vicinity of an ex-Si TFT at the stage where pixel electrode pattern formation is completed in the manufacturing process of a liquid crystal flat display. Since the basic structure of a conventional liquid crystal display is the same except for the material of the pixel electrode, the conventional technology will be described with reference to FIG.
• a gate electrode pattern 2 is formed on a translucent glass substrate 1, and then a SiN gate insulating film 3, an a-Si: H (i) film 4 are formed by plasma CVD. Then, the channel protective film 5 and the ⁇ -Si: H (n) film 6 are continuously formed and patterned into a desired shape. Further, a metal film mainly composed of A1 is deposited by vacuum deposition or sputtering, and a source electrode 7 having a predetermined pattern and a drain electrode 8 having a predetermined pattern are formed by a photolithography technique, and the a-Si TFT element portion is formed. Complete. On top of this, an ITO film is deposited by sputtering, and a pixel electrode pattern 9 electrically connected to the source electrode 7 is formed by photolithography.
• the reason for depositing the ITO film after the A1 film is to prevent deterioration of the electrical contact characteristics between the ⁇ -Si: H film and the source and drain electrodes.
• A1 is one of the excellent materials in the sense that it is inexpensive and has low specific resistance to prevent deterioration of the display performance of the liquid crystal display due to increased resistance of the gate and source / drain electrode wiring.
• the ITO pixel electrode pattern is covered with an HC1-HNO—HO-based etching solution.
• A1 is also an ITO etchant, HC1-HNO-H 2 O-based etchant.
• HNO in the etching solution is thinly formed on the surface of A1, forms an A1 oxide film, and is added to prevent elution of A1.
• the etching rate is the etching rate.
• Patent Document 2 In view of such a problem, for example, in Patent Document 2 below, patterning of the A1 gate, the transparent electrode and the pixel electrode on the source / drain electrode pattern is performed by etching using an oxalic acid-based etching solution. However, it is disclosed to facilitate patterning. In addition, in Patent Document 2, it is proposed to use a transparent electrode having a composition such as indium oxide monooxide and zinc oxide for the purpose of providing a method for producing a high-definition liquid crystal display. Yes.
• Liquid crystal display devices and organic EL display devices are promising among thin displays because they have features such as low power consumption and easy full colorization.
• development relating to the enlargement of the display screen of these devices has been active.
• an active matrix system in which at-SiTFT or p-SiTFT is arranged in a matrix as a switching element for each pixel to drive each pixel is widely used, and development is also active.
• An active matrix liquid crystal flat display using this method for a liquid crystal display device is attracting attention as a high-performance color display without degradation of the contrast ratio even when the resolution is increased to 800 x 600 pixels or higher. .
• a transparent electrode such as ITO (Indium Tin Oxide) is used as a pixel electrode, and an A1 alloy thin film is used as a source electrode of a transistor (FET).
• FET transistor
• FIG. 4 is a cross-sectional view showing a device in the middle of producing a transparent conductive film laminated circuit board provided with A1 metal wiring.
• FIG. 4 itself is a diagram of the present invention as well as a diagram of the prior art.
• FIG. 4 shows a cross section in the vicinity of the a-Si TFT at the stage where the pixel electrode pattern formation is completed in the manufacturing process of the liquid crystal flat display.
• Conventional LCD display Since the basic structure of the ray is the same except for the material of the pixel electrode, the conventional technology will be described with reference to FIG.
• a gate electrode pattern 1002 is formed on a translucent glass substrate 1001, and then a SiN gate insulating film 1003, an a-Si: H (i) film 1004 are formed using a plasma CVD method.
• the channel protective film 1005 and the a-Si: H (n) film 1006 are continuously formed and patterned into a desired shape.
• a metal film mainly composed of A1 is deposited by vacuum evaporation or sputtering, and a source electrode 1007 having a predetermined pattern and a drain electrode 1008 having a predetermined pattern are formed by photolithography, and the a-Si TFT element portion is formed.
• An ITO film is deposited thereon by a sputtering method, and a pixel electrode pattern 1009 electrically connected to the source electrode 1007 is formed by a photolithography technique.
• A1 is one of the excellent materials in the sense that it is inexpensive and has low specific resistance to prevent deterioration of the display performance of the liquid crystal display due to increased resistance of the gate and source / drain electrode wiring.
• the ITO pixel electrode pattern is covered with the HC1-HNO-HO etching solution.
• A1 is also an ITO etchant, HC1-HNO-H 2 O-based etchant.
• HNO in the etching solution is thinly formed on the surface of A1, forms an A1 oxide film, and is added to prevent elution of A1.
• the etching rate is an etching rate. That is, the etching rate ratio means a ratio of etching rates.
• Patent Document 2 an oxalic acid-based etching solution is used for patterning the transparent electrode and the pixel electrode on the A1 gate, the source / drain electrode pattern. It is disclosed to perform by etching and facilitate patterning. Further, in Patent Document 2, it is proposed to use a transparent electrode having a composition that also has indium zinc oxide and zinc oxide strength for the purpose of providing a method for producing a high-definition liquid crystal display.
• Patent Document 2 the contact resistance generated between the A1 gate line Z transparent electrode and the A1 source / drain electrode Z pixel electrode is not negligible. It is known to be. For this reason, a method of covering the A1 line with a barrier metal such as Ti, Cr, or Mo is usually adopted. Such a technique is described in Patent Document 3, Patent Document 4, Patent Document 5, and Patent Document 6.
• Patent Document 11 Such a problem is described in Patent Document 11 below.
• Al-NiAlloy One 1. 31V
• IZO can be expected to suppress the battery reaction in which the electromotive force is smaller than that of ITO, but this IZO generates an electromotive force of at least -0.74V. It is difficult to completely suppress the battery reaction. In order to completely suppress the battery reaction, it is necessary to suppress the electromotive force between these A1Z transparent electrodes to less than -0.5V.
• the transparent electrode means IZO or ITO.
• Patent Document 1 Japanese Patent Laid-Open No. 63-184726
• Patent Document 2 Japanese Patent Laid-Open No. 11-264995
• Patent Document 3 Japanese Patent Laid-Open No. 10-65174
• Patent Document 4 Japanese Patent Laid-Open No. 11-184195
• Patent Document 5 Japanese Patent Laid-Open No. 11-258625
• Patent Document 6 Japanese Patent Laid-Open No. 11-253976
• Patent Document 7 JP-A-7-45555
• Patent Document 8 JP-A-7-301705
• Patent Document 9 JP-A-1-289140
• Patent Document 10 Japanese Patent Application Laid-Open No. 2003-017706 (Japanese Patent Application No. 2001-200710)
• Patent Document 11 Japanese Patent Application Laid-Open No. 2004-214606
• Patent Document 12 JP-A-60-068508
• Patent Document 13 Japanese Patent Laid-Open No. 08-171824
• Patent Document 14 Japanese Patent Application Laid-Open No. 09-035535
• the inventors of the present invention have made Zn SnO into a sputtering target having a specific composition, particularly zinc oxide, under such a background.
• the taper angle of the electrode obtained in this way was 30 degrees and the force was 89 degrees, and it was found that a good taper angle was obtained. Furthermore, during TMAH used in the etching process, even when A1 and the transparent conductive film of the present invention are electrically connected, no battery reaction occurs, and disconnection due to melting or corrosion of A1 wiring does not occur. I saw and started.
• the first group of the present invention has been made in view of the above-described problems of the conventional technology.
• a transparent conductive material containing a specific metal for a pixel electrode and a transparent electrode By using a transparent conductive material containing a specific metal for a pixel electrode and a transparent electrode, a TFT can be obtained. (Thin film transistor)
• An object of the present invention is to simplify the method of manufacturing a substrate.
• Another object of the present invention of the first group is to generate a large contact resistance between the A1 gate, the Z transparent electrode, the A1 source 'drain, and the pixel electrode without direct contact between them. (Material / composition).
• another object of the present invention of the first group is to provide a metal oxide transparent conductive film capable of suppressing a battery reaction caused by various chemical solutions, and by using this, a liquid crystal display device, To provide TFT substrates and TFT array substrates that can be used in organic EL display devices.
• the second group of the present invention has been made in view of the above-mentioned problems of the conventional technology, and it is possible to use a transparent conductive material containing a specific metal for the transparent conductive film.
• An object of the present invention is to simplify the manufacturing method of a substrate in which A1 wiring and a transparent conductive film are laminated.
• another object of the present invention of the second group is a configuration in which a large contact resistance is not generated between the A1 wiring and the transparent conductive film without any barrier metal (material 'set). ).
• another object of the present invention of the second group is to provide a metal oxide transparent conductive film capable of suppressing battery reactions caused by various chemical solutions, and to provide A1 wiring by using this metal oxide transparent conductive film.
• Another object of the present invention is to provide a production method capable of efficiently producing a transparent conductive film laminated substrate.
• the conventional transparent conductive film laminated substrate provided with the A1 wiring has the following problems.
• the battery reaction between the wiring 1 and the transparent conductive film may cause the A1 wiring to be thinned or disconnected during etching or the like.
• the present invention has been made to solve such problems, and the object thereof is as follows. It is as follows.
• the inventors of the present invention propose a transparent electrode material capable of reducing the electromotive force generated between A1 and the transparent electrode under such a background. For the purpose.
• the third group of the present invention uses a transparent conductive material made of an oxide mainly composed of a specific indium oxide-zinc oxide-oxide tin for a pixel electrode or a transparent electrode. Therefore, it aims at simplifying the manufacturing method of a TFT substrate.
• the main component means a main component, and generally means that the component is 50 percent or more by weight or volume, or by the number ratio of atoms.
• the fact that indium oxide-zinc oxide tin monoxide is the main component means that the sum of these composition ratios is approximately 50% or more.
• the third group of the present invention is a transparent electrode that can suppress the value of the contact resistance between the A1 gate Z transparent electrode and the A1 source / drain Z pixel electrode even smaller than the conventional one.
• 'It is also an object to provide a material for a pixel electrode.
• Another object of the third group of the present invention is to provide a metal oxide transparent conductive film (material) capable of sufficiently suppressing a battery reaction even in a TMAH aqueous solution.
• Another object of the present invention of the third group is to provide a TFT substrate (thin film transistor substrate) using the metal oxide transparent conductive film as a transparent electrode pixel electrode.
• This TFT substrate can be used as a substrate for driving liquid crystal in a liquid crystal display device.
• This TFT substrate is a kind of substrate called a metal wiring 'transparent conductive film laminated circuit substrate'.
• this TFT substrate can also be used for an EL display device.
• the TFT substrate (thin film transistor substrate) using the metal oxide transparent conductive film as a transparent electrode / pixel electrode can be manufactured at a low cost by simplifying the manufacturing method and suppressing the manufacturing cost. It is an object of the present invention.
• the inventors of the present invention have developed a transparent electrode material that can reduce the electromotive force generated between A1 and the transparent electrode under such a background. Developed earnestly. That is, one of the objects of the fourth group of the present invention is such a transparent material. Is to propose.
• the fourth group of the present invention is based on the use of a transparent conductive material made of an oxide mainly composed of specific zinc oxide tin monoxide for a pixel electrode or a transparent electrode. Therefore, it aims at simplifying the manufacturing method of a TFT substrate.
• the main component means a main component, and generally means that the component is 50% or more by weight or volume, or by the number ratio of atoms.
• zinc oxide-tin oxide is the main component means that the total of these composition ratios is generally 50% or more.
• the fourth group of the present invention is a transparent electrode in which the value of the contact resistance between the A1 gate Z transparent electrode and the A1 source / drain Z pixel electrode can be kept smaller than the conventional one even if they are in direct contact with each other.
• 'It is also an object to provide a material for a pixel electrode.
• Another object of the fourth group of the present invention is to provide a metal oxide transparent conductive film (material) capable of sufficiently suppressing a battery reaction even in a TMAH aqueous solution.
• Another object of the fourth group of the present invention is to provide a TFT substrate (thin film transistor substrate) using the metal oxide transparent conductive film as a transparent electrode and a pixel electrode.
• This TFT substrate can be used as a substrate for driving liquid crystal in a liquid crystal display device.
• This TFT substrate is a kind of substrate called a metal wiring 'transparent conductive film laminated circuit substrate'.
• the metal wiring is A1 wiring, it is also called a transparent conductive film laminated circuit board provided with A1 wiring.
• this TFT substrate can be used for a liquid crystal display device and an organic EL display device.
• the TFT substrate thin film transistor substrate
• the manufacturing method can be simplified and the manufacturing cost can be reduced.
• the purpose of the fourth group of the present invention is to provide devices and organic EL display devices at low cost.
• a transparent conductive material containing a specific metal is used for the pixel electrode and the transparent electrode, whereby the TFT substrate manufacturing method can be simplified.
• a TFT substrate or a TFT array substrate is used for a display device, a display device (for example, a liquid crystal display device) capable of halftone display can be provided.
• the method for manufacturing the transparent conductive film laminated substrate provided with the A1 wiring can be simplified.
• the transparent conductive film laminated substrate provided with the A1 wiring of the present invention is used in, for example, a display device, a display device capable of halftone display (for example,
• a liquid crystal display device can be provided.
• a transparent conductive material mainly composed of indium zinc oxide monoxide and tin oxide having a specific composition is used for the pixel electrode or the transparent electrode.
• the method can be simplified.
• another object of the present invention is to provide a pixel electrode material that can keep the contact resistance between the A1 source and drain and the pixel electrode in a direct contact with each other even when it is in direct contact.
• an electrode constituting a pixel by driving a liquid crystal or the like is called a pixel electrode.
• the power is merely a difference in location, and the pixel electrode and the transparent electrode are substantially the same.
• the battery reaction can be sufficiently suppressed even in the TMAH aqueous solution, so that the battery reaction in the manufacturing process can be suppressed. .
• the manufacturing process can be simplified, so that the TFT substrate can be manufactured at low cost.
• a liquid crystal display device and an organic EL display device can be provided at low cost.
• Another object of the present invention is to provide a TFT substrate (thin film transistor substrate) using the metal oxide transparent conductive film as a transparent electrode / pixel electrode.
• This TFT substrate can be used as a substrate for driving liquid crystal in a liquid crystal display device.
• This TFT substrate is a kind of substrate called a metal wiring 'transparent conductive film laminated circuit substrate'.
• this TFT substrate can also be used for an organic EL display device. Furthermore, the TFT substrate (thin film transistor substrate) using the metal oxide transparent conductive film as a transparent electrode 'pixel electrode can be provided at a low cost by simplifying the manufacturing method and suppressing the manufacturing cost. Is the purpose.
• the transparent conductive material mainly composed of zinc oxide tin monoxide having a specific composition is used for the pixel electrode or the transparent electrode, the manufacturing method of the TFT substrate is simplified. You can do it.
• the present invention it is possible to provide a material for a transparent electrode that can keep the value of the contact resistance between the A1 gate and the transparent electrode smaller than before even when the A1 gate and the transparent electrode are in direct contact with each other.
• a pixel electrode material that can keep the contact resistance between the A1 source 'drain and the pixel electrode in direct contact with each other even when the A1 source' drain is directly in contact with the pixel electrode.
• an electrode constituting a pixel by driving a liquid crystal or the like is called a pixel electrode.
• the power is merely a difference in location, and the pixel electrode and the transparent electrode are substantially the same.
• the battery reaction can be sufficiently suppressed even in the TMAH aqueous solution, so that the battery reaction in the manufacturing process can be suppressed. .
• the manufacturing process can be simplified, and the TFT substrate can be manufactured at low cost.
• a liquid crystal display device and an organic EL display device can be provided at low cost.
• the present invention can provide a TFT substrate (thin film transistor substrate) using the metal oxide transparent conductive film as a transparent electrode / pixel electrode.
• This TFT substrate can be used as a substrate for driving liquid crystal in a liquid crystal display device.
• This TFT substrate is a kind of substrate called a metal wiring 'transparent conductive film laminated circuit substrate'.
• the manufacturing method is simplified, the manufacturing cost is suppressed, and the liquid crystal is inexpensively manufactured.
• Display devices and organic EL display devices can be provided. Means for solving the problem
• the object of the first group of the present invention is to use, as the pixel electrode, a transparent conductive film made of an amorphous conductive oxide mainly composed of zinc oxide and tin oxide. This is achieved by patterning with an etching solution that is an aqueous solution of oxalic acid or a mixed acid of nitric acid 'phosphoric acid' and acetic acid. That is, the present invention is as follows.
• the present invention relates to a TFT substrate used in a display device, the transparent substrate, and a pixel that is provided on the transparent substrate and controls a pixel of the display device And a thin film transistor that is provided on the transparent substrate and drives the pixel electrode.
• the thin film transistor includes at least an A1 gate electrode, a gate insulating film, a first semiconductor layer, and a second semiconductor layer.
• the pixel electrode is directly bonded to the A1 gate electrode and Z or the A1 source 'drain electrode, and the pixel electrode is mainly composed of zinc oxide.
• a TFT substrate characterized by comprising a conductive oxide.
• the present invention is characterized in that the pixel electrode further includes tin oxide and is made of a conductive oxide mainly composed of zinc oxide ′ oxide tin ( 1 1) TFT substrate.
• the main component is a main component! If the content is approximately 50% or more, it can be said to be the main component.
• zinc oxide and tin oxide are the main components means that the total ratio of the metals contained is approximately 50% or more in terms of volume ratio, mass ratio, and number of atoms.
• the atomic ratio is approximately 50% or more, preferably 70% or more, and more preferable. Or more than 85% is called “main component”.
• acid zinc is used as the main component in the above-mentioned (1-1), and acid zinc and tin oxide are used as the main components in (1-2).
• other ingredients may be included.
• other components include magnesium oxide, gallium oxide, aluminum oxide, and the like.
• the A1 gate line and the A1 source / drain electrode mean A1 itself, an A1 alloy containing A1 as a main component, and the like. In the case of the A1 alloy, other metals may be appropriately contained in addition to A1. Other metals include heavy metals or lanthanoid metals from Ilia to Villa in the periodic table.
• Nd, Ni, Co, Zr and the like are preferably used.
• the content is preferably 0.1 to less than 5% by weight depending on the required performance of the A1 gate line and A1 source / drain electrode. More preferably, it is 0.5 to 2.0% by weight. If the content is less than 0.1% by weight, the addition effect is almost complete. A projection such as hillocks may be formed on the A1 thin film. On the other hand, if the content exceeds 5 weight percent, the resistance value of A1 (A1 alloy) may increase.
• a plurality of TFTs are generally provided on a substrate.
• the TFT array substrate corresponds to an example of the TFT substrate of the present invention.
• the composition ratio [211] 7 ([211] + [311]) of zinc in the oxide mainly composed of zinc oxide and tin oxide is 0.5.
• the TFT substrate according to (2) characterized by ⁇ 0.85.
• [Zn] represents the number of zinc atoms
• [Sn] represents the number of tin atoms.
• [Zn] represents the unit mass of zinc atoms and the number of atoms per unit volume
• [Sn] represents the unit mass of zinc atoms and the number of atoms per unit volume
• the present invention is characterized in that a taper angle of an end portion of the pixel electrode made of the oxide mainly composed of zinc oxide and tin oxide is 30 to 89 degrees.
• This is the TFT substrate described in (1-2) or (1-3).
• the taper angle is less than 30 degrees, the distance between the electrode edge portions becomes long, and when the liquid crystal or organic EL is driven using the substrate of the present invention, the contrast between the pixel peripheral portion and the inside of the pixel is increased. It can be very different. Also, if the taper angle exceeds 89 degrees, there is a risk of electrode cracking or peeling at the electrode edge. In particular, when driving a liquid crystal, the alignment film may be defective, and in the case of an organic EL, the counter electrode may be broken.
• the present invention provides a method for producing a TFT substrate according to any one of the above (1-2)-(14), wherein a transparent conductive film mainly composed of zinc oxide and tin oxide is patterned.
• a TFT substrate can be simply manufactured by a simple method.
• ([Zn] Z ([Zn] + [Sn]) 0 is more than 0.6 and less than 0.8, more preferably this value is more than 0.7 and less than 0.75.
• the transparent conductive film mainly composed of zinc oxide and tin oxide is an amorphous film.
• the film is not an amorphous film, it is difficult to control the taper, and it is very difficult to keep the taper angle within the range of 30 to 89 degrees.
• the taper angle is less than 30 degrees, the distance between the electrode edge portions becomes long, and when the liquid crystal or organic EL is driven using the substrate of the present invention, the contrast between the pixel peripheral portion and the inside of the pixel is increased. It can be very different. Also, if the taper angle exceeds 89 degrees, there is a risk of electrode cracking or peeling at the electrode edge. In particular, when driving a liquid crystal, the alignment film may be defective, and in the case of an organic EL, the counter electrode may be broken.
• oxalic acid is preferably used as the etching solution. If the oxalic acid concentration is less than lwt%, the etching rate is slow, which is not practical. If it exceeds 10wt%, oxalate crystals may precipitate.
• the oxalic acid concentration is preferably 2 wt% to 7 wt%, more preferably 2 wt% to 5 wt%. If an acid other than oxalic acid is used, the electromotive force in the solution increases and may cause a battery reaction with A1.
• the etching temperature is preferably 20 to 50 ° C. Below 20 ° C, the etching rate is slow and impractical. Above 50 ° C, the concentration of the oxalic acid aqueous solution may fluctuate due to water evaporation. Preferably, the etching temperature is 25 ° C to 45 ° C, more preferably 30 ° C to 45 ° C.
• the mobility of the transparent electrode is preferably 10 cm 2 ZV 'SEC or more. More preferably, it is 20cm 2 ZV'SEC or more.
• a third metal can be added within a range that does not affect the mobility.
• the third metal is called “third metal” in the sense of the third metal after zinc and tin. In short, this term is used to mean “other metal”. .
• a metal oxide having a low refractive index for the purpose of improving the transmittance.
• metal oxides used for such applications include MgO, B 2 O, Ga 2 O, and GeO.
• a metal oxide having a small specific resistance can be added.
• Representative examples of metal oxides used for such purposes include rhenium oxide, iridium oxide, ruthenium oxide, and the like.
• these heavy metal oxides may be colored, so care must be taken in the amount added, and it is also important to add them within a range that does not affect the transmittance.
• an evaporation method, a sputtering method, a CVD method, a spray method, a dipping method, or the like is preferably used, and among these, a sputtering method is preferably used.
• the present invention provides the transparent conductive material mainly composed of zinc oxide and tin oxide.
• a development process in which an aqueous solution of 1 to 5 wt% of tetramethylammonium hydroxide is used as a resist developer, and an aqueous solution having an oxalic acid concentration of 1 wt% to 10 wt% as an etchant is used.
• Sani zinc composition ratio in ⁇ [Zn] Z ([Zn] + [Sn]) is a TFT substrate manufacturing method of which is a 0.5 to 0.85.
• [Zn] represents the number of zinc atoms
• [Sn] represents the number of tin atoms.
• the first group of the present invention (11) includes (1) a development process and a peeling process. It is the one that has been attached.
• TMAH tetramethyl ammonium hydroxide
• concentration of TMAH is preferably 1-5 wt%. If it is less than lwt%, resist development failure may occur and wiring may be short-circuited. If the concentration exceeds 5 wt%, the resist pattern may be thinned or peeled off, and the electrode pattern may be thinned or disconnected. More preferably, a concentration of 2 to 4 wt% is suitable.
• a solution containing ethanolamine is used as the stripper.
• a diethanolamine aqueous solution 40 wt% is used as the stripping solution.
• the object of the second group of the present invention is to apply a transparent conductive film made of an amorphous conductive oxide mainly composed of zinc oxide and tin oxide on a transparent substrate provided with A1 wiring. This is achieved. Furthermore, the feature of the present invention is that the transparent conductive film is directly bonded to the A1 wiring without using a metal or the like.
• the production method of the present invention is characterized in that the transparent conductive film is etched and patterned with an etching solution which is an aqueous oxalic acid solution.
• the present invention comprises a transparent substrate, an A1 wiring provided on the transparent substrate, and a conductive oxide mainly composed of zinc oxide. And a transparent conductive film directly bonded to the transparent conductive film multilayer substrate provided with A1 wiring.
• the transparent conductive film further contains tin oxide, zinc oxide
• a transparent conductive film laminated substrate provided with A1 wiring according to (2-1) characterized by containing tin oxide as a main component.
• contact resistance with a magnitude that cannot be ignored was generated between the A1 wiring and the conventional transparent conductive film.
• the value of contact resistance can be made lower than before.
• the main component means a main component, and can be said to be a main component if the content is approximately 50% or more.
• that zinc oxide and tin oxide are the main components means that the total ratio of the metals contained is approximately 50% or more in terms of volume ratio, mass ratio, and number of atoms.
• a case where the ratio of the number of atoms is approximately 50% or more, preferably 70% or more, more preferably 85% or more is referred to as “main component”.
• acid zinc is used as the main component in the above (2-1), and acid zinc and tin oxide are used as the main components in (2-2) and the like.
• other ingredients may be included. Examples of other components include magnesium oxide, gallium oxide, aluminum oxide, and the like.
• Nd, Ni, Co, Zr and the like are preferably used.
• the content is preferably 0.1 to less than 5% by weight depending on the required performance of the A1 wiring. More preferably, it is 0.5 to 2.0% by weight. If the content is less than 0.1% by weight, the effect of addition is almost negligible. A protrusion such as hillock may occur on the A1 wiring (A1 thin film). On the other hand, if the content exceeds 5% by weight, the resistance value of A1 (A1 alloy) may increase.
• the A1 wiring is often provided on the substrate in the form of a thin film, but any wiring may be used without being limited to the thin film.
• the composition ratio [211] 7 ([211] + [311]) of zinc in the oxide mainly composed of zinc oxide ′ tin oxide is 0.5. It is a transparent conductive film laminated substrate provided with A1 wiring as described in said (2-2) characterized by being -0.85.
• [Zn] is the zinc atom
• [Sn] represents the number of tin atoms.
• the organic EL layer tends to be thin in the case of the organic EL electrode.
• a short circuit is likely to occur between the electrode made of the transparent conductive film and the opposing electrode, which may cause a display defect.
• [Zn] represents the unit mass of zinc atoms and the number of atoms per unit volume
• [Sn] represents the unit mass of zinc atoms and the number of atoms per unit volume
• the present invention is characterized in that a taper angle of an end portion of the transparent conductive film made of an oxide mainly composed of zinc oxide and tin oxide is 30 to 89 degrees.
• the taper angle is less than 30 degrees, the distance of the transparent conductive film edge portion becomes long.
• the contrast between the pixel periphery and the inside of the pixel may differ greatly.
• the taper angle exceeds 89 degrees, there is a risk of electrode cracking or peeling at the edge of the transparent conductive film.
• the alignment film may be defective, and when the organic EL is driven, the counter electrode may be disconnected.
• the present invention provides an A1 arrangement according to any one of the above (2-2)-(2-4).
• a pattern is formed so that a transparent conductive film mainly composed of zinc oxide and tin oxide is patterned so that the taper angle of its end is 30 to 89 degrees.
• a patterning step wherein the patterning step uses an aqueous solution having a concentration of oxalic acid of 1 wt% to 10 wt% as an etchant, and the temperature of the etchant is set in a range of 20 to 50 ° C.
• An etching step of etching the transparent conductive film, wherein the composition ratio [Zn] / ([Zn] + [Sn]) of zinc in the oxide mainly composed of zinc oxide and tin oxide is 0.5 to A method for producing a transparent conductive film laminate substrate provided with A1 wiring, characterized by being 0.8.
• [Zn] represents the number of zinc atoms
• [Sn] represents the number of tin atoms.
• the A1 wiring transparent conductive film laminated substrate can be simply manufactured by a simple method.
• [Zn] Z ([Zn] + [Sn]) is more than 0.6 and less than 0.8, and more preferably this value is more than 0.7 and less than 0.75.
• the transparent conductive film mainly composed of zinc oxide and tin oxide is an amorphous film.
• the film is not an amorphous film, it is difficult to control the taper, and it is very difficult to keep the taper angle within the range of 30 to 89 degrees.
• the taper angle When the taper angle is smaller than 30 degrees, the distance between the electrode edge portions becomes long, and when the liquid crystal or organic EL is driven using the substrate of the second group of the present invention, the pixel peripheral portion and the inside of the pixel The contrast may vary greatly. Also, if the taper angle exceeds 89 degrees, there is a risk of electrode cracking or peeling at the electrode edge. In particular, when driving a liquid crystal, the alignment film may be defective. In the case of organic EL, the counter electrode is broken. It may cause.
• oxalic acid is used as the etching solution. If the oxalic acid concentration is less than 1 wt%, the etching rate is slow, which is not practical, and if it exceeds 10 wt%, there is a problem that oxalate crystals may precipitate.
• the oxalic acid concentration is preferably 2 wt% to 7 wt%, more preferably 2 wt% to 5 wt%. If an acid other than oxalic acid is used, the electromotive force in the solution increases and may cause a battery reaction with A1.
• the etching temperature is preferably 20 to 50 ° C. This is because if the temperature is lower than 20 ° C, the etching rate is slow and impractical. If the temperature exceeds 50 ° C, the concentration of the oxalic acid aqueous solution may fluctuate due to evaporation of water.
• the etching temperature is 25 ° C to 45 ° C, more preferably 30 ° C to 45 ° C.
• the mobility of the transparent conductive film is preferably 10 cm 2 ZV 'SEC or more. More preferably, it is 20cm 2 ZV ⁇ SEC or more.
• a third metal can be added as long as the mobility is not affected.
• the third metal is called “third metal” in the sense of the third metal after zinc and tin. In short, this term is used to mean “other metal”. .
• metal oxide having a small refractive index for the purpose of improving the transmittance.
• metal oxides used for such applications include MgO, B 2 O, Ga 2 O, and GeO.
• a metal oxide having a small specific resistance can be added.
• Representative examples of metal oxides used for such purposes include rhenium oxide, iridium oxide, ruthenium oxide, and the like.
• these heavy metal oxides may be colored, so care must be taken in the amount added, and it is also important to add them within a range that does not affect the transmittance.
• a method for forming the transparent conductive layer As a method for forming the transparent conductive layer, a vapor deposition method, a sputtering method, a CVD method, a spray method, a deposition method, and the like. A sputtering method or the like is preferably used, and among these, a sputtering method is preferably used.
• the present invention provides a zinc oxide ′ tin oxide.
• a patterning step of patterning the transparent conductive film comprising as a main component and forming a taper angle of 30 to 89 degrees at an end thereof, wherein the patterning step includes the transparent conductive film.
• the resist applied on the film is developed using a 1 to 5 wt% aqueous solution of tetramethyl ammonium hydroxide as a resist developer, and the concentration of oxalic acid is 1 wt% to 10 wt as an etchant.
• a composition step [Zn] Z ([Zn] + [Sn]) of zinc in the oxide mainly composed of zinc oxide and tin oxide is 0.5 to 0.85.
• [Zn] represents the number of zinc atoms
• [Sn] represents the number of tin atoms.
• the present invention (2-6) is obtained by adding a development step and a peeling step to (2-5).
• TMAH Tetramethylammonium hydroxide
• the concentration of TMAH is preferably 1-5 wt%. If it is less than lwt%, resist development failure may occur and wiring may be short-circuited. If the concentration exceeds 5 wt%, the resist pattern may be thinned or peeled off, and the electrode pattern may be thinned or disconnected. More preferably, a concentration of 2 to 4 wt% is suitable.
• a solution containing ethanolamine is used as the stripping solution.
• a diethanolamine aqueous solution 40 wt% is used as the stripping solution.
• the object of the third group of the present invention is to use indium zinc oxide as a pixel electrode. This is achieved by using a transparent conductive film made of an amorphous conductive oxide mainly composed of tin monoxide.
• the above-described object is achieved by patterning by suppressing the electromotive force in TMAH of the transparent conductive film to less than 0.81 V and performing etching using an aqueous oxalic acid solution as an etching solution. .
• the present invention employs the following means.
• the present invention provides a transparent substrate, a wiring provided on the transparent substrate, an A1 wiring made of A1 or an A1 alloy cover, and an indium oxide-acid.
• a transparent conductive film laminated circuit board provided with A1 wiring comprising a transparent conductive film made of a conductive oxide mainly composed of zinc tin oxide and directly bonded to the A1 wiring .
• the contact resistance can be made lower than before even when directly bonded to the A1 wiring. Further, according to the transparent conductive film having such a composition, the battery reaction with the A1 wiring can be effectively suppressed.
• the A1 wiring is a wiring made of A1 or an A1 alloy cable, and is particularly preferably an A1 alloy (including a metal other than A1).
• the content of metals other than A1 in the A1 wiring is preferably in the range of 0.05 wt% to 10 wt%. If it is less than 0.05 wt%, the effect of addition is small, and the value of the contact resistance with the transparent conductive film may increase. In addition, the battery reaction may appear. On the other hand, if it exceeds 10 wt%, the resistance value of the A1 wiring itself becomes large, and there is a risk of problems such as signal delay when used in liquid crystal display devices and organic EL devices.
• the content of metals other than A1 is more preferably in the range of 0.1 wt% to 5 wt%, and still more preferably in the range of 1 to 3 wt%. This metal other than A1 is called “second metal” here.
• Ni is particularly preferable as the metal (second metal) other than A1. Other metals may be used.
• the third metal a heavy metal or a lanthanoid metal of Ilia to Villa in the periodic table may be included.
• the third metal means the third metal following Al, which is the first metal, and the second metal mentioned above other than A1. In short, it means “other metal”.
• the third metal Nd, Co, Zr or the like is preferably used.
• the content should be in the range of 0.01 to 5 wt%, which depends on the required A1 wiring performance. More preferably 0.5-3. If the content is less than 0.01 wt%, the effect of addition is almost negligible. Protrusions such as hillocks may occur on the A1 wiring. On the other hand, if the content exceeds 5 wt%, the resistance value of the A1 wiring may increase.
• the predetermined indium oxide zinc monoxide tin oxide having the specific composition of the third group of the present invention (3-1) is naturally at least three kinds of substances, indium oxide. It is very important to contain all of zinc oxide and tin oxide. If any one of the components is missing, the electromotive force in the TMAH increases during manufacturing, and it may be difficult to sufficiently suppress the battery reaction with the A1 wiring.
• composition of the oxide mainly composed of indium oxide zinc monoxide and tin monoxide is
• [In] represents the number of indium atoms
• [Zn] represents the number of zinc atoms
• [Sn] represents the number of tin atoms.
• the object of the present invention can be sufficiently achieved. Specifically, if the value is outside this range, the resistance value of the transparent conductive film itself may be unacceptably large, and the value of the electromotive force in the TMAH becomes large during manufacturing. In some cases, it may be difficult to sufficiently suppress the battery reaction with the wiring.
• [In] / ([In] + [Zn] + [ The value of Sn]) is 0.05 to 0.95. If this value is less than 0.05, the resistance value of the transparent conductive film may increase or the stability of the transparent electrode composed of the transparent conductive film may be lost. On the other hand, when this value exceeds 0.95, the transparent conductive film is crystallized, and etching may be difficult with an oxalic acid-based etchant. In general, if etching cannot be performed with an oxalic acid-based etchant, aqua regia or hydrochloric acid 'iron-based etchant must be used. In this case, the a1 wiring is corroded by aqua regia or hydrochloric acid. These aqua regia and hydrochloric acid cannot be used.
• the numerical range of the ratio of the composition of indium is preferably 0.1 to 0.9. More preferably, it is 0.3 to 0.9, and even more preferably 0.5 to 0.9.
• the value of [Zn] / ([ln] + [Zn] + [Sn]) is 0.05 to 0.8. If this value is less than 0.05, etching with a oxalic acid-based etchant is difficult when crystallizing when the transparent conductive film is heated or when crystallizing when the substrate is heated. There will be, etc.
• the numerical range of the composition ratio of zinc is preferably 0.1 to 0.75. More preferably, it is 0.1 to 0.7.
• the value of [Sn] / ([ln] + [Zn] + [Sn]) is 0.01-0.3. If this value is less than 0.01, the effect of reducing the electromotive force of the transparent conductive film is reduced. As a result, the electromotive force may not be sufficiently small. On the other hand, when this value exceeds 0.3, etching with oxalic acid may be difficult, or the etching rate with oxalic acid may decrease.
• composition ratio of tin is preferably 0.02-0.2. More preferably, it is 0.02 to 0.15.
• [Zn] Z [Sn] which is the ratio of the number of atoms of zinc and tin, is usually 0.1 to 10, preferably It is preferably 0.2 to 5, more preferably 0.3 to 3, and particularly preferably 0.5 to 2. If the ratio of the number of atoms is outside these ranges, the stability in TMAH may be deteriorated.
• the transparent conductive film is amorphous. If it becomes crystalline, there is a possibility that a defective product whose etching characteristics do not become the desired characteristics may be generated.
• the mobility of the transparent conductive film is preferably 10 cm 2 ZV 'SEC or more. More preferably, it is 20cm 2 ZV ⁇ SEC or more.
• the fourth metal can be added within a range that does not affect the mobility.
• the fourth metal is called “fourth metal” in the sense of the fourth metal following indium, zinc and tin, and this word is used in the meaning of "other metals"
• metal oxide having a small refractive index for the purpose of improving the transmittance.
• metal oxides used for such applications include MgO, B 2 O, Ga 2 O, and GeO.
• a metal oxide having a small specific resistance can be added for the purpose of lowering the specific resistance.
• metal oxides used for such purposes include rhenium oxide, iridium oxide, ruthenium oxide, and the like.
• these heavy metal oxides may be colored, so care must be taken in the amount to be added, and it should be fully considered that they are added within a range that does not affect the transmittance.
• the present invention also relates to a conductive oxide mainly composed of indium zinc oxide and tin monoxide at 30 ° C of tetramethylammonium hydroxide (TMAH) 2
• TMAH tetramethylammonium hydroxide
• TMAH tetramethylammonium hydroxide
• the A1 alloy includes one or more metals selected from the group consisting of Ni, W, Mo, Nb, Zr, and Nd, and the content thereof is 0.1-: A transparent conductive film laminated circuit board provided with the A1 wiring according to any one of the above (3-1) to (3-3), characterized in that it is LOwt%.
• the difference in electromotive force between the A1 wiring containing one or more metals selected from the group consisting of Ni, W, Mo, Nb, Zr, and Nd and the conductive oxide is 0. It is very important for the present invention that the voltage is 5 V or less.
• the difference in electromotive force is basically determined by the content of other metals in the A1 wiring containing one or more metals selected from the group consisting of Ni, W, Mo, Nb, Zr, and Nd. It depends on the composition of the conductive oxide.
• the conductive oxide can reduce the difference in electromotive force to 0.5 V or less. It has been clarified by experiments of the present inventors that the range of yarn formation is widened.
• the present invention relates to the oxide transparent conductive film material used for the laminated circuit board according to (3-1) and the like, and the indium oxide-zinc oxide-tin oxide is a main component.
• Oxide composition is
• the oxide transparent conductive film material is characterized.
• [In] represents the number of indium atoms
• [Zn] represents the number of zinc atoms
• [Sn] represents the number of tin atoms.
• the present invention is an invention having the scope of the invention as a conductive oxide material which is a constituent element of the invention of the above (3-2). Its features are basically the same as (3-2) above.
• the present invention relates to the oxide transparent conductive film material used for the laminated circuit board described in (3-1) or the like, wherein the indium oxide-zinc oxide-tin oxide is used.
• the main component of the oxide is that the electromotive force of the tetramethylammonium hydroxide oxide (TMAH) at 30 ° C based on the AgZAgCl standard electrode in 2.4% aqueous solution is 0.6V or less. It is an oxide transparent conductive film material.
• the present invention is an invention having the scope of the invention as a material of a conductive oxide which is a constituent element of the above invention (3-3). Its features are basically the same as (3-3) above.
• the present invention relates to a method for producing a transparent conductive film laminated circuit board provided with the A1 wiring according to any one of (3-1) to (3-4) above, wherein indium oxide-zinc oxide —Pattern that forms a predetermined electrode by patterning the transparent conductive film mainly composed of oxidized oxide.
• a patterning step wherein the patterning step includes developing a resist coated on the transparent conductive film using a tetramethylammonium hydroxide aqueous solution as a resist developer, and an etching solution.
• the composition of the acid oxide mainly composed of indium oxide-zinc oxide-tin oxide is:
• the method for producing a transparent conductive film laminated circuit board provided with Al wiring is characterized in that the Al wiring is made of an Al alloy cable containing Ni.
• [In] represents the number of indium atoms
• [Zn] represents the number of zinc atoms
• [Sn] represents the number of tin atoms.
• the ratio of the number of zinc and tin atoms on the surface of the transparent conductive film (connection portion with the conductor) [Zn] Z [S ⁇ ] ⁇ preferably ⁇ .
• it is in the range of 0.005 to 2, and particularly preferably in the range of 0.01 to 0.95.
• [Zn] / [Sn] value ⁇ ) From 01 / J, etching may become unstable. On the other hand, when this value is greater than 5, zinc reacts with atmospheric oxygen or moisture, which may increase the resistance of the connection.
• the transparent conductive film laminated substrate of (3-1)-(3-4) can be efficiently produced.
• the concentration of TMAH in the TMAH aqueous solution used as the resist developer is preferably 0.5 to 8 wt%. A more preferred range is 1 to 5 wt%.
• TMAH concentration of TMAH
• concentration of TMAH is less than 0.5 wt%
• the concentration of TMAH is more than 8 wt%
• the developing ability is too high and it may be difficult to control. Developing ability is too high If control becomes impossible, problems such as pattern shift and pattern peeling may occur.
• An oxalic acid aqueous solution is used as the etching solution.
• the concentration should be appropriately selected from 0.5 wt% to 10 wt%. However, it is preferable to select a force ranging from lwt% to 5wt%. If the concentration of oxalic acid is less than 0.5 wt%, the etching rate may be slow, or the life of the etching solution may be shortened. On the other hand, when the concentration of oxalic acid exceeds 10 wt%, indium oxalate zinc oxalate and tin oxalate may precipitate based on the solubility of the aqueous solution. As a result, there is a risk of causing etching defects. In addition, when indium oxalate or the like is deposited on the substrate, it is a “foreign matter”, which causes a decrease in yield when manufacturing liquid crystal panels and organic EL panels.
• the temperature of the etching solution is set to 20 ° C to 50 ° C.
• the temperature is lower than 20 ° C, it is necessary to cool the etching solution to a temperature lower than 20 ° C, which is not practical.
• a special heating device may be required, which eventually causes a problem in practice.
• the temperature exceeds 50 ° C., it is necessary to manage the concentration of the solution accompanying the evaporation of water, so that the management work tends to be complicated.
• a more preferable temperature range is 25 ° C to 45 ° C.
• the present invention provides an edge of the transparent conductive film made of an acid oxide mainly composed of indium oxide-zinc tin monoxide.
• (3-7) The method for producing a transparent conductive film laminated circuit board provided with A1 wiring according to (3-7), wherein the patterning is performed so that the taper angle of the portion is 35 to 89 degrees.
• the taper angle is less than 35 degrees, the distance between the edges of the transparent conductive film will be longer.
• the contrast between the pixel periphery and the inside of the pixel may differ greatly.
• the taper angle exceeds 89 degrees, there is a risk of electrode cracking or peeling at the edge of the transparent conductive film.
• the alignment film may be defective, and when the organic EL is driven, the counter electrode may be disconnected.
• the taper angle is preferably 40 to 80 degrees force S, and more preferably 45 to 70 degrees.
• the thickness of the transparent conductive film is usually 10 to 300 nm, preferably 20 to 150 nm, and particularly preferably 30 to 110 nm. If it is thinner than lOnm, there may be a problem in uniformity and the resistance may increase. On the other hand, if it is thicker than 300 nm, the taper angle may not be within the desired range, and etching residues may remain.
• a method for forming the transparent conductive film various conventionally known methods can be employed. For example, a vapor deposition method, a sputtering method, a CVD method, a spray method, or a dipping method is suitably used. Among these, the sputtering method is particularly preferably used.
• the object of the fourth group of the present invention is achieved by using a transparent conductive film made of an amorphous conductive oxide containing zinc oxide tin monoxide as a main component as a pixel electrode.
• the above-described object is achieved by patterning by suppressing the electromotive force in TMAH of the transparent conductive film to less than 0.6 V, and performing etching using an aqueous oxalic acid solution as an etching solution. .
• the present invention employs the following means.
• the present invention is an oxide mainly composed of zinc oxide-tin oxide, which is tetramethylammonium hydroxide (TMAH) at 30 ° C 2.
• TMAH tetramethylammonium hydroxide
• An amorphous oxide transparent conductive film material having an electromotive force of 0.6 V or less based on an AgZAgCl standard electrode in a 4% aqueous solution.
• a transparent conductive film prepared using a transparent conductive film material having such a composition is directly connected to the A1 wiring. Even if it joins, a contact resistance can be made into a value lower than before. Moreover, according to the transparent conductive film having such a composition, the battery reaction with the A1 wiring can be effectively suppressed.
• (4-1) of the present invention is based on the AgZAgCl standard electrode of a transparent conductive film material in tetramethylammonium hydroxide (TMAH) 2.4% aqueous solution at 30 ° C. It is very important that the generated electromotive force is 0.6V or less.
• TMAH tetramethylammonium hydroxide
• the electromotive force of the conductive oxide is within the range of “standard electromotive force of A1 wiring + 0.7 V” or less, even if a battery reaction occurs, the speed of the battery reaction slows down.
• the experimental ability of the inventors of the present application is that the battery reaction can be suppressed in a sufficiently practical sense as long as it is within the range of the lower value of “standard electromotive force of A1 wiring +0.5 V”. found
• [Zn] Z ([Zn] + [Sn]) representing the composition of the acid oxide is in the range of 0.5 to 0.9.
• [Zn] represents the number of zinc atoms
• [Sn] represents the number of tin atoms.
• composition of the acid oxide is in such a numerical range, the object of the present invention can be sufficiently achieved.
• the battery reaction can be suppressed.
• the electrode may be dissolved during the subsequent etching process, causing electrode thinning or wire breakage.
• the resistance value of the transparent conductive film itself may increase, or the transparent conductive film may crystallize instead of being amorphous.
• the [0241] when [Zn] / ([Zn] + [Sn]) is outside the range of 0.5 to 0.9, there is a possibility of electrode thinning or wire breakage. In addition, so-called undercuts may occur at the edge of the transparent electrode, which may be a problem.
• the value of this formula is ⁇ , preferably ⁇ to 0.67 to 0.8, more preferably ⁇ to 0.7 to 0.8.
• the transparent conductive film is amorphous. If it becomes crystalline, defects may occur due to etching characteristics.
• [Zn] represents the unit mass of zinc atoms, the number of atoms per unit volume, and [Sn]
• the mobility of the transparent conductive film is preferably 10 cm 2 ZV 'sec or more. More preferably, it is 20 cm 2 ZV ⁇ sec or more.
• a third metal can be added within a range that does not affect the mobility.
• the third metal is called “third metal” in the sense of the third metal after zinc and tin, and this term is used simply to mean “other metal”.
• a metal oxide having a low refractive index for the purpose of improving the transmittance.
• metal oxides used for such applications include MgO, B 2 O, Ga 2 O, and GeO.
• a metal oxide having a small specific resistance can be added.
• Representative examples of metal oxides used for such purposes include rhenium oxide, iridium oxide, ruthenium oxide, and the like.
• these heavy metal oxides may be colored, so care must be taken in the amount added, and it should be fully considered that they are added within a range that does not affect the transmittance.
• the present invention relates to a transparent substrate, a wiring provided on the transparent substrate, an A1 wiring made of A1 or A1 alloy, and a conductive material mainly composed of zinc oxide tin oxide. Oxide And a transparent conductive film directly bonded to the A1 wiring, and a transparent conductive film laminated circuit board provided with the A1 wiring.
• the contact resistance can be made lower than before even if it is directly bonded to the A1 wiring. Further, according to the transparent conductive film having such a composition, the battery reaction with the A1 wiring can be effectively suppressed.
• an A1 alloy when used as the A1 wiring, it can contain one or more metals selected from the group consisting of Ni, W, Mo, Nb, Zr and Nd.
• the content of one or more metals selected from the group consisting of Ni, W, Mo, Nb, Zr and Nd in the A1 alloy is preferably in the range of 0.05 wt% to 10 wt%. If it is less than 0.05 wt%, the effect of addition is small, and the value of the contact resistance with the transparent conductive film may increase. In addition, the battery reaction may appear.
• the content of these additive metals is more preferably in the range of 0.1 wt% to 5 wt%, and still more preferably in the range of 1 to 3 wt%.
• the metal wiring side third metal may include heavy metals or lanthanoid metals from Ilia to Villa of the periodic table.
• the third metal on the metal wiring side means the third metal. That is, A1 is the first metal.
• the second metal is one or more metals selected from the group consisting of Ni, W, Mo, Nb, Zr, and Nd. In the sense of the third metal other than these, the term “third metal on the metal wiring side” is used. In short, it means “other metal”.
• the heavy metal or lanthanoid metal of Ilia to Villa in the periodic rate table described above for example, Au, Ag, Zn, Cu, Sr, Sm and the like are preferably used.
• the content should be in the range of 0.01 to 5 wt%, which depends on the required A1 wiring performance. More preferably 0.5-3. When the content is less than 0.01 wt%, the effect of addition is almost negligible. A protrusion such as hillock may occur on the A1 wiring. On the other hand, if the content exceeds 5 wt%, the resistance value of the A1 wiring may increase.
• zinc oxide tin monoxide having a specific composition of the fourth group of the present invention (4-3) is Of course, it is very important to contain at least these two substances, zinc oxide and tin oxide. If any one of the components is missing, the electromotive force in the TMAH increases during manufacturing, and it may be difficult to sufficiently suppress the battery reaction with the A1 wiring.
• the present invention provides a conductive oxide mainly composed of zinc oxide tin monoxide, tetramethylammonium hydroxide (TMAH) 2.4% aqueous solution at 30 ° C.
• TMAH tetramethylammonium hydroxide
• the composition of the conductive oxide containing zinc oxide tin monoxide as a main component is [Zn] Z ([Zn] + [Sn] W O. 5-0 9.
• the object of the present invention can be sufficiently achieved. This is because if the value of the above formula is less than 0.5, the effect of suppressing the cell reaction in TMAH may not be sufficiently exerted, or etching with an aqueous oxalic acid solution may be difficult.
• the present invention is characterized in that the A1 alloy contains one or more metals selected from the group consisting of Ni, W, Mo, Nb, Zr and Nd.
• the present invention comprises Ni, W, Mo, Nb, Zr and Nd in the A1 alloy.
• Group power The layered substrate of a transparent conductive film having an A1 wiring according to (4-6), characterized in that the content power of one or more metals selected is 0.05 to 10 wt%.
• the difference in electromotive force between the A1 wiring made of A1 or A1 alloy cable and the conductive oxide is 0.5 V or less. Is very important.
• the difference in electromotive force basically depends on the content of metals such as Ni, W, Mo, Nb, Zr and Nd in the A1 wiring made of A1 or A1 alloy cable, and the conductive oxide. It depends on the composition. In the end, in order to suppress battery reactions that are problematic in practice, it is necessary to reduce the “difference” in the electromotive force of each substance in order to realize the purpose.
• the content of one or more metals selected from the group consisting of Ni, W, Mo, Nb, Zr and Nd is 0.05% to 1 ( ⁇ % range makes it easy to suppress the difference in electromotive force to 0.5 V or less by the inventors' experiments. That is, according to the present invention (4-7) Therefore, it becomes easier to set the difference in electromotive force to ⁇ 0.5V or less.
• the present invention provides a method for producing a transparent conductive film laminated circuit board provided with the A1 wiring according to any one of (43) to (47), wherein zinc oxide tin monoxide is a main component.
• Development process to develop using as a developer, and concentration of oxalic acid as an etchant is lwt% ⁇ 10wt.
• the composition of the oxide is in the range of [Zn] Z ([Zn] + [Sn] W O. 5 to 0.9
• the A1 wiring is composed of A1 alloy power including Ni.
• the concentration of TMAH in the TMAH aqueous solution used as the resist developer is preferably 0.5 to 8 wt%. A more preferred range is 1 to 5 wt%.
• TMAH concentration of TMAH
• the concentration of TMAH is less than 0.5 wt%, the developing ability may be deteriorated, or the life of the developer may be shortened.
• the concentration of TMAH is more than 8 wt%, the developing ability is too high and it may be difficult to control. If the development capability is too high and control becomes impossible, problems such as pattern misalignment and pattern peeling may occur.
• An oxalic acid aqueous solution is used as the etching solution.
• the concentration should be appropriately selected from 0.5 wt% to 10 wt%. However, it is preferable to select a force ranging from lwt% to 5wt%. If the concentration of oxalic acid is less than 0.5 wt%, the etching rate may be slow, or the life of the etching solution may be shortened. On the other hand, when the concentration of oxalic acid exceeds 10 wt%, zinc oxalate or tin oxalate may precipitate based on the solubility of the aqueous solution. As a result, there is a risk of causing etching failure. In addition, when the zinc oxalate or the like is deposited on the substrate, it is a “foreign matter”, which causes a decrease in yield when manufacturing a liquid crystal panel or an organic EL panel.
• the temperature of the etching solution is set to 20 ° C to 50 ° C.
• the temperature is lower than 20 ° C, it is necessary to cool the etching solution to a temperature lower than 20 ° C, which is not practical.
• a special heating device may be required, which eventually causes a problem in practice.
• the temperature exceeds 50 degrees, it is necessary to manage the solution concentration as the water evaporates. The gap tends to be complicated.
• a more preferable temperature range is 25 ° C to 45 ° C.
• the taper angle of the end portion of the transparent conductive film having an acidic strength mainly composed of the zinc oxide monoxide soot is 35.
• the taper angle is smaller than 35 degrees, the distance of the transparent conductive film edge portion becomes long.
• the contrast between the pixel periphery and the inside of the pixel may differ greatly.
• the taper angle exceeds 89 degrees, there is a risk of electrode cracking or peeling at the edge of the transparent conductive film.
• the alignment film may be defective, and when the organic EL is driven, the counter electrode may be disconnected.
• a method for forming the transparent conductive film various conventionally known methods can be employed. For example, a vapor deposition method, a sputtering method, a CVD method, a spray method, or a dipping method is suitably used. Among these, the sputtering method is particularly preferably used.
• FIG. 1 is a cross-sectional view centering on an ex Si TFT portion for explaining a liquid crystal display device according to the present embodiment.
• FIG. 2 is a perspective view showing a state in which a laminated film is formed on a slide glass.
• FIG. 3 is a process diagram showing a state in which a laminated substrate in which an amorphous transparent conductive film and an A driving wire according to the present embodiment are directly bonded is manufactured.
• FIG. 4 is a cross-sectional view centering on an oc Si TFT portion for explaining the liquid crystal display device according to the present embodiment.
• FIG. 5 is a process diagram showing a state of manufacturing a laminated circuit board in which an amorphous transparent conductive film and a Ni-containing A1 wiring according to the present embodiment are directly bonded.
• FIG. 6 is an explanatory diagram showing a state in which the contact resistance between an A1 thin film and a transparent conductive film is measured using the Kelvin probe method. Explanation of symbols
• sputtering targets having various configurations were prepared, and the characteristics and the characteristics of the transparent conductive film produced using the sputtering targets were examined.
• the mixing time was 20 hours.
• the obtained mixed slurry was taken out, filtered, dried and granulated.
• the obtained granulated product was molded by a cold isostatic press while applying a pressure of 294 MPa (3 tZcm 2 ).
• the compact was sintered as follows. First, sintering was performed in a sintering furnace at 1500 ° C. for 5 hours in an atmosphere in which oxygen was introduced at a rate of 5 LZmin per 0.1 lm 3 of the furnace volume. At this time, the temperature was raised to 1 000 ° C by l ° CZmin and from 1000 to 1500 ° C by 3 ° CZmin. After that, oxygen introduction was stopped, and the temperature was decreased from 1500 ° C to 1300 ° C at 10 ° C Zmin. Then, in an atmosphere in which argon gas was introduced at a rate of lOLZmin per 0.1 lm 3 of the furnace volume, the temperature was kept at 1300 ° C. for 3 hours and then allowed to cool. As a result, a sintered body containing zinc oxide / tin oxide having a relative density of 90% or more was obtained.
• the surface of the sintered compact target a obtained as described above is set as the sputter surface.
• the sputtering target was constructed by polishing to a diameter of 100 mm and processing to a thickness of 5 mm and bonding a backing plate using an indium alloy. At this time, the density of the sputtering target was 5.72 gZcm 3 .
• the tin oxide is dispersed, in particular, it is substituted and dissolved in the zinc site of the zinc oxide. That is, the form in which the tin is contained in the target is SnO or SnO.
• Any tin oxide may be dispersed in the acid-zinc sintered body, but ZnSnO,
• the average diameter of the crystal grains determined by mapping image processing of Sn atoms in EPMA was 3.87 m.
• tin atoms are dispersed and dissolved in zinc sites of acid zinc, so that tin is dispersed at the atomic level in the zinc oxide sintered body.
• This is effective for stable discharge and low resistance of the transparent conductive thin film.
• the Balta resistance of the target is 360 ⁇ cm, and stable sputtering is expected.
• the obtained sputtering target was mounted on a sputtering apparatus, and the substrate temperature was set to 200 ° C at a final vacuum of 5 X 10 _4 Pa and a deposition pressure of 0.1 lPa. went .
• the results are shown in Tables 1 and 2.
• Table 1 is a table showing the properties of the used sputtering
• Table 2 is a table showing the physical measurement results of the transparent conductive film obtained.
• the specific resistance and mobility of the transparent conductive thin film obtained as a result of sputtering are It was determined by measurement.
• the transmittance was measured with a self-recording spectrophotometer.
• Table 2 also shows the etching rate when the concentration of the aqueous solution of oxalic acid is changed.
• the taper angle of the obtained pattern was determined by SEM (Scanning Electron Microscope) observation. The results are shown in Table 3.
• Example 1-1 the value of the specific resistance of the transparent conductive film (transparent electrode) could be reduced. Furthermore, since the light transmittance is higher than the conventional value, it is considered that a brighter display device can be realized.
• the etching rate with 3.5 wt% oxalic acid aqueous solution is 105, OOOA / min (30 ° C), 220, 000A / min (40 ° C), 180, OOOA / min (35 ° C) And good etsu Ching characteristics were observed (Table 3).
• the taper angle became 86 degrees (Table 3). Since it is not an extremely small or large value, it is considered that a transparent electrode having excellent durability can be formed.
• TCP connection was performed using ACF (Anisotoropic Conductive Film), 60 ° C, 90% RH (relative humidity). : Relative Humidity) and observed changes in connection resistance. The results are shown in Table 4.
• the TCP connection resistance immediately after connection is 4.2 ⁇ , 5.6 ⁇ after 240 hours, and 6.2 ⁇ after 480 hours, 96 hours After that, it became 6.5 ⁇ .
• the degree of increase in contact resistance over time is very small, and even when used in a display device, performance degradation due to increased resistance is considered to be very small. In other words, if a substrate using the transparent conductive film of Example 11 is used, a display device with high durability can be configured.
• Example 1 2 Example 1 3
• Example 14 Example 1 5 ''
• Zinc oxide powder having an average particle size of 1 ⁇ m or less and tin oxide powder having an average particle size of 1 ⁇ m or less were used as raw material powders.
• Zinc oxide powder and tin oxide powder were blended in a predetermined ratio and made into a resin pot, and mixed by a wet ball mill. At that time, use hard ZrO balls and mix
• the time was 20 hours.
• the mixed slurry was taken out, filtered, dried and granulated.
• the granulated product was filled into a circular mold and formed into a disk shape by applying a pressure of 3 ton Zcm 2 using a cold isostatic press.
• the compact was placed in an atmosphere adjustment furnace and sintered.
• sintering sintering was performed at 1500 ° C. for 5 hours while introducing oxygen into the furnace at a rate of 5 liters Z per 0.1 lm 3 of the furnace volume.
• the temperature was increased from 1000 ° C to 1 ° CZ and from 1000 ° C to 1500 ° C at a rate of 3 ° CZ.
• the introduction of oxygen was stopped and the temperature was decreased from 1500 ° C to 1300 ° C at a rate of 10 ° C / min.
• Example 1-2 is an example using the sintered compact target b
• Example 1-3 is an example using a sintered body target c
• Example 1-4 is an example using a sintered body target d
• Example 1-5 is an example using a sintered body target e. It is the Example using.
• Each sputtering target was obtained by processing to 152 mm and a thickness of 5 mm.
• the tin oxide is dispersed, and in particular, it is substituted and dissolved in the zinc site of zinc oxide. That is, the form in which the tin is contained in the target is SnO or SnO.
• Any tin oxide may be dispersed in the acid-zinc sintered body, but ZnSnO,
• Table 1 shows the average diameter of crystal grains obtained by mapping image processing of Sn atoms in EPMA! RU
• tin atoms disperse in the zinc site of the acid-zinc solution so that tin is dispersed at the atomic level in the acid-zinc sintered body.
• the discharge is stable, and it is effective for making the obtained transparent conductive thin film have a low resistance.
• the Balta resistance of the target is all less than 500 ⁇ cm, enabling stable sputtering. This measurement is also shown in Table 1.
• TCP connection was performed using ACF (Anisotoropic Conductive Film), and the connection was made at 60 ° C, 9 ° C.
• the value of) is 0.75.
• the target density was 5.86 gZcm 3 and the average particle size was 3.82 ⁇ m.
• the specific resistance was 350 ⁇ cm (Table 1).
• the specific resistance of the transparent conductive film formed using this sputtering target b was 0.04 Q cm, and the mobility was 45 cm 2 ZV 'sec.
• the light transmittance was 86.3% (wavelength 550 nm) (Table 2).
• the specific resistance value is sufficiently low, and the transparency is also used for the display device. A sufficient value was shown.
• the etching rate with 3.5 wt% oxalic acid aqueous solution was 65, OOOA / min (30 ° C), 1 32, 000AZmin (40 ° C), 96, OOOAZmin (35 ° C) Characteristics were observed (Table 3).
• the taper angle was 75 degrees (Table 3). Since extremely small values are not large values, it is considered that transparent electrodes with excellent durability can be formed.
• Example 13 the value of [Zn] / ([Zn] + [Sn]) is 0.70.
• the target density is 5.83 gZcm 3 and the average particle size is 3.
• the specific resistance of the transparent conductive film formed using this sputtering target c was 0.009 Q cm, and the mobility was 48 cm 2 ZV 'sec.
• the light transmittance was 86.5% (wavelength 550 nm) (Table 2).
• the etching rate with a 3.5 wt% oxalic acid aqueous solution was 500 AZmin (30 ° C), 1,100 AZmin (40 ° C), and 950AZmin (35 ° C), and good etching characteristics were observed ( Table 3).
• the taper angle was 48 degrees (Table 3). Since extremely small V ⁇ values are not large values, it is thought that transparent electrodes with excellent durability can be formed.
• Example 14 the value of [Zn] / ([Zn] + [Sn]) is 0.67.
• the target density was 5.92 gZcm 3 and the average particle size was 3.5 ⁇ m.
• the specific resistance was 420 ⁇ cm (Table 1).
• the specific resistance of the transparent conductive film formed using this sputtering target d was 0.006 Q cm, and the mobility was 46 cm 2 ZV 'sec.
• the light transmittance was 86.3% (wavelength 550 nm) (Table 2).
• the etching rate with a 3.5 wt% oxalic acid aqueous solution was 30 AZmin (30 ° C), 7 lA / min (40 ° C), and 55 AZmin (35 ° C). 3) As a result of etching, the taper angle was 42 degrees (Table 3). Since it is not an extremely small value or a large value, it is considered that a transparent electrode having excellent durability can be formed.
• a display device with high durability can be configured by using the substrate using the transparent conductive film of Example 1-4.
• Example 15 As shown in these tables, the value of [Zn] / ([Zn] + [Sn]) is 0.55.
• the target density was 6. lOgZcm 3 and the average particle size was not measurable.
• the specific resistance was 480 ⁇ cm (Table 1).
• the specific resistance of the transparent conductive film formed using this sputtering target d is 0.03 Q cm.
• the mobility was 35 cm 2 ZV 'sec.
• the light transmittance was 85.9% (wavelength 550 nm) (Table 2).
• the etching rate with a 3.5 wt% oxalic acid aqueous solution was 10AZmin (30 ° C), 25A / min (40 ° C), and 22AZmin (35 ° C), and good etching characteristics were observed (Table 1). 3) As a result of etching, the taper angle was 38 degrees (Table 3). Since it is not an extremely small value or a large value, it is considered that a transparent electrode having excellent durability can be formed.
• the transparent conductive film in Examples 1-1 to 1-5 as described above can reduce the contact resistance with A1 as compared with the conventional one, so that it can drive liquid crystals and the like. Excellent.
• a display device that can display halftones satisfactorily can be configured.
• Comparative Examples 1-1 and 1-2 Examples different from the compositions of Examples 11 to 15 are given as Comparative Examples 1-1 and 1-2.
• the results of Comparative Examples 1-1 and 12 are also shown in Table 1, Table 2, Table 3, and Table 4.
• Comparative Example 11 is a case where the value of the composition ratio [211] 7 ([211] + [311]) of the number of zinc atoms is 0.97.
• the measured values of Comparative Example 1-1 are as shown in Tables 1 to 4.
• the specific resistance of the target has a low value of 280 ⁇ cm, and the specific resistance of the transparent conductive film formed was 0.86 ⁇ cm, which is one of the above Examples 1-1 to 1-5. Is also high.
• the mobility is as low as 15 cm 2 ZV 'sec, and the light transmittance is as low as 79.8% (wavelength: 550 nm).
• the performance when used in a display device is as described above.
• Example 1 1 to 1 5 It is considered inferior to.
• the etching rate with a 3.5 wt% oxalic acid aqueous solution was a force that showed a high value in Examples 11 to 15.
• the taper angle became 134 degrees, and the obtained transparent electrode There is a risk of wire thinning or disconnection.
• Comparative Example 12 is a case where the value of the composition ratio [211] 7 ([211] + [311]) of the number of zinc atoms is 0.40.
• the measured values of Comparative Example 1-2 are as shown in Tables 1 to 4.
• the specific resistance of the target was 4400 ⁇ cm
• the specific resistance of the formed transparent conductive film was 0.08 ⁇ cm.
• the mobility is as low as 8 cm 2 ZV 'sec, and the light transmittance is as low as 79.8% (wavelength: 550 nm). It is considered inferior to 1 1 to 15.
• the seven glass slides with seals will now be sputtered using different targets. Specifically, sputtering was performed using the targets of Examples 11 to 15 and the targets of Comparative Examples 1-1 to 1-2. As a result, seven types of transparent conductive films 34 were laminated on the A1 thin film 32.
• This sputtering is performed so that the transparent conductive film 34 has a thickness of lOOnm. Went.
• the temperature was room temperature.
• ITO was laminated in the same manner as a reference example.
• Example 1-1 is referred to as Example 1
• Examples 12 to 15 are referred to as Examples 2 to 5
• Comparative Examples 1-1 and 1 are referred to as Comparative Examples 1 and 2.
• the substrate on which only pure A1 was formed was immersed in a 20 ° C TMAH2.4 wt% aqueous solution, and the dissolution of the A1 film was observed. However, the dissolution of A1 was not confirmed. In this way, since the A1 single film does not dissolve, the A1ZITO laminated film, which is the laminated structure of the “A1Z transparent conductive film”, confirms that the dissolution of A1 is confirmed in the A1ZITO laminated film. Is equivalent to confirming that a battery reaction has occurred! /.
• the A1 thin film will not be dissolved during etching by TMAH. It will be understood that the multilayer circuit board can be manufactured smoothly.
• Example TMAH (2.4 wt%): into 20 ° C aqueous solution
• AI thin film / ITO thin film multilayer substrate AI layer is completely dissolved
• the glass substrate with a thin film having a thickness of lOOnm obtained in Example 1-1 described above was used as a target for investigating the resistance.
• aqueous solution obtained by adding 10 vol% of water to a 30 vol% diethanolamine and 70 vol% DMSO (dimethylsulfoxide) as a resist stripper was used.
• the glass substrate with a thin film prepared in Example 11 described above was immersed in an aqueous solution of the above release agent at 45 ° C for 5 minutes. Then, the surface SEM of the glass substrate with the thin film after immersion was observed to observe unevenness and roughness of the surface, but no unevenness and roughness were observed.
• the line width is 50 m, and Measured contact resistance at the laminated interface (Kelvin probe method)
• a thin layer of A1 wiring and a thin layer of a transparent conductive film are laminated on a predetermined substrate so as to be orthogonal (in a cross shape), and the contact resistance between them is measured by the Kelvin probe method. Both line widths are 50 m.
• the transparent conductive film includes the transparent conductive film used in Examples 11 to 15 described above, and the transparent conductive film used in Comparative Examples 1-1 to 1-2 described above. Was used.
• measurements were also made on an example using conventional ITO as a transparent conductive film. In this way, contact resistance was measured by making eight types of transparent conductive films perpendicular to the A1 thin film (thin wires). The measurement results are shown in Table 6.
• Example 1-1 is As Example 1, 3 ⁇ 4 Example ⁇ 2 to ⁇ 5 are 3 ⁇ 4 Example 2 to, and ⁇ ⁇ and ⁇ 2 are proportional ⁇ , 2 and ⁇ .
• the insect contact resistance is 0.4 ⁇ , 0.6 ⁇ , and 0.5. 7 ⁇ , 1.2 ⁇ . 1. 5 ⁇ , both showing low resistance of less than 2 ⁇ .
• the force was 0.4 ⁇ .
• the value was as high as 12 ⁇ .
• the example using cocoon as the transparent conductive film showed a high contact resistance of 140 ⁇ .
• Example 1-9 of the first group of the present invention the state of manufacturing a TFT substrate according to the present invention will be described with reference to FIG.
• metal A1 (99% Al, l% Nd) is deposited on a light-transmitting glass substrate 1 to a thickness of 1500 angstroms by high frequency sputtering. This is formed into a gate electrode 2 and a gate electrode wiring having desired shapes by a photoetching method using a phosphoric acid-acetic acid-nitric acid aqueous solution as an etching solution.
• the glass substrate 1 corresponds to a preferred example of the transparent substrate in the claims.
• a gate insulating film 3 to be a silicon nitride (SiN) film is deposited to a thickness of 3 000 angstroms by glow discharge CVD.
• a Si: H (i) film 4 is deposited to a thickness of 3500 angstroms, and a silicon nitride (SiN) film 5 serving as a channel protection layer is deposited to 3000 angstroms.
• SiN films 3 and 5 use SiN-NH-N mixed gas as the discharge gas.
• — Si: H (i) The film 4 uses a SiH—N-based mixed gas. This SiN film 5 is C A desired channel protective layer was formed by dry etching using HF gas. Next, ⁇ - Si: H (n) film 6 is formed in a 3000 ⁇ film thickness using SiH — H — PH mixed gas.
• a CrZAl bilayer film is deposited thereon by vacuum deposition or sputtering in the order of 0.1 ⁇ m Cr and 0.3 ⁇ m Al.
• A1 is H PO -CH COO
• Etching is performed using a photoetching method. As a result, the pattern of the desired source electrode 7 and the pattern of the drain electrode 8 are formed, and the source electrode 7 and the drain electrode 8 are formed.
• Cr is provided on the lower surface of the source electrode 7 and the drain electrode 8 and is not provided on the surface in contact with the amorphous transparent conductive film 9. That is, as will be described later, the A1 portion constituting the source electrode 7 and the drain electrode 8 is directly bonded to the amorphous transparent conductive film 9.
• ⁇ -Si the coating was dry-etched using CHF gas and hydrazine ( ⁇ NH ⁇
• the desired pattern ⁇ can be obtained by using wet etching with H 2 O) aqueous solution.
• a Si: H (n) 6 located below the source electrode 7 corresponds to a preferred example of the first semiconductor layer in the claims, and located below the drain electrode 8.
• an insulating film 10 to be a silicon nitride (SiN) film is deposited with a predetermined film thickness by a glow discharge CVD method. Then, contact holes are formed between the source and drain electrodes, the transparent electrode, and the pixel electrode by a dry etching method using CHF gas.
• SiN silicon nitride
• An amorphous transparent conductive film 9 mainly composed of zinc oxide and tin oxide obtained in Example 11 is formed on the substrate on which the pattern of the source electrode 7 and the drain electrode 8 having the metal A1 force is formed. Is deposited by sputtering. The amorphous transparent conductive film 9 is connected to the source electrode 7 and the like through a contact hole (see FIG. 1). [0359] The discharge gas used in the formation of the amorphous transparent conductive film 9 is formed by depositing the amorphous transparent conductive film 9 by a method using Ar gas mixed with pure argon or a small amount of O gas of about lvol%. 1200
• This amorphous transparent conductive film 9 is the transparent conductive film used in Examples 1-3 above.
• this amorphous transparent conductive film 9 was analyzed by X-ray diffraction, no peak was observed and it was confirmed that the amorphous transparent conductive film 9 was an amorphous film.
• the amorphous transparent conductive film 9 has a specific resistance of about 0.009 ⁇ 'cm, and can be used as a sufficient electrode.
• This amorphous transparent conductive film 9 was etched by photo etching using an aqueous solution of 3.5% by weight of oxalic acid as an etchant so as to obtain a desired electrode pattern.
• This electrode pattern is a “pixel electrode pattern” that is electrically connected to at least the pattern of the source electrode 7. At this time, the source electrode 7 and the drain electrode 8 made of A1 were not eluted by the etching solution.
• the electrode lead-out portions of the gate line 12 and the source / drain lines are also covered with a transparent electrode made of the same conductive film as the amorphous transparent conductive film 9 .
• a so-called TFT substrate can be manufactured by a simple manufacturing method.
• such a TFT substrate does not generate a large contact resistance between the transparent conductive film and the A driving wire.
• sputtering targets according to various configurations were created, and the characteristics and the characteristics of the transparent conductive film manufactured using the characteristics were inspected.
• the mixing time was 20 hours.
• the obtained mixed slurry was taken out, filtered, dried and granulated.
• the obtained granulated product was molded by a cold isostatic press while applying a pressure of 294 MPa (3 ton / cm 2 ).
• the compact was sintered as follows. First, sintering was performed in a sintering furnace at 1500 ° C. for 5 hours in an atmosphere in which oxygen was introduced at a rate of 5 LZmin per 0.1 lm 3 of the furnace volume. At this time, the temperature was raised to 1 000 ° C by l ° CZmin and from 1000 to 1500 ° C by 3 ° CZmin. After that, oxygen introduction was stopped, and the temperature was decreased from 1500 ° C to 1300 ° C at 10 ° C Zmin. Then, in an atmosphere in which argon gas was introduced at a rate of lOLZmin per 0.1 lm 3 of the furnace volume, the temperature was kept at 1300 ° C. for 3 hours and then allowed to cool. As a result, a zinc oxide / tin oxide-containing sintered body having a relative density of 90% or more was obtained.
• the surface to be sputtered of the sintered compact target a thus obtained is polished with a cup mortar, processed to a diameter of 100 mm and a thickness of 5 mm, and a backing plate is formed using an indium alloy.
• the sputtering target was configured by bonding. At this time, the density of the sputtering target was 5.72 gZcm 3 .
• tin oxide power is dispersed, in particular, it is substituted and dissolved in zinc sites of acid zinc. That is, the form in which the tin is contained in the target is in the form of tin oxide such as SnO and SnO, and the zinc oxide sintered body
• It may be in the form of a composite oxide in between and dispersed in the acid-zinc sintered body.
• the average diameter of the crystal grains determined by mapping image processing of Sn atoms in EPMA was 3.87 m.
• tin atoms are dispersed and dissolved in zinc sites of zinc oxide zinc, so that tin is dispersed at the atomic level in the zinc oxide sintered body.
• This is effective for stable discharge and low resistance of the transparent conductive thin film.
• the Balta resistance of the target is 360 ⁇ cm, and stable sputtering is expected.
• the obtained sputtering target was attached to an RF magnetron sputtering apparatus, and the substrate temperature was set to 200 ° C at an ultimate vacuum of 5 X 10 _4 Pa and a deposition pressure of 0.1 lPa. Membrane was performed.
• Tables 1 and 2 above Table 1 shows the spatter used.
• Table 2 shows the properties of tulling, and Table 2 shows the physical measurement results of the obtained transparent conductive film.
• Table 3 shows the etching rate when the concentration of oxalic acid in aqueous solution and the temperature were changed. Further, the taper angle of the obtained pattern was determined by observation with a scanning electron microscope (SEM). This result is also shown in Table 3.
• Example 2— ⁇ is considered as 3 ⁇ 4 Example
• Example 2-2 to Example 2-5 is considered as 3 ⁇ 4 Example 2-
• Example 2-1 the value of the specific resistance of the transparent conductive film (transparent electrode) could be reduced. Furthermore, since the light transmittance is higher than the conventional value, it is considered that a brighter display device can be realized.
• the etching rate with a 3.5 wt% oxalic acid aqueous solution is 105,000 A / min (30 ° C), 220, 000 A / min (40 ° C), 180, 000 A / min (35 ° C). Good etching characteristics were observed (Table 3). As a result of etching, the taper angle became 86 degrees (Table 3). Since it is not an extremely small or large value, it is considered that a transparent electrode having excellent durability can be formed.
• the TCP connection resistance immediately after connection is 4.2 ⁇ , 5.6 ⁇ after 240 hours, and 6.2 ⁇ after 480 hours, 96 hours After that, 6.5 ⁇ It was.
• the degree of increase in contact resistance over time is very small, and even when used in a display device, it is considered that the deterioration in performance due to the increase in resistance is very small.
• a display device with high durability can be configured.
• Example 2-2 to Example 2-5 Comparative Example 2-1 and Comparative Example 2-2, which are not limited to Example 2-1 alone.
• Example 2-1 is referred to as Example 1
• Examples 2-2 to Examples 2-5 are referred to as Examples 2 to 5 and Comparative Example 1.
• — 1 and Comparative Example 1 2 are listed as Comparative Examples 1 and 2
• Example 2-2 Example 2-3, Example 2-4, Example 2-5
• Zinc oxide powder having an average particle size of 1 ⁇ m or less and tin oxide powder having an average particle size of 1 ⁇ m or less were used as raw material powders.
• Zinc oxide powder and tin oxide powder were blended in a predetermined ratio and made into a resin pot, and mixed by a wet ball mill. At that time, use hard ZrO balls and mix
• the time was 20 hours.
• the mixed slurry was taken out, filtered, dried and granulated.
• the granulated product was filled into a circular mold and formed into a disk shape by applying a pressure of 3 ton Zcm 2 using a cold isostatic press.
• the compact was placed in an atmosphere adjustment furnace and sintered.
• sintering sintering was performed at 1500 ° C. for 5 hours while introducing oxygen into the furnace at a rate of 5 liters Z per 0.1 lm 3 of the furnace volume.
• the temperature was increased from 1000 ° C to 1 ° CZ and from 1000 ° C to 1500 ° C at a rate of 3 ° CZ.
• the introduction of oxygen was stopped and the temperature was decreased from 1500 ° C to 1300 ° C at a rate of 10 ° C / min.
• Example 2-2 is an example using a sintered compact target b
• Example 2-3 is an example using a sintered compact target c
• Example 2-4 is a sintered compact. This is an example using the target d
• Examples 2-5 are examples using the sintered compact target e.
• the surface to be sputtered of the obtained sintered body (targets b to e) was polished with a cup mortar to obtain a diameter.
• Each sputtering target was obtained by processing to 152 mm and a thickness of 5 mm.
• the tin oxide is dispersed, and in particular, it is substituted and dissolved in the zinc site of acid zinc. That is, the form in which the tin is contained in the target is SnO or SnO.
• Any tin oxide may be dispersed in the acid-zinc sintered body, but ZnSnO,
• the average diameter of crystal grains was determined by mapping image processing of Sn atoms in EPMA, and the results are shown in Table 1.
• tin atoms are dispersed and dissolved in zinc sites of acid zinc, so that tin is dispersed at the atomic level in the zinc oxide sintered body.
• This is effective for stable discharge and low resistance of the transparent conductive thin film.
• the Balta resistance of the target is all less than 500 ⁇ cm, enabling stable sputtering. This measurement is shown in Table 1.
• TCP connection was performed using ACF (Anisotoropic Conductive Film), and the connection was made at 60 ° C, 9 ° C.
• Example 2-2 as shown in these tables, [Zn] / ([Zn] + [Sn]
• the value of) is 0.75.
• the target density was 5.86 gZcm 3 and the average particle size was 3.82 ⁇ m.
• the specific resistance was 350 ⁇ cm (Table 1).
• the specific resistance of the transparent conductive film formed using this sputtering target b was 0.04 Q cm and the mobility was 45 cm 2 ZV 'sec.
• the light transmittance was 86.3% (wavelength 550 nm) (Table 2).
• the etching rate with 3.5 wt% oxalic acid aqueous solution is 65,000 A / min (30 ° C), 1
• the specific resistance of the transparent conductive film formed using this sputtering target c was 0.009 Q cm, and the mobility was 48 cm 2 ZV 'sec.
• the light transmittance was 86.5% (wavelength 550 nm) (Table 2).
• the etching rate with a 3.5 wt% oxalic acid aqueous solution was 500 AZmin (30 ° C), 1,100 AZmin (40 ° C), and 950AZmin (35 ° C), and good etching characteristics were observed ( Table 3).
• the taper angle was 48 degrees (Table 3). Since extremely small V ⁇ values are not large values, it is thought that transparent electrodes with excellent durability can be formed.
• the value of) is 0.67.
• the target density was 5.92 gZcm 3 and the average particle size was 3.5 ⁇ m.
• the specific resistance was 420 ⁇ cm (Table 1).
• the etching rate with a 3.5 wt% oxalic acid aqueous solution was 30AZmin (30 ° C), 7lA / min (40 ° C), 55AZmin (35 ° C), and good etching characteristics were observed (Table 1). 3) As a result of etching, the taper angle was 42 degrees (Table 3). Since it is not an extremely small value or a large value, it is considered that a transparent electrode having excellent durability can be formed.
• a display device with high durability can be configured by using the substrate using the transparent conductive film of Example 2-4.
• the specific resistance of the transparent conductive film formed using this sputtering target d was 0.03 Q cm, and the mobility was 35 cm 2 ZV 'sec.
• the light transmittance was 85.9% (wavelength 550 nm) (Table 2).
• the specific resistance value is sufficiently low, and the transparency is also used for the display device. A sufficient value was shown.
• the etching rate with 3.5 wt% oxalic acid aqueous solution was 10AZmin (30 ° C), 25A / min (40 ° C), 22AZmin (35 ° C), and good etching characteristics were observed (Table 3)
• the taper angle was 38 degrees (Table 3). Since it is not an extremely small value or a large value, it is considered that a transparent electrode having excellent durability can be formed.
• the transparent conductive film in Examples 2-1 to 2-5 as described above can reduce the contact resistance with A1, compared with the conventional case, it has the ability to drive liquid crystal and the like. Excellent. As a result, when it is used as a pixel electrode for driving liquid crystal or the like, a display device that can display halftones satisfactorily can be configured.
• Comparative Examples 2-1 and 2-2 Examples having different compositions from those of Examples 2-1 to 2-5 are given as Comparative Examples 2-1 and 2-2.
• the results of Comparative Examples 2-1 and 2-2 are also shown in Table 1, Table 2, Table 3, and Table 4.
• Comparative Example 2-1 is the case where the value of the composition ratio [211] 7 ([211] + [311]) of the number of zinc atoms is 0.97.
• the measured values of Comparative Example 2-1 are as shown in Tables 1 to 4.
• the specific resistance of the target has a low value of 280 ⁇ cm.
• the specific resistance of the formed transparent conductive film is 0.86 ⁇ cm, which is one of the above Examples 2-1 to 2-5. Is also high.
• the mobility is as low as 15 cm 2 ZV 'sec, and the light transmittance is as low as 79.8% (wavelength: 550 nm).
• the performance when used in a display device is as described above. It is considered inferior to Examples 2-1 to 2-5.
• the etching rate with a 3.5 wt% oxalic acid aqueous solution was a force that showed a high value in Examples 2-1 to 2-5.
• the taper angle was 134 degrees, and was obtained.
• transparent electrode There is a risk of wire thinning or disconnection.
• Comparative Example 2-2 is a case where the value of the composition ratio [211] 7 ([211] + [311]) of the number of zinc atoms is 0.40.
• the measured values of Comparative Example 2-2 are as shown in Tables 1 to 4.
• the specific resistance of the target was 4400 ⁇ cm
• the specific resistance of the formed transparent conductive film was 0.08 ⁇ cm.
• the mobility is as low as 8 cm 2 ZV 'sec, and the light transmittance is as low as 79.8% (wavelength: 550 nm). 2; Considered inferior to L-2-5.
• FIG. 3 is an explanatory diagram showing an outline of the manufacturing process of the A1 wiring transparent conductive film laminated substrate according to the present embodiment. In this explanatory view, the manufacturing process of the A1 wiring transparent conductive film laminated substrate using the amorphous transparent conductive film according to the above Examples 2-1 to 2-5 is shown.
• FIG. 3 (1) a glass substrate 1 is shown.
• This glass substrate 1 corresponds to a preferred example of the transparent substrate in the claims.
• an A1 alloy thin film 20 is deposited on the glass substrate 1.
• an amorphous transparent conductive film 22 is deposited so as to cover the A1 wiring 20a.
• the amorphous transparent conductive film 22 has, for example, any one of the above Examples 2-1 to 2-5.
• the deposition of the amorphous transparent conductive film 22 is preferably performed by sputtering, for example.
• the amorphous transparent conductive film 22 is etched to form a transparent electrode 22a patterned in a predetermined shape.
• This formation is typically performed as follows. First, after applying a predetermined resist, a predetermined mask is superimposed and exposure with ultraviolet rays or the like is performed. After exposure, development is performed to remove unnecessary resist, and etching is performed. After etching, remove the remaining resist Remove using stripping solution. In this way, as shown in FIG. 3 (5), the transparent electrode 22a having a desired shape is formed so as to be directly joined to the A1 wiring 20a.
• an aqueous solution of oxalic acid having a concentration of 1% to 10% is used as an etchant.
• the aqueous solution temperature at this time is 20 ° C to 50 ° C.
• a diethanolamine aqueous solution (40 wt%) was used as the stripping solution. As described above, when these aqueous solutions are used, the local cell reaction hardly occurs and the elution of A1 can be suppressed.
• the transparent electrode 22a by applying each of the above aqueous solutions using the amorphous transparent conductive film having the composition of Example 2-1 to Example 2-5, the transparent electrode 22a
• the taper angle of the end can be in the range of 30 to 89 degrees.
• transparent electrode 2 comprising A1 wiring 20a and amorphous transparent conductive film 22
• An interlayer insulating film 24 may be provided between 2a and 2a.
• a through hole 24a opened in the interlayer insulating film 24 is provided. This is shown in Figure 3 (6).
• a pure A1 sputtering target is mounted on the sputtering equipment, and the ultimate vacuum is 5 X 10—
• Sputtering was performed by setting the substrate temperature to room temperature at 4 Pa, film forming pressure: 0. IPa, and a 200 nm thick A1 thin film 32 was formed on a predetermined slide glass 30.
• This sputtering was performed so that the transparent conductive film 34 had a thickness of lOOnm.
• the temperature was room temperature.
• ITO was laminated in the same manner as a reference example.
• Example 2-1 is a 3 ⁇ 4 example
• 3 ⁇ 4 Example 2- ⁇ ⁇ 2_5 is a 3 ⁇ 4 example 2-5 W ratio.
• Example 2— ⁇ , 2— 2 is the ratio ⁇ , 2
• the substrate on which only pure A1 was deposited was immersed in a 2.4 wt% aqueous solution at 20 degrees, and dissolution of the A1 film was observed. However, the dissolution of A1 was not confirmed.
• the A1ZITO laminated film which is the laminated structure of the “A1Z transparent conductive film”, confirms that the dissolution of A1 is confirmed in the A1ZITO laminated film. Is equivalent to confirming that a battery reaction has occurred! /.
• the present embodiment 2-2 if the transparent conductive film of Examples 2-1 to 2-5 is used, the A1 thin film will not be dissolved during etching by TMAH. Therefore, it is understood that the multilayer circuit board can be manufactured smoothly.
• Example 2-7 Experiments were conducted regarding resistance to the release agent.
• the glass substrate with a thin film having a thickness of lOOnm obtained in Example 2-1 described above was used as a target for investigating the resistance.
• aqueous solution obtained by adding 10 vol% of water to a 30 vol% diethanolamine and 70 vol% DMSO (dimethylsulfoxide) as a resist remover was used.
• Example 2-1 The glass substrate with a thin film prepared in Example 2-1 described above was immersed in an aqueous solution of the above release agent at 45 ° C for 5 minutes. Then, the surface SEM of the glass substrate with the thin film after immersion was observed to observe unevenness and roughness of the surface, but no unevenness and roughness were observed.
• the line width was set to 50 m, and the A-translated line and the transparent conductive film were arranged so as to be orthogonal to each other, and the contact resistance at the laminated interface was measured (Kelvin probe method). That is, a thin layer of A1 wiring and a thin layer of a transparent conductive film are laminated on a predetermined substrate so as to be orthogonal (in a cross shape), and the contact resistance between them is measured by the Kelvin probe method. Both line widths are 50 m.
• the transparent conductive film includes the transparent conductive film used in Example 2-1 to Example 2-5 described above and the transparent conductive film used in Comparative Example 2-1 to Comparative Example 2-2 described above.
• a membrane was used.
• measurements were also made on an example using conventional ITO as a transparent conductive film. In this way, contact resistance was measured by making eight types of transparent conductive films orthogonal to the A1 thin film (thin wires). The measurement results are shown in Table 6 described above.
• Example 2-1 Are described as Example 1, Examples 2-1 to 2-5 as Examples 2 to 5, and Comparative Examples 2-1 and 2-2 as Comparative Examples 1 and 2.
• the insect contact resistance is 0.4 ⁇ , 0.6 ⁇ , 0.7 ⁇ , 1.2 ⁇ . 1. 5 ⁇ , both showing low resistance of less than 2 ⁇ .
• the transparent conductive film used in Comparative Example 2-1 0.
• the value was as high as 12 ⁇ .
• the example using ITO as the transparent conductive film showed a high contact resistance of 140 ⁇ .
• Example 2-9 of the second group of the present invention the state of manufacturing a TFT substrate according to the present invention will be described with reference to FIG.
• metal A1 (99% Al, l% Nd) is deposited on a light-transmitting glass substrate 1 to a thickness of 1500 angstroms by high frequency sputtering. This is formed into a gate electrode 2 and a gate electrode wiring having desired shapes by a photoetching method using a phosphoric acid-acetic acid-nitric acid aqueous solution as an etching solution.
• the glass substrate 1 corresponds to a preferred example of the transparent substrate in the claims.
• a gate insulating film 3 to be a silicon nitride (SiN) film is deposited to a thickness of 3 000 angstroms by glow discharge CVD.
• an a-Si: H (i) film 4 is deposited to a thickness of 3500 angstroms, and a silicon nitride (SiN) film 5 as a channel protection layer is deposited to 3000 angstroms.
• SiN films 3 and 5 use SiN-NH-N mixed gas as the discharge gas.
• a desired channel protective layer was formed by dry etching using HF gas.
• the ⁇ -Si: H (n) film 6 is formed to 3000 ⁇ by using SiH — H — PH mixed gas.
• a CrZAl bilayer film is deposited thereon by vacuum deposition or sputtering in the order of 0.1 ⁇ m Cr and 0.3 ⁇ m Al.
• This two layers A1 is H PO-CH COO
• Etching is performed using a photoetching method. As a result, the pattern of the desired source electrode 7 and the pattern of the drain electrode 8 are formed, and the source electrode 7 and the drain electrode 8 are formed.
• Cr is provided on the lower surface of the source electrode 7 and the drain electrode 8 and is not provided on the surface in contact with the amorphous transparent conductive film 9. That is, as will be described later, the A1 portion constituting the source electrode 7 and the drain electrode 8 is directly connected to the amorphous transparent conductive film. It is joined to 9.
• the desired pattern ⁇ can be obtained by using wet etching with H 2 O) aqueous solution.
• an insulating film 10 to be a silicon nitride (SiN) film is deposited with a predetermined film thickness by a glow discharge CVD method. Then, contact holes are formed between the source and drain electrodes, the transparent electrode, and the pixel electrode by a dry etching method using CHF gas.
• SiN silicon nitride
• An amorphous transparent conductive film 9 mainly composed of zinc oxide and tin oxide obtained in Example 1 was formed on the substrate on which the pattern of the source electrode 7 and the drain electrode 8 having the metal A1 force was formed. Deposited by sputtering. The amorphous transparent conductive film 9 is connected to the source electrode 7 and the like through a contact hole (see FIG. 1).
• the discharge gas used when forming the amorphous transparent conductive film 9 is formed by depositing the amorphous transparent conductive film 9 by a method using Ar gas mixed with pure argon or a small amount of O gas of about lvol%. 1200
• This amorphous transparent conductive film 9 is the transparent conductive film used in Example 3 above.
• this amorphous transparent conductive film 9 was analyzed by X-ray diffraction, no peak was observed, confirming that it was an amorphous film.
• the specific resistance of the amorphous transparent conductive film 9 is about 0.009 ⁇ 'cm, and can be used as a sufficient electrode.
• This amorphous transparent conductive film 9 was etched by photo etching using an aqueous solution of 3.5% by weight of oxalic acid as an etchant so as to obtain a desired electrode pattern.
• This electrode pattern is a “pixel electrode pattern” that is electrically connected to at least the pattern of the source electrode 7. At this time, the source electrode 7 and the drain electrode 8 made of A1 were not eluted by the etching solution.
• the electrode lead-out portions of the gate line 12 and the source / drain lines are also covered with a transparent electrode made of the same conductive film as the amorphous transparent conductive film 9 .
• a light-shielding film pattern is formed thereon to complete an a-Si TFT active matrix substrate.
• TFT-LCD type flat A surface display was manufactured. This TFT-LCD type flat display was able to perform halftone display (gradation display) well.
• TFT substrate As described above, according to this embodiment, it is possible to manufacture a so-called TFT substrate with a simple manufacturing method! In addition, such a TFT substrate does not generate a large contact resistance between the transparent conductive film and the A1 wiring.
• TFT substrate an example of a TFT substrate is shown, but it goes without saying that the present invention can be applied to any substrate provided with A1 wiring and provided with a transparent conductive film.
• sputtering targets according to various configurations were created, and the characteristics and the characteristics of the transparent conductive film manufactured using the characteristics were inspected.
• the compact was sintered as follows. First, sintering was performed in a sintering furnace at 1500 ° C. for 5 hours in an atmosphere in which oxygen was introduced at a rate of 5 LZmin per 0.1 lm 3 of the furnace volume. At this time, the temperature was raised to 1 000 ° C by l ° CZmin and from 1000 to 1500 ° C by 3 ° CZmin. After that, oxygen introduction was stopped, and the temperature was decreased from 1500 ° C to 1300 ° C at 10 ° C Zmin. Then, in an atmosphere in which argon gas was introduced at a rate of lOLZmin per 0.1 lm 3 of the furnace volume, the temperature was kept at 1300 ° C.
• the surface to be sputtered of the sintered body thus obtained is polished with a cup mortar, processed to a diameter of 100 mm and a thickness of 5 mm, and a backing plate is pasted using an indium alloy.
• a sputtering target a was configured. At this time, the density of the sputtering target was 6.68 gZcm 3 .
• m is preferably a hexagonal layered compound represented by 2 to 20.
• the form in which the zinc is contained in the sputtering target is In 2 O (ZnO) or In 2 O 3.
• Indium oxide and zinc oxide compounds such as (ZnO) and InO (ZnO)
• the average diameter of the crystal particles determined by image processing of the SEM photograph was 3.67 m.
• Tin atoms disperse and dissolve in the indium sites of indium oxide, so that tin is dispersed at the atomic level in the oxide-indium sintered body. It is stable and effective for reducing the resistance of the obtained transparent conductive thin film. As a result, the Balta resistance of the target is 0.97 mQ cm, which enables stable RF and DC sputtering.
• the obtained sputtering target a was mounted on a sputtering apparatus, and the ultimate vacuum was reached.
• Table 7 is a table showing the properties of the used sputtering
• Table 8 is a table showing the physical measurement results of the obtained transparent conductive film.
• the specific resistance and mobility of the transparent conductive thin film obtained as a result of sputtering are It was determined by measurement.
• the transmittance was measured with a self-recording spectrophotometer.
• Table 9 shows the etching rates when the aqueous solution concentration and temperature of oxalic acid were changed.
• the taper angle of the obtained pattern was determined by SEM (Scanning Electron Micros cope) observation. The results are also shown in Table 9.
• Example 3-1 In Table 7, Table 8, and Table 9, not only Example 3-1, but also Example 3-2, Example 3-3, Example 3-4, and Example 3-5 are described.
• Example 3-1 the density of the sputtering target was 6.75 g / cm 3 and the average particle size was 3.
• the specific resistance was as low as 0.97 m Q cm.
• the specific resistance of the transparent conductive film (transparent electrode) prepared using the sputtering target of Example 3-1 was 0.0005 Q cm, and the transparent conductive film (transparent electrode) ) was 25 cm 2 ZV. Sec.
• the light transmittance (wavelength 550 ⁇ m) was 80 including the glass substrate.
• the thickness of the transparent conductive film (transparent electrode) is 100 nm.
• the etching rate when this transparent conductive film was etched with Shinoic acid was 30 ° C. It was 1100 AZmin when an aqueous oxalic acid solution was used, 2200 AZmin when an aqueous oxalic acid solution at 40 ° C was used, and 1800 AZmin when an aqueous oxalic acid solution at 35 ° C was used. As a result of etching, the taper angle was 45 degrees (see Table 9).
• Example 3-2 Example 3-3, Example 3-4, Example 3-5
• Indium oxide powder having an average particle size of 1 ⁇ m or less, zinc oxide powder having an average particle size of 1 ⁇ m or less, and tin oxide powder having an average particle size of 1 ⁇ m or less were used as raw material powders. Prepare a mixture of indium oxide powder, zinc oxide powder and tin oxide powder in a resin-made pot. And mixed with a wet ball mill.
• the granulated product was filled in a circular mold and formed into a disk shape by applying a pressure of 3 ton Zcm 2 using a cold isostatic press.
• each compact was placed in an atmosphere adjustment furnace and sintered.
• sintering sintering was performed at 1500 ° C for 5 hours while introducing oxygen into the furnace at a rate of 5 liters Z per 0.1 m 3 of the furnace volume.
• the temperature was increased from 1000 ° C to 1 ° CZ and from 1000 ° C to 1500 ° C at a rate of 3 ° CZ.
• the introduction of oxygen was stopped, and the temperature was decreased from 1500 ° C to 1300 ° C at a rate of 10 ° CZ.
• Example 3-2 is an example using the sintered body target 2
• Example 3-3 is an example using the sintered body target 3
• Example 3-4 is a sintered body. This is an example using the body target 4
• Examples 3-5 are examples using the sintered body target 5.
• the surfaces to be sputtered surfaces of the obtained sintered compact targets 2 to 5 were polished with a cup mortar and processed into a diameter of 152 mm and a thickness of 5 mm to obtain sputtering targets.
• Zinc oxide and tin oxide power can be dispersed, especially when zinc oxide is In O (ZnO) m
• m is preferably a hexagonal layered compound represented by 2 to 20.
• the form in which the zinc is contained in the sputtering target is In 2 O 3 (ZnO).
• the average diameter of the crystal particles determined by image processing of the SEM photograph is shown in Table 7.
• Tin atoms disperse and dissolve in the indium sites of indium oxide, so that tin is dispersed at the atomic level in the oxide-indium sintered body. It is stable and effective for reducing the resistance of the obtained transparent conductive thin film. As a result, the target resistance becomes low as shown in Table 7, and stable RF and DC sputtering becomes possible.
• the Balta resistance of the sputtering target is less than 1000 m ⁇ cm, and stable DC or RF sputtering is possible.
• the measurement results are also shown in Table 7.
• Example 7 The ratio of each component in Example 3-2 is shown in Table 7,
• the density of the sputtering target was 6.68 g / cm 3 and the average particle size was 3.71 m.
• the specific resistance was as low as 1.2 m Q cm.
• the specific resistance of the transparent conductive film (transparent electrode) produced using the sputtering target having this composition was 0.0007 ⁇ cm, and the mobility was 25 cm 2 ZV.sec.
• the light transmittance (wavelength: 550 nm) was 78 (see Table 8).
• the thickness of the transparent conductive film created here is lOOnm.
• the etching rate when this transparent conductive film is etched with shinocic acid is 600 AZmin when using 30 ° C oxalic acid aqueous solution, and 1200 AZmin when using 40 ° C oxalic acid aqueous solution.
• a 35 ° C aqueous oxalic acid solution was used, it was 1000 AZmin.
• the taper angle was 45 degrees (see Table 9).
• Table 10 shows the environmental test of TCP connection by ACF. The test environment is the same as in Example 3-1.
• Example 3-2 the TCP connection resistance immediately after connection is 4.5 ⁇ , after 240 hours it is 4.6 ⁇ , and after 480 hours it is 4. The resistance increased to 4.9 ⁇ after 960 hours, and the increase in resistance was small.
• the specific resistance of the transparent conductive film (transparent electrode) prepared using the sputtering target having this composition was 0.0009 ⁇ cm, and the mobility was 20 cm 2 ZV.sec.
• the light transmittance (wavelength: 550 nm) was 77 (see Table 8).
• the thickness of the transparent conductive film created here is lOOnm.
• the etching rate when this transparent conductive film was etched with shinocic acid was 300 AZmin when using 30 ° C oxalic acid aqueous solution, and 600 AZmin when using 40 ° C oxalic acid aqueous solution.
• the taper angle was 65 degrees (see Table 9).
• Table 10 shows the environmental test of TCP connection by ACF.
• the test environment is the same as in Example 3-1.
• the TCP connection resistance immediately after connection is 4.8 ⁇ , and after 240 hours it is 4.8 ⁇ , and after 480 hours it is 4.
• the resistance increased to 4.9 ⁇ after 960 hours, and the increase in resistance was small.
• the specific resistance of the transparent conductive film (transparent electrode) produced using the sputtering target of this composition was 0.001 ⁇ cm, and the mobility was 18 cm 2 ZV.sec.
• the light transmittance (wavelength: 550 nm) was 76 (see Table 8).
• the thickness of the transparent conductive film created here is lOOnm.
• the etching rate when this transparent conductive film is etched with Shinoic acid is 1000 AZmin when using a 30 ° C oxalic acid aqueous solution, and 2000 AZmin when using a 40 ° C oxalic acid aqueous solution.
• an aqueous oxalic acid solution at 35 ° C it was 1800 AZmin.
• the taper angle became 70 degrees (see Table 9).
• Table 10 shows the environmental test of TCP connection by ACF.
• the test environment is the same as in Example 3-1.
• the TCP connection resistance immediately after connection is 5.1 ⁇ , it is 5.2 ⁇ after 240 hours, and 5.4 ⁇ after 480 hours. Yes, after 960 hours, it became 5.5 ⁇ , and the increase in resistance was small.
• the density of the sputtering target was 6.51 g / cm 3 and the average particle size was 3.98 / zm.
• the specific resistance was as low as 92m Q cm.
• the specific resistance of the transparent conductive film (transparent electrode) produced using the sputtering target of this composition was 0.009 ⁇ « ⁇ , and the mobility was 15 cm 2 ZV.sec.
• the light transmittance (wavelength: 550 nm) was 82 (see Table 8).
• the thickness of the transparent conductive film created here is lOOnm.
• the etching rate when this transparent conductive film is etched with Shinoic acid is 1000 AZmin when using a 30 ° C oxalic acid aqueous solution, and 2000 AZmin when using a 40 ° C oxalic acid aqueous solution. When using an aqueous oxalic acid solution at 35 ° C, it was 1800 AZmin. As a result of etching, the taper angle was 75 degrees (see Table 9).
• Table 10 shows the environmental test of TCP connection by ACF.
• the test environment is the same as in Example 3-1.
• the TCP connection resistance immediately after connection is 5.3 ⁇ , after 240 hours it is 5.5 ⁇ , and after 480 hours it is 5.
• the resistance increased to 5.8 ⁇ after 960 hours, and the increase in resistance was small.
• Comparative Examples 3-1, 3-2 and 3-3 Examples with different yarn formation from Examples 3-1 to 3-5 above are listed as Comparative Examples 3-1, 3-2 and 3-3.
• the results of Comparative Examples 3-1, 3-2, and 3-3 are also shown in Table 7, Table 8, Table 9, and Table 10.
• Comparative Example 3-1 does not contain Zn as a component.
• the density of the sputtering target was 6.85 gZcm 3 and the average particle size was 3.75 / zm.
• the specific resistance was 1. Om Q cm.
• the specific resistance of the transparent conductive film (transparent electrode) prepared using the sputtering target having this composition was 0.0004 ⁇ cm, and the mobility was 40 cm 2 ZV.sec.
• the light transmittance (wavelength: 550 nm) was 83.
• the thickness of the transparent conductive film created here is lOOnm.
• the etching rate when this transparent conductive film was etched with shinocic acid was 50 AZmin when an aqueous oxalic acid solution at 30 ° C was used, and 90 when an aqueous oxalic acid solution at 40 ° C was used.
• a Zmin which was 150 A Zmin when a 35 ° C aqueous oxalic acid solution was used.
• the etching rate was slower than in Examples 3-1 to 3-5.
• the taper angle was 125 degrees (see Table 9).
• Table 10 shows the environmental test of TCP connection by ACF. The test environment is the same as in Example 3-1.
• the TCP connection resistance immediately after connection is 7.2 ⁇ , 18 ⁇ after 240 hours, 34 ⁇ after 480 hours, 960 hours After the lapse of time, the resistance became 58 ⁇ , and the resistance increased with time.
• Comparative Example 3-2 does not contain Sn as a component. Further, as shown in Table 7, the density of the sputtering target was 6.54 gZcm 3 and the average particle size was 3.81 / zm. The specific resistance was 1. Om Q cm.
• the specific resistance of the transparent conductive film (transparent electrode) produced using the sputtering target having this composition was 0.0006 ⁇ cm, and the mobility was 25 cm 2 ZV.sec.
• the light transmittance (wavelength: 550 nm) was 80.
• the thickness of the transparent conductive film created here is lOOnm.
• the etching rate when this transparent conductive film was etched with shinocic acid was 900 AZmin when using a 30 ° C oxalic acid aqueous solution, and 1800 when using a 40 ° C oxalic acid aqueous solution.
• V was 1500 AZmin.
• the taper angle was 45 degrees (see Table 3).
• Table 10 shows the environmental test of TCP connection by ACF.
• the test environment is the same as in Example 3-1.
• the TCP connection resistance immediately after connection is 6.5 ⁇ , 15 ⁇ after 240 hours, 28 ⁇ after 480 hours, 960 hours After the lapse of 52 ⁇ , the resistance increased with the passage of time.
• Comparative Example 3-3 does not contain In as a component. Also As shown in Table 7, the density of the sputtering target was 6.21 gZcm 3 and the average particle size was 3.68 m. The specific resistance was not measurable.
• the specific resistance of the transparent conductive film prepared by using the sputtering target of this composition is 0. 06 Omega cm, mobility was 15cm 2 ZV.sec.
• the light transmittance (wavelength: 550 nm) was 74.
• the thickness of the transparent conductive film prepared here is lOOnm.
• Transparent films with a thickness of lOOnm were formed at room temperature using targets 1 to 3-2.
• the last one slide glass was coated with Kapton seal and ITO film was formed as a reference.
• a glass substrate on which the transparent conductive film of Example 3-1 was laminated with lOOnm was used as a resist stripper. Soaked.
• the resist stripping solution was prepared by adding 10 vol.% Water to a 30 vol.% Diethanolamine 30 vol.% DMSO (dimethylsulfoxide) 70 vol.% Resist stripping agent. The glass with thin film was immersed in this resist stripping solution at 45 ° C. for 5 minutes.
• the contact resistance between both layers in the laminated film of A1 and the transparent conductive film was measured.
• a thin wire (line width 50 ⁇ m) of the A1 thin film and a thin wire (line width 50 / z m) of the transparent conductive film are provided on the glass substrate so as to be orthogonal to each other.
• Measurement of contact resistance at the interface between the two layers was performed. This measurement is shown in Fig. 6.
• the measurement results are shown in Table 12.
• AI thin film / Comparative Example 3-2 Thin film multilayer substrate 30 As shown in Table 12, the contact resistance between the transparent conductive film of Examples 3-1 to 3-5 and the A1 thin film was found in Kawasaki from Example 3-1 to 3-5, 0.3 ⁇ , The values were 0.4 ⁇ , 0.6 ⁇ , 1.1 ⁇ , and 1.4 ⁇ , and the deviation was low enough to be used as a display device.
• the other metal is preferably one or more metals selected from the group forces consisting of Ni, W, Mo, Nb, Zr, and Nd.
• the content of the metal other than A1 is preferably 0.1 to L0 wt%.
• FIG. 5 is an explanatory diagram showing an outline of the manufacturing process of the A1 wiring transparent conductive film laminated circuit board according to the present embodiment. In this explanatory view, a part of the manufacturing process of the Affi line transparent conductive film laminated circuit board using the amorphous transparent conductive film according to the above Examples 3-1 to 3-5 is shown.
• a Ni-containing A1 wiring 1028 is provided on a glass substrate 1001, and an amorphous transparent conductive film 1029 is deposited on the Ni-containing A1 wiring 1028.
• This amorphous transparent conductive film 1029 is an amorphous transparent conductive film according to Examples 3-1 to 3-5.
• this amorphous transparent conductive film 1029 is etched into a desired shape pattern.
• This etching process is a process for creating electrodes having a predetermined shape and is also called patterning.
• the glass substrate 1001 in FIG. 5 (1) corresponds to a preferred example of the transparent substrate in the claims.
• a predetermined resist is applied with the state force shown in Fig. 5 (1).
• exposure with ultraviolet rays or the like is performed with a predetermined mask superimposed.
• development is performed to remove unnecessary resist.
• a TMAH alkaline aqueous solution is used as the developer.
• Ni-containing A1 wiring in TMAH aqueous solution Since the difference in electromotive force between 1029 and the amorphous transparent conductive film 1029 is small, it is possible to suppress battery reaction during development processing. This development process removes the resist in portions other than the desired electrode shape.
• etching using an oxalic acid etchant is performed.
• the portion other than the desired shape as the electrode is removed, and the remaining portion forms the transparent electrode 1029a having the desired shape.
• the remaining resist is removed using a stripping solution.
• diethanolamine aqueous solution 40 wt% is used.
• the transparent electrode 1029a having a desired shape as shown in Fig. 5 (2) can be formed by the processing as described above.
• an amorphous transparent conductive film having the composition shown in Examples 3-1 to 3-5 above was prepared using oxalic acid having a concentration of lwt% to 10% and a water temperature of 20 ° C to 50 ° C.
• the taper angle of the end of the transparent electrode 1029a to be formed can be made 35 to 89 degrees. By realizing such a taper angle, it is possible to produce a laminated substrate having excellent durability.
• the interlayer insulating film 1030 is often provided between them for convenience of circuit configuration.
• the situation in this case is shown in Fig. 5 (3).
• the contact hole 1030a is provided in the electrically connected portion and directly joined.
• the Ni-containing A1 wiring using the alloy containing Ni in the A1 wiring is used, and the amorphous transparent conductive film having a specific composition is used.
• the A1 wiring and the transparent conductive film can be directly joined, and A1 does not elute in the manufacturing process.
• the contact resistance can be suppressed to a small value.
• metal A1 (99% Al, l% Nd) is deposited on a light-transmitting glass substrate 1001 by high-frequency sputtering to a thickness of 1500 angstroms. This is formed into a gate electrode 1002 and a gate electrode wiring having a desired shape by a photoetching method using a phosphoric acid acetic acid nitric acid-based aqueous solution as an etching solution.
• the glass substrate 1001 corresponds to a preferred example of the transparent substrate in the claims.
• a gate insulating film 1003 to be a silicon nitride (SiN) film is deposited to a thickness of 3000 angstroms by glow discharge CVD.
• an ⁇ Si: H (i) film 1004 is deposited to a thickness of 3500 angstroms
• a silicon nitride (SiN) film 1005 to be a channel protective layer is deposited to 3000 angstroms.
• SiN films 1003 and 1005 are SiN — NH ⁇
• the a-Si: H (i) film 1004 uses a SiH-N-based mixed gas, respectively.
• SiN film 1005 a desired channel protective layer was formed by dry etching using CHF gas.
• a-Si: H (n) film 1006 is mixed with SiH-H-PH mixed gas.
• a CrZAl bilayer film is deposited thereon in the order of 0.1 ⁇ m Cr and 0.3 ⁇ m Al by vacuum deposition or sputtering.
• This two layers A1 is H PO-CH COO
• Etching is performed using a photoetching method. As a result, a desired source electrode 1007 pattern and drain electrode 1008 pattern are formed, and the source electrode 1007 and the drain electrode 1008 are formed.
• the A1 alloy used in the Cr / Al bilayer film is an A1 alloy containing 0.1 wt% to 10 wt% of Ni.
• Cr is provided on the lower surface of the source electrode 1007 and the drain electrode 1008 as shown in FIG. 4, and is not provided on the surface in contact with the amorphous transparent conductive film 1009. That is, as described later, the A1 partial force constituting the source electrode 1007 and the drain electrode 1008 is directly bonded to the amorphous transparent conductive film 1009.
• ⁇ -Si coating film was etched using CHF gas and hydrazine ( ⁇ ⁇ ⁇ ⁇
• the desired pattern ⁇ can be obtained by using wet etching with aqueous solution.
• a pattern of Si: H (i) film 1004 and a—Si: H (n) film 1006 are formed.
• an ⁇ -Si: H (i) film 1004 and an ⁇ -Si: ⁇ ( ⁇ ) film 1006 are formed.
• the a-Si TFT part is completed through the above process.
• an insulating film 1010 to be a silicon nitride (SiN) film is deposited with a predetermined film thickness by a glow discharge CVD method. Thereafter, contact holes are formed between the source and drain electrodes, the transparent electrode, and the pixel electrode by a dry etching method using CHF gas.
• the non-component mainly composed of indium oxide, zinc oxide, and tin oxide obtained in Example 3-1 the non-component mainly composed of indium oxide, zinc oxide, and tin oxide obtained in Example 3-1.
• a crystalline transparent conductive film 1009 is deposited by sputtering.
• the amorphous transparent conductive film 1009 is connected to the source electrode 1007 and the like through a contact hole (see FIG. 4).
• the discharge gas used for forming the amorphous transparent conductive film 1009 is pure argon or Ar gas mixed with a trace amount of O gas of about 1 vol%.
• a film thickness of 1200 ⁇ was deposited. This In O -ZnO -WO film is separated by X-ray diffraction.
• this amorphous transparent conductive film 1009 is about 5.0 X 10 " 4 ⁇ 'cm, and it is a film that can be used as an electrode.
• Etchant was used to etch to a desired electrode pattern using an aqueous solution of 3.5% by weight of oxalic acid as an etchant.
• This electrode pattern is a pixel that is electrically connected to at least the pattern of the source electrode 1007.
• the electrode lead-out portions of the gate line 1012 and the source / drain lines are also covered with a transparent electrode made of the same conductive film as the amorphous transparent conductive film 1009.
• a light-shielding film pattern is formed thereon to complete an a-Si TFT active matrix substrate.
• a TFT-LCD flat display was manufactured using this substrate. This TFT-LCD flat display is a halftone display (Gradation display) could be performed well.
• the present embodiment it is possible to manufacture a so-called TFT substrate by a simple manufacturing method without the need to provide a barrier metal or the like.
• the TFT substrate does not generate a large contact resistance between the transparent conductive film and the A1 wiring.
• an example of a TFT substrate has been shown, but it goes without saying that the present invention can be applied to any substrate provided with a transparent conductive film provided with A1 wiring. .
• sputtering targets according to various configurations were created, and the characteristics and the characteristics of the transparent conductive film manufactured using the characteristics were inspected.
• the mixing time was 20 hours.
• the obtained mixed slurry was taken out, filtered, dried and granulated.
• the obtained granulated product was molded by a cold isostatic press while applying a pressure of 294 MPa (3 tZcm 2 ).
• the compact was sintered as follows. First, sintering was performed in a sintering furnace at 1500 ° C. for 5 hours in an atmosphere in which oxygen was introduced at a rate of 5 LZmin per 0.1 lm 3 of the furnace volume. At this time, the temperature was raised to 1 000 ° C by l ° CZmin and from 1000 to 1500 ° C by 3 ° CZmin. After that, oxygen introduction was stopped, and the temperature was decreased from 1500 ° C to 1300 ° C at 10 ° C Zmin. Then, in an atmosphere in which argon gas was introduced at a rate of lOLZmin per 0.1 lm 3 of the furnace volume, the temperature was kept at 1300 ° C. for 3 hours and then allowed to cool. As a result, a zinc oxide / tin oxide-containing sintered body having a relative density of 90% or more was obtained.
• the sputter surface of the sintered compact target thus obtained is polished with a cup mortar, processed to a diameter of 100 mm and a thickness of 5 mm, and a backing plate is prepared using an indium alloy.
• the sputtering target a was configured by bonding. Sputtering at this time
• the density of target a was 5.72 gZcm 3 .
• the tin oxide is dispersed, and in particular, it is substituted and dissolved in the zinc site of the acid zinc. That is, the form in which the tin is contained in the target is SnO or SnO.
• Any tin oxide may be dispersed in the acid-zinc sintered body, but ZnSnO,
• the average diameter of the crystal grains determined by mapping image processing of Sn atoms in EPMA was 3.87 m.
• tin atoms are dispersed and dissolved in zinc sites of zinc oxide zinc, so that tin is dispersed at the atomic level in the zinc oxide sintered body.
• This is effective for stable discharge and low resistance of the transparent conductive thin film.
• the Balta resistance of the sputtering target a becomes 360 ⁇ cm, which is considered to enable stable RF sputtering.
• the obtained sputtering target a was attached to a sputtering apparatus, and the ultimate vacuum was reached.
• Tables 1 and 2 are tables showing the properties of the sputtering target used, and Table 2 is a table showing physical measurement results of the obtained transparent conductive film.
• Table 3 shows the etching rates when the aqueous solution concentration and temperature of oxalic acid were changed.
• the taper angle of the obtained pattern was determined by SEM (Scanning Electron Micros cope) observation. This result is also shown in Table 3 above.
• Example 41 is described as Example 1
• Examples 4-2 to 4-5 are described as Examples 2 to 5.
• the value of the specific resistance of the transparent conductive film (transparent electrode) can be reduced, and the value of the AgZAgCl standard electrode potential is set close to that of the A1 thin film. We were able to.
• the transparent conductive film in Example 41 has a small electrode potential difference from the A1 thin film. This is true in all solutions of oxalic acid aqueous solution, TMAH and the above stripping solution. Therefore, it is possible to effectively prevent the local battery reaction from occurring, and to effectively prevent the dissolution of A1.
• the etching rate with a 3.5 wt% oxalic acid aqueous solution was 105, OOOA / min (30 ° C), 220, 000AZmin (40.C), 180, OOOAZmin (35.C), and good etching characteristics. Were observed (Table 3). As a result of etching, the taper angle was 86 degrees (Table 3). Since it is not an extremely small or large value, it is considered that a transparent electrode with excellent durability can be formed.
• the TCP connection resistance immediately after connection is 4.2 ⁇ , 5.6 ⁇ after 240 hours, 6.2 ⁇ after 480 hours, and 96 hours. After that, it became 6.5 ⁇ .
• the degree of increase in contact resistance over time is very small, and even when used in a display device, it is considered that the deterioration in performance due to the increase in resistance is very small.
• a display device with high durability can be configured.
• Zinc oxide powder having an average particle size of 1 ⁇ m or less and tin oxide powder having an average particle size of 1 ⁇ m or less were used as raw material powders.
• Zinc oxide powder and tin oxide powder were blended in a predetermined ratio and made into a resin pot, and mixed by a wet ball mill. At that time, use hard ZrO balls and mix
• the time was 20 hours.
• the mixed slurry was taken out, filtered, dried and granulated.
• the granulated product was filled into a circular mold and formed into a disk shape by applying a pressure of 3 ton Zcm 2 using a cold isostatic press.
• the compact was placed in an atmosphere adjustment furnace and sintered. During sintering, sintering was performed at 1500 ° C. for 5 hours while introducing oxygen into the furnace at a rate of 5 liters Z per 0.1 lm 3 of the furnace volume. At this time, the temperature was increased from 1000 ° C to 1 ° CZ and from 1000 ° C to 1500 ° C at a rate of 3 ° CZ. After the sintering, the introduction of oxygen was stopped and the temperature was decreased from 1500 ° C to 1300 ° C at a rate of 10 ° C / min.
• Example 4-2 is an example using a sintered body target b
• Example 4-3 is an example using a sintered body target c
• Example 4-4 is a sintered body target.
• Example 4 is an example using d
• Example 4-5 is an example using the sintered compact target e.
• the surface to be sputtered of the obtained sintered bodies was polished with a cup mortar and processed into a diameter of 152 mm and a thickness of 5 mm to obtain sputtering targets.
• tin oxide is dispersed, and in particular, it is substituted and dissolved in zinc sites of acid zinc. It is preferable. That is, the form in which the above tin is contained in the target is in the form of tin oxide such as SnO and SnO,
• Example 3 2 4 or other oxides and zinc oxides In the form of complex oxides between tin monoxide, it may be dispersed in the acid-zinc sintered body. As a result of such dispersion, the average diameter of the crystal grains became as shown in Table 1. As in Example 4-1, in Examples 4-2-4-5, the average diameter of the crystal grains was measured. Table 1 shows the results obtained by processing (EPMA Sn atom mapping image processing).
• the tin atoms are dispersed and dissolved in zinc sites of zinc oxide, so that tin is dispersed at the atomic level in the zinc oxide sintered body.
• This is effective for stable discharge and low resistance of the transparent conductive thin film.
• the Balta resistance of the target is all less than 500 ⁇ cm, enabling stable sputtering. This measurement is shown in Table 1.
• TCP connection was made with ACF (Anisotoropic Conductive Film), 60 ° C, 90% RH (relative humidity) : Relative Humidity) and observed changes in connection resistance. Nests are shown in Table 4 above,
• Example 42 as shown in these tables, the value of [Zn] / ([Zn] + [Sn]) is 0.75.
• the target density was 5.86 gZcm 3 and the average particle size was 3.82 um.
• the specific resistance was 350 ⁇ cm (Table 1).
• the specific resistance of the transparent conductive film formed using this sputtering target b was 0.04 Q cm and the mobility was 45 cm 2 ZV 'sec.
• the light transmittance was 86.3% (wavelength 550 nm), and the AgZAgCl standard electrode potential was -0.78 V (Table 2).
• the specific resistance values were all sufficiently low, and the transparency was also sufficient for use in a display device.
• the AgZAgCl standard electrode potential is + 0.18V compared to the potential of the A1 thin film, and the difference is very small, and the battery reaction is sufficiently suppressed.
• the etching rate with 3.5 wt% oxalic acid aqueous solution is 65,000 A / min (30 ° C), 1 32,000 AZmin (40 ° C), 96, 000 AZmin (35 ° C), and good etching Characteristics were observed (Table 3).
• the taper angle was 75 degrees (Table 3). Since extremely small values are not large values, it is considered that transparent electrodes with excellent durability can be formed.
• Example 43 as shown in these tables, the value of [Zn] / ([Zn] + [Sn]) is 0.70.
• the target density is 5.83 gZcm 3 and the average particle size is 3.
• the specific resistance of the transparent conductive film formed using this sputtering target c was 0.009 Q cm, and the mobility was 48 cm 2 ZV 'sec.
• the light transmittance was 86.5% (wavelength 550 nm), and the AgZAgCl standard electrode potential was -0.72 V (Table 2).
• the specific resistance values were all sufficiently low, and the transparency was sufficient for use in the display device.
• the AgZAgCl standard electrode potential is + 0.24V compared to the potential of the A1 thin film, and the difference is very small, and the battery reaction is sufficiently suppressed.
• Etching rates with 3.5 wt% oxalic acid aqueous solution were 500 AZmin (30 ° C), 1,100 AZmin (40 ° C), and 950AZmin (35 ° C), and good etching characteristics were observed (Table 3). As a result of etching, the taper angle was 48 degrees (Table 3). Since extremely small V ⁇ values are not large values, it is thought that transparent electrodes with excellent durability can be formed.
• Example 44 as shown in these tables, the value of [Zn] / ([Zn] + [Sn]) is 0.67.
• Target density was 5. 92gZcm 3, the average particle size is 3. 5 ⁇ m Met.
• the specific resistance was 420 ⁇ cm (Table 1).
• the specific resistance of the transparent conductive film formed using this sputtering target d was 0.006 Q cm, and the mobility was 46 cm 2 ZV 'sec.
• the light transmittance was 86.3% (wavelength 550 nm), and the AgZAgCl standard electrode potential was -0.68 V (Table 2).
• the specific resistance values were all sufficiently low, and the transparency was sufficient for use in the display device.
• the AgZAgCl standard electrode potential is +0.28 V compared to the potential of the A1 thin film, and the difference is very small, and the battery reaction is sufficiently suppressed.
• the etching rate with a 3.5 wt% oxalic acid aqueous solution was 30 AZmin (30 ° C), 7 lA / min (40 ° C), and 55AZmin (35 ° C), and good etching characteristics were observed (Table 5). 3)
• the taper angle was 42 degrees (Table 3). Since it is not an extremely small value or a large value, it is considered that a transparent electrode having excellent durability can be formed.
• Example 45 as shown in these tables, the value of [Zn] / ([Zn] + [Sn]) is 0.55.
• the target density was 6. lOgZcm 3 and the average particle size was not measurable.
• the specific resistance was 480 ⁇ cm (Table 1).
• the specific resistance of the transparent conductive film formed using this sputtering target d was 0.03 Q cm, and the mobility was 35 cm 2 ZV 'sec.
• the light transmittance was 85.9% (wavelength 550 nm), and the AgZAgCl standard electrode potential was -0.61 V (Table 2).
• the specific resistance values were all sufficiently low, and the transparency was sufficient for use in the display device.
• the AgZAgCl standard electrode potential is +0.35 V compared to the potential of the A1 thin film, and the difference is very small, and the battery reaction is sufficiently suppressed.
• the etching rate with a 3.5 wt% oxalic acid aqueous solution was 10 AZmin (30 ° C), 25 A / Min (40 ° C) and 22AZmin (35 ° C) were observed, and good etching characteristics were observed (Table 3).
• the taper angle was 38 degrees (Table 3). Since it is not an extremely small value or a large value, it is considered that a transparent electrode having excellent durability can be formed.
• the transparent conductive film in Examples 41 to 4-5 as described above can reduce the contact resistance with A1 compared to the conventional case, and therefore has the ability to drive liquid crystal and the like. Are better.
• a display device that can display halftones satisfactorily can be configured.
• Comparative Examples 4-1 and 4-2 Examples having different compositions from those of Examples 4 1 to 4 5 are given as Comparative Examples 4-1 and 4-2.
• the results of Comparative Examples 4-1 and 4 2 are also shown in Table 1, Table 2, Table 3, and Table 4.
• 3 ⁇ 4 Example 4 ⁇ to 4 5 are 3 ⁇ 4 Example ⁇ to
• Comparative Examples 4 ⁇ and 4 2 are comparative ⁇ and bible.
• Comparative Example 41 is a case where the value of the composition ratio [211] 7 ([211] + [311]) of the number of zinc atoms is 0.97.
• the measured values of Comparative Example 4-1 are as shown in Tables 1 to 4.
• the specific resistance of the target has a low value of 280 ⁇ cm.
• the specific resistance of the transparent conductive film formed is 0.86 ⁇ cm, which is higher than any of the above Examples 4 1-45 It is a value.
• a gZAgCl standard electrode potential is -0.98V, which is close to that of A1 thin film.
• the mobility is as low as 15cm 2 ZV'sec, and the light transmittance is as low as 79.8% (wavelength: 550nm). It is considered inferior to Examples 4-1 to 4-5.
• the etching rate with a 3.5 wt% oxalic acid aqueous solution was high in Examples 4 1 to 4 5.
• the taper angle becomes 134 degrees, and the obtained transparent electrode may be thinned or disconnected.
• Comparative Example 42 is a case where the value of the composition ratio [211] 7 ([211] + [311]) of the number of zinc atoms is 0.40.
• the measured values of Comparative Example 4-2 are as shown in Tables 1 to 4.
• the specific resistance of the target was 4400 ⁇ cm
• the specific resistance of the formed transparent conductive film was 0.08 ⁇ cm.
• the AgZAgCl standard electrode potential is -0.25 V, which is -0.71 V compared to that of the A1 thin film, which is very different. As a result, the battery reaction can hardly be suppressed, and it is considered difficult to prevent the elution of A1.
• the mobility is as low as 8 cm 2 ZV 'sec, and the light transmittance is as low as 79.8% (wavelength: 550 nm).
• the performance when used in a display device is as follows: It is thought that it is inferior compared with the said Examples 41-45.
• Example 4-6a (Stability of Al thin film in TMAH)
• Sputtering was performed for each of a case where a pure A1 sputtering target was mounted on a sputtering apparatus and a predetermined metal wire was placed on the sputtering target, and a case where nothing was placed.
• the details of each case are as follows.

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