WO2010116981A1 - Indium oxide-based electrically conductive transparent film, and process for production thereof - Google Patents

Indium oxide-based electrically conductive transparent film, and process for production thereof Download PDF

Info

Publication number
WO2010116981A1
WO2010116981A1 PCT/JP2010/056195 JP2010056195W WO2010116981A1 WO 2010116981 A1 WO2010116981 A1 WO 2010116981A1 JP 2010056195 W JP2010056195 W JP 2010056195W WO 2010116981 A1 WO2010116981 A1 WO 2010116981A1
Authority
WO
WIPO (PCT)
Prior art keywords
indium
transparent conductive
mol
molar ratio
film
Prior art date
Application number
PCT/JP2010/056195
Other languages
French (fr)
Japanese (ja)
Inventor
誠一郎 高橋
徳彦 宮下
真 池田
Original Assignee
三井金属鉱業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 三井金属鉱業株式会社 filed Critical 三井金属鉱業株式会社
Publication of WO2010116981A1 publication Critical patent/WO2010116981A1/en

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy

Definitions

  • the present invention relates to a transparent conductive film that can be formed as an amorphous film, the amorphous film can be easily patterned by weak acid etching, can be crystallized more easily, and the crystallized film has low resistance and high transmittance.
  • ITO film An indium oxide-tin oxide (In 2 O 3 —SnO 2 composite oxide, hereinafter referred to as “ITO”) film has high visible light transmittance and high electrical conductivity, so that it can be used as a transparent conductive film such as a liquid crystal display device or glass. However, it is difficult to obtain an amorphous film.
  • ITO indium oxide-tin oxide
  • an indium oxide-zinc oxide (IZO) transparent conductive film is known as an amorphous film.
  • IZO indium oxide-zinc oxide
  • the present invention can be formed as an amorphous film, and the amorphous film can be easily patterned by weak acid etching, can be crystallized more easily, and the crystallized film has low resistance and transmittance. It is an object of the present invention to provide an indium oxide-based transparent conductive film and a method for producing the same.
  • the present invention adds a specific additive element and the partial pressure of water is 1.0 ⁇ 10 ⁇ 4 Pa or more and 1.0 ⁇ 10 ⁇ 1 Pa or less. It has been found that a film formed under conditions can raise the crystallization temperature to, for example, 100 ° C. or higher over a wide composition range, and an amorphous film can be obtained even under film formation conditions of, for example, about 100 ° C. And completed.
  • the first aspect of the present invention is an oxidation containing indium oxide and tin as required, and at least one additive element selected from the group consisting of Sr, Li, La, Ca, Mg and Y.
  • the film was formed as an amorphous film using a sputtering target having a sintered body and having a partial pressure of water of 1.0 ⁇ 10 ⁇ 4 Pa to 1.0 ⁇ 10 ⁇ 1 Pa. It is in the transparent conductive film characterized by these.
  • the amorphous film can be easily patterned by weak acid etching, can be crystallized more easily, and the crystallized film has low resistance and high transmittance. Is.
  • a second aspect of the present invention is the transparent conductive film according to the first aspect, wherein the amorphous film contains hydrogen.
  • the film since the film is formed under the condition of a predetermined moisture pressure, it contains hydrogen.
  • the transparent conductive film according to the first or second aspect wherein the amorphous conductive film is crystallized by annealing and then crystallized. is there.
  • the additive element is strontium
  • the film composition is a molar ratio y of tin to 1 mol of indium. Is in the range of less than the value of ( ⁇ 4.1 ⁇ 10 ⁇ 2 Ln (x) ⁇ 9.3 ⁇ 10 ⁇ 2 ) represented by the molar ratio x of strontium to 1 mol of indium. It is in the conductive film.
  • an amorphous film is formed when the film is formed at a temperature lower than 100 ° C., and then the film can be crystallized when annealed at 100 ° C. to 300 ° C.
  • the additive element is strontium
  • the film composition is a molar ratio y of tin to 1 mol of indium. Is less than the value of ( ⁇ 4.1 ⁇ 10 ⁇ 2 Ln (x) ⁇ 9.3 ⁇ 10 ⁇ 2 ) represented by the molar ratio x of strontium to 1 mol of indium and ( ⁇ 1.6 ⁇ 10 ⁇ 2 Ln (x) ⁇ 3.7 ⁇ 10 ⁇ 2 ) or more.
  • the film is amorphous when formed at a temperature lower than 100 ° C., and can be crystallized when annealed at 100 ° C. to 300 ° C. thereafter.
  • the additive element is lithium
  • the molar ratio y of tin to 1 mol of indium is indium 1
  • the transparent conductive film is characterized by being in a range less than the value of ( ⁇ 1.6 ⁇ 10 ⁇ 1 Ln (x) ⁇ 5.9 ⁇ 10 ⁇ 1 ) represented by a molar ratio x of lithium to mole. .
  • an amorphous film is formed when the film is formed at a temperature lower than 100 ° C., and the film can be crystallized after annealing at 100 ° C. to 300 ° C.
  • the additive element is lithium
  • the film composition is a molar ratio y of tin to 1 mol of indium. Is less than the value of ( ⁇ 1.6 ⁇ 10 ⁇ 1 Ln (x) ⁇ 5.9 ⁇ 10 ⁇ 1 ) expressed by the molar ratio x of lithium to 1 mol of indium and ( ⁇ 3.5 ⁇ 10 ⁇ 2 Ln (x) ⁇ 1.6 ⁇ 10 ⁇ 1 ) or more.
  • an amorphous film is formed when the film is formed at a temperature lower than 100 ° C., and then the film can be crystallized when annealed at 100 ° C. to 300 ° C.
  • the additive element is lanthanum
  • the film composition is a molar ratio y of tin to 1 mol of indium. Is in a range of less than the value of ( ⁇ 6.7 ⁇ 10 ⁇ 2 Ln (x) ⁇ 2.2 ⁇ 10 ⁇ 1 ) represented by the molar ratio x of lanthanum to 1 mol of indium. It is in the conductive film.
  • an amorphous film can be formed when the film is formed at a temperature lower than 100 ° C., and then the film can be crystallized when annealed at 100 ° C. to 300 ° C.
  • the additive element is lanthanum
  • the film composition is a molar ratio y of tin to 1 mol of indium. Is less than the value of ( ⁇ 6.7 ⁇ 10 ⁇ 2 Ln (x) ⁇ 2.2 ⁇ 10 ⁇ 1 ) expressed by the molar ratio x of lanthanum to 1 mol of indium and ( ⁇ 2.9 ⁇ 10 ⁇ 2 Ln (x) ⁇ 1.3 ⁇ 10 ⁇ 1 ) or more.
  • the film when the film is formed at a temperature lower than 100 ° C., it becomes an amorphous film, and thereafter, it can be crystallized when annealed at 100 ° C. to 300 ° C.
  • the additive element is calcium
  • the molar ratio y of tin to 1 mol of indium is indium 1
  • the transparent conductive film is characterized by being in a range of less than a value of ( ⁇ 4.1 ⁇ 10 ⁇ 2 Ln (x) ⁇ 9.3 ⁇ 10 ⁇ 2 ) represented by a molar ratio of calcium to mole x. .
  • an amorphous film is formed when the film is formed at a temperature lower than 100 ° C., and then the film can be crystallized when annealed at 100 ° C. to 300 ° C.
  • the additive element is calcium
  • the molar ratio y of tin to 1 mol of indium is indium 1 represented by a molar ratio x of calcium to moles (-4.1 ⁇ 10 -2 Ln (x ) -9.3 ⁇ 10 -2) less than the value and (-1.6 ⁇ 10 -2 Ln ( x)
  • a transparent conductive film characterized by being in the range of ⁇ 3.7 ⁇ 10 ⁇ 2 ) or more.
  • an amorphous film can be formed when the film is formed at a temperature lower than 100 ° C., and then the film can be crystallized when annealed at 100 ° C. to 300 ° C.
  • the additive element is magnesium
  • the molar ratio y of tin to 1 mole of indium is indium 1
  • the transparent conductive film is characterized by being in a range less than the value of ( ⁇ 4.1 ⁇ 10 ⁇ 2 Ln (x) ⁇ 9.3 ⁇ 10 ⁇ 2 ) represented by a molar ratio x of magnesium to mol. .
  • an amorphous film can be formed when the film is formed at a temperature lower than 100 ° C., and then the film can be crystallized when annealed at 100 ° C. to 300 ° C.
  • the additive element is magnesium
  • the molar ratio y of tin to 1 mol of indium is indium 1 Less than the value of ( ⁇ 4.1 ⁇ 10 ⁇ 2 Ln (x) ⁇ 9.3 ⁇ 10 ⁇ 2 ) expressed by the molar ratio x of magnesium to mol and ( ⁇ 1.6 ⁇ 10 ⁇ 2 Ln ( x)
  • a transparent conductive film characterized by being in the range of ⁇ 3.7 ⁇ 10 ⁇ 2 ) or more.
  • the film when the film is formed at a temperature lower than 100 ° C., it becomes an amorphous film, and thereafter, it can be crystallized when annealed at 100 ° C. to 300 ° C.
  • the additive element is yttrium
  • the film composition has a molar ratio y of tin to 1 mol of indium. Is in a range less than a value of ( ⁇ 2.5 ⁇ 10 ⁇ 2 Ln (x) ⁇ 5.8 ⁇ 10 ⁇ 2 ) represented by a molar ratio x of yttrium to 1 mol of indium. It is in the conductive film.
  • an amorphous film is formed when formed at a temperature lower than 100 ° C., and crystallization can be performed when annealed at 100 ° C. to 300 ° C. thereafter.
  • the additive element is yttrium
  • the film composition has a molar ratio y of tin to 1 mol of indium. Is less than the value of ( ⁇ 2.5 ⁇ 10 ⁇ 2 Ln (x) ⁇ 5.8 ⁇ 10 ⁇ 2 ) expressed by the molar ratio x of yttrium to 1 mol of indium and ( ⁇ 2.2 ⁇ 10 ⁇ 2 Ln (x) ⁇ 1.5 ⁇ 10 ⁇ 1 ) or more.
  • the film when the film is formed at a temperature lower than 100 ° C., it becomes an amorphous film, and thereafter, it can be crystallized when annealed at 100 ° C. to 300 ° C.
  • the sixteenth aspect of the present invention contains indium oxide and tin as required, and Sr (strontium), Li (lithium), La (lanthanum), Ca (calcium), Mg (magnesium) and Y (yttrium).
  • a sputtering target comprising an oxide sintered body containing an additive element is at least one selected from the group consisting of less than 100 ° C., the partial pressure of water 1.0 ⁇ 10 -4 Pa or more and 1.0
  • an amorphous film is formed under a condition of ⁇ 10 ⁇ 1 Pa or less.
  • the amorphous film can be easily patterned by weak acid etching, can be crystallized more easily, and the crystallized film has low resistance and high transmittance. Is.
  • a seventeenth aspect of the present invention in the method for producing a transparent conductive film according to the sixteenth aspect, after forming an amorphous film, it is crystallized by annealing at 100 ° C. to 300 ° C. to obtain a transparent conductive film.
  • a method for producing a transparent conductive film after forming an amorphous film, it is crystallized by annealing at 100 ° C. to 300 ° C. to obtain a transparent conductive film.
  • an amorphous film can be formed at a temperature lower than 100 ° C., and then annealed at 100 ° C. to 300 ° C. for crystallization, thereby improving the environmental resistance.
  • the additive element is strontium
  • the molar ratio y of tin to 1 mol of indium is indium 1
  • the additive element is strontium
  • the molar ratio y of tin to 1 mol of indium is indium 1 Less than the value of ( ⁇ 4.1 ⁇ 10 ⁇ 2 Ln (x) ⁇ 9.3 ⁇ 10 ⁇ 2 ) expressed by the molar ratio x of strontium to mole and ( ⁇ 1.6 ⁇ 10 ⁇ 2 Ln ( x)
  • a film having a film composition in the range of ⁇ 3.7 ⁇ 10 ⁇ 2 ) or higher is formed under conditions where the partial pressure of water is 1.0 ⁇ 10 ⁇ 4 Pa or higher and 1.0 ⁇ 10 ⁇ 3 Pa or lower. It is in the manufacturing method of the transparent conductive film characterized by carrying out a film
  • the additive element is lithium
  • the molar ratio y of tin to 1 mole of indium is indium 1
  • the additive element is lithium
  • the molar ratio y of tin to 1 mol of indium is indium 1 Less than the value of ( ⁇ 1.6 ⁇ 10 ⁇ 1 Ln (x) ⁇ 5.9 ⁇ 10 ⁇ 1 ) expressed by the molar ratio x of lithium to mol and ( ⁇ 3.5 ⁇ 10 ⁇ 2 Ln ( x)
  • a film having a film composition in the range of ⁇ 1.6 ⁇ 10 ⁇ 1 ) or more is formed under a condition where the partial pressure of water is 1.0 ⁇ 10 ⁇ 4 Pa or more and 1.0 ⁇ 10 ⁇ 3 Pa or less. It is in the manufacturing method of the transparent conductive film characterized by carrying out a film
  • the additive element is lanthanum
  • the molar ratio y of tin to 1 mol of indium is indium 1
  • the additive element is lanthanum
  • the molar ratio y of tin to 1 mol of indium is indium 1 It is less than the value of ( ⁇ 6.7 ⁇ 10 ⁇ 2 Ln (x) ⁇ 2.2 ⁇ 10 ⁇ 1 ) expressed by the molar ratio x of lanthanum to mol and ( ⁇ 2.9 ⁇ 10 ⁇ 2 Ln ( x)
  • a film having a film composition in the range of ⁇ 1.3 ⁇ 10 ⁇ 1 ) or more is formed under conditions where the partial pressure of water is 1.0 ⁇ 10 ⁇ 4 Pa or more and 1.0 ⁇ 10 ⁇ 3 Pa or less. It is in the manufacturing method of the transparent conductive film characterized by carrying out a film
  • the additive element is calcium
  • the molar ratio y of tin to 1 mol of indium is indium 1
  • the additive element is calcium
  • the molar ratio y of tin to 1 mol of indium is indium 1 Less than the value of ( ⁇ 4.1 ⁇ 10 ⁇ 2 Ln (x) ⁇ 9.3 ⁇ 10 ⁇ 2 ) expressed by the molar ratio x of calcium to mol and ( ⁇ 1.6 ⁇ 10 ⁇ 2 Ln ( x)
  • a film having a film composition in the range of ⁇ 3.7 ⁇ 10 ⁇ 2 ) or higher is formed under conditions where the partial pressure of water is 1.0 ⁇ 10 ⁇ 4 Pa or higher and 1.0 ⁇ 10 ⁇ 3 Pa or lower. It is in the manufacturing method of the transparent conductive film characterized by carrying out a film
  • the additive element is magnesium
  • the molar ratio y of tin to 1 mol of indium is indium 1 to deposit a film of the film composition in the range of less than the value of which is expressed as a molar ratio x of magnesium to molar (-4.1 ⁇ 10 -2 Ln (x ) -9.3 ⁇ 10 -2) It is in the manufacturing method of the transparent conductive film characterized.
  • the additive element is magnesium
  • the molar ratio y of tin to 1 mol of indium is indium 1 Less than the value of ( ⁇ 4.1 ⁇ 10 ⁇ 2 Ln (x) ⁇ 9.3 ⁇ 10 ⁇ 2 ) expressed by the molar ratio x of magnesium to mol and ( ⁇ 1.6 ⁇ 10 ⁇ 2 Ln ( x)
  • a film having a film composition in the range of ⁇ 3.7 ⁇ 10 ⁇ 2 ) or higher is formed under conditions where the partial pressure of water is 1.0 ⁇ 10 ⁇ 4 Pa or higher and 1.0 ⁇ 10 ⁇ 3 Pa or lower. It is in the manufacturing method of the transparent conductive film characterized by carrying out a film
  • the additive element is yttrium
  • the molar ratio y of tin to 1 mol of indium is indium 1
  • the additive element is yttrium
  • the molar ratio y of tin to 1 mol of indium is indium 1 Less than the value of ( ⁇ 2.5 ⁇ 10 ⁇ 2 Ln (x) ⁇ 5.8 ⁇ 10 ⁇ 2 ) expressed by the molar ratio x of yttrium to mol, and ( ⁇ 2.2 ⁇ 10 ⁇ 2 Ln ( x)
  • a film having a film composition in the range of ⁇ 1.5 ⁇ 10 ⁇ 1 ) or more is formed under a condition where the partial pressure of water is 1.0 ⁇ 10 ⁇ 4 Pa or more and 1.0 ⁇ 10 ⁇ 3 Pa or less. It is in the manufacturing method of the transparent conductive film characterized by carrying out a film
  • a film is formed under the condition that tin and a specific additive element are added to indium oxide, and the partial pressure of water is 1.0 ⁇ 10 ⁇ 4 Pa or more and 1.0 ⁇ 10 ⁇ 1 Pa or less.
  • the film thus obtained can be made relatively easily an amorphous film, can be easily patterned by weak acid etching after the film formation, can be crystallized more easily, and the crystallized film has low resistance and high transmittance. There exists an effect that a transparent conductive film can be manufactured.
  • the sputtering target for transparent conductive film used for forming the indium oxide-based transparent conductive film of the present invention is mainly composed of indium oxide and contains tin, and Sr (strontium), Li (lithium), La (lanthanum). ), Ca (calcium), Mg (magnesium), and Y (yttrium), and is an oxide sintered body containing at least one specific additive element selected from the group consisting of Y (yttrium). Alternatively, it may be present as a complex oxide or as a solid solution, and is not particularly limited.
  • the content of the additive element is such that the film formed at a film forming temperature of 100 ° C. or less under the condition that the partial pressure of water is 1.0 ⁇ 10 ⁇ 4 Pa or more and 1.0 ⁇ 10 ⁇ 1 Pa or less is an amorphous film. What is necessary is just to select so that it may form into a film, although it changes with the kind of additive element, and film-forming conditions, it can select from the range of 0.00001 mol or more and less than 0.10 mol with respect to 1 mol of indium.
  • the content of tin is selected from the range of 0.001 to 0.3 mol, preferably 0.005 to 0.3 mol, with respect to 1 mol of indium, and sputtering containing tin in such a range. It is desirable to form a film using a target. Within this range, the density and mobility of carrier electrons in the sputtering target can be appropriately controlled to keep the conductivity in a good range. Further, addition beyond this range is not preferable because the mobility of carrier electrons of the sputtering target is lowered and the conductivity is deteriorated.
  • content of the additive element and tin in the transparent conductive film formed with the sputtering target having such a specific composition is the same content as the content in the used sputtering target.
  • the entire amount of a single film may be dissolved and analyzed by ICP.
  • FIB or the like an element analyzer (EDS, WDS, Auger analysis, etc.) attached to the SEM, TEM, etc. ) Can also be specified.
  • Such a sputtering target has a resistance value that can be sputtered by DC magnetron sputtering, it can be sputtered by relatively inexpensive DC magnetron sputtering.
  • a high-frequency magnetron sputtering apparatus may be used.
  • the same composition is obtained.
  • an amorphous indium oxide-based transparent conductive film having a relatively low crystallization temperature can be formed.
  • hydrogen is taken into the amorphous film. That is, the formed amorphous film contains hydrogen.
  • the amorphous film is formed at the predetermined moisture pressure described above or substantially 1.0 ⁇ without water. It can be confirmed whether or not the film is formed at less than 10 ⁇ 4 Pa.
  • an atmospheric gas generally Ar, a gas containing oxygen as necessary, which is introduced into the film formation chamber during film formation, for example, It is only necessary to introduce water vapor through a mass flow controller or the like with a pressure of the order of 10 ⁇ 4 Pa, and when the ultimate vacuum is less than 10 ⁇ 4 Pa and a high vacuum, about 1/100 to 1/10 of the atmospheric gas.
  • the pressure is Note that, under the condition that the ultimate degree of vacuum is about 10 ⁇ 4 to 10 ⁇ 3 Pa and the degree of vacuum is poor, the main component of the residual gas is water. That is, since the ultimate vacuum corresponds approximately to the partial pressure of water, a desired partial pressure of water can be obtained without particularly introducing water vapor.
  • Such an indium oxide-based transparent conductive film according to the present invention contains a predetermined amount of an additive element, so that film formation is performed at room temperature or higher and a crystallization temperature, that is, a temperature condition lower than 100 ° C. or higher.
  • the film is formed in an amorphous state.
  • such an amorphous film has an advantage that it can be etched with a weakly acidic etchant.
  • such an etching has an effect that a fine pattern can be formed without any residue.
  • the etching is included in the patterning step and is for obtaining a predetermined pattern.
  • the resistivity of the transparent conductive film obtained varies depending on the additive element and the tin content, but the resistivity is 1.0 ⁇ 10 ⁇ 4 to 1.0 ⁇ 10 ⁇ 3 ⁇ ⁇ cm.
  • the crystallization temperature of the deposited film varies depending on the content of additive elements and tin contained, and increases as the content increases.
  • the crystallization temperature is increased.
  • Such a temperature region is used in a normal semiconductor manufacturing process, it can be crystallized in such a process. In this temperature range, those that crystallize at 100 ° C. to 300 ° C. are preferred, crystals that crystallize at 150 ° C. to 250 ° C. are more preferred, and those that crystallize at 200 ° C. to 250 ° C. are most preferred.
  • annealing refers to heating at a desired temperature for a certain period of time in air, atmosphere, or vacuum.
  • the fixed time is generally several minutes to several hours, but a short time is preferred industrially if the effect is the same.
  • the transparent conductive film after being crystallized by annealing has improved transmittance on the short wavelength side, for example, the average transmittance at a wavelength of 400 to 500 nm is 85% or more. This also eliminates the problem that the film which is a problem in IZO is yellowish. In general, a higher transmittance on the short wavelength side is preferred.
  • the crystallized transparent conductive film has improved etching resistance and cannot be etched with a weakly acidic etchant that can be etched with an amorphous film. This improves the corrosion resistance in the subsequent process and the environmental resistance of the device itself.
  • the crystallization temperature after film formation can be set to a desired temperature, so that heat treatment at a temperature higher than the crystallization temperature is not applied after film formation.
  • the amorphous state may be maintained, or after patterning after film formation, crystallization may be performed by heat treatment at a temperature equal to or higher than the crystallization temperature to change the etching resistance.
  • the film can be formed as an amorphous film needs to be formed at a film formation temperature lower than the crystallization temperature in the composition of the film formed as described above, and the content of tin and additive elements is small. less becomes the crystallization temperature as the composition is low, tin and although the crystallization temperature as the composition containing a large amount of the additive element is high tends, 1.0 the partial pressure of water 1.0 ⁇ 10 -4 Pa or more ⁇
  • the crystallization temperature of each composition is about 50 to 100 ° C. as compared with the case where the film is formed with a partial pressure of water of less than 1.0 ⁇ 10 ⁇ 4 Pa. Can be high.
  • the crystallization temperature is less than 100 ° C., particularly near room temperature, and the film formation conditions for obtaining an amorphous film are In a fairly severe composition range, the crystallization temperature is increased to, for example, 100 ° C. or higher by setting the partial pressure of water to 1.0 ⁇ 10 ⁇ 4 Pa or more and 1.0 ⁇ 10 ⁇ 1 Pa or less.
  • an amorphous film can be obtained even under film forming conditions of about 100 ° C.
  • an amorphous film having a crystallization temperature of 100 ° C. or more is formed even in a film formation under a normal condition in which the content of the additive element is relatively high and the partial pressure of water is lower than 1.0 ⁇ 10 ⁇ 4 Pa.
  • the crystallization temperature due to annealing slightly increases. Needless to say, an amorphous film can be formed.
  • the partial pressure of water is lower than 1.0 ⁇ 10 ⁇ 4 Pa, the effect of increasing the crystallization temperature as described above is not remarkable, while the partial pressure of water is the upper limit (1.0 ⁇ 10 10 -1 Pa), the resulting film is amorphous, but the crystallization temperature rises, and since it does not crystallize even under 300 ° C. annealing conditions, the specific resistance is not reduced and the film is annealed. Even if it is crystallized, the specific resistance of the film does not decrease, and it becomes difficult to obtain a crystallized film of 5.0 ⁇ 10 ⁇ 4 ⁇ ⁇ cm or less, which is not preferable.
  • the amorphous film formed under such a moisture pressure condition contains hydrogen, and the presence of hydrogen can be confirmed by the test method described above.
  • amorphous film when the film is formed under a normal condition where the partial pressure of water is lower than 1.0 ⁇ 10 ⁇ 4 Pa, in the composition range where an amorphous film having a crystallization temperature of 100 ° C. or higher cannot be formed, An amorphous film can be obtained by adjusting the pressure to 1.0 ⁇ 10 ⁇ 4 Pa or more and 1.0 ⁇ 10 ⁇ 1 Pa or less, but such a composition range depends on the kind of the additive element. Hereinafter, such a composition range will be described.
  • the additive element is Sr
  • an amorphous film is formed only when the partial pressure of water is 1.0 ⁇ 10 ⁇ 4 Pa or more and 1.0 ⁇ 10 ⁇ 1 Pa or less, and thereafter 100 ° C. to 300 ° C. in the composition range of crystallization when annealed, the molar ratio of tin to indium mole y (mol) is represented by the molar ratio x of Sr relative to 1 mol of indium (-4.1 ⁇ 10 - 2 Ln (x) ⁇ 9.3 ⁇ 10 ⁇ 2 ).
  • the partial pressure of water is 1.0 It becomes an amorphous film under the condition of x10 ⁇ 4 Pa or more and 1.0 ⁇ 10 ⁇ 3 Pa or less, and then crystallizes when annealed at 100 ° C. to 300 ° C., which is more preferable in consideration of the film forming process. .
  • the additive element is Li
  • an amorphous film is formed only when the partial pressure of water is 1.0 ⁇ 10 ⁇ 4 Pa or more and 1.0 ⁇ 10 ⁇ 1 Pa or less, and then 100 ° C. to 300 ° C.
  • the molar ratio y (mol) of tin to 1 mol of indium is represented by the molar ratio x of Li to 1 mol of indium ( ⁇ 1.6 ⁇ 10 ⁇ 1 Ln (x) ⁇ 5.9 ⁇ 10 ⁇ 1 ).
  • the molar ratio y of tin to 1 mol of indium is represented by the molar ratio x of Li to 1 mol of indium ( ⁇ 1.6 ⁇ 10 ⁇ 1 Ln (x)
  • the partial pressure of water is 1. It becomes an amorphous film under conditions of 0 ⁇ 10 ⁇ 4 Pa or more and 1.0 ⁇ 10 ⁇ 3 Pa or less, and then crystallizes when annealed at 100 ° C. to 300 ° C. Become.
  • the additive element is La
  • an amorphous film is formed only when the partial pressure of water is 1.0 ⁇ 10 ⁇ 4 Pa or more and 1.0 ⁇ 10 ⁇ 1 Pa or less.
  • the composition range that crystallizes when annealed at 300 ° C. is expressed by the molar ratio y of tin to 1 mol of indium expressed as the molar ratio x of La to 1 mol of indium ( ⁇ 6.7 ⁇ 10 ⁇ 2 Ln (x) ⁇ 2.2 ⁇ 10 ⁇ 1 ).
  • the molar ratio y of tin to 1 mol of indium is represented by the molar ratio x of La to 1 mol of indium ( ⁇ 6.7 ⁇ 10 ⁇ 2 Ln (x) ⁇ 2.2 ⁇ 10 ⁇ 1 ) and less than ⁇ 2.9 ⁇ 10 ⁇ 2 Ln (x) ⁇ 1.3 ⁇ 10 ⁇ 1 ), the partial pressure of water is 1.0. It becomes an amorphous film under the condition of x10 ⁇ 4 Pa or more and 1.0 ⁇ 10 ⁇ 3 Pa or less, and then crystallizes when annealed at 100 ° C. to 300 ° C., which is more preferable in consideration of the film forming process. .
  • the additional element of Ca for the first time become the amorphous film by a partial pressure below 1.0 ⁇ 10 -4 Pa or 1.0 ⁇ 10 -1 Pa under the conditions of water, then, 100 ° C. ⁇
  • the molar ratio y of tin to 1 mol of indium is expressed by the molar ratio x of Ca to 1 mol of indium ( ⁇ 4.1 ⁇ 10 ⁇ 2 Ln (x) ⁇ 9.3 ⁇ 10 ⁇ 2 ).
  • the molar ratio y of tin to 1 mol of indium is expressed by the molar ratio x of Ca to 1 mol of indium ( ⁇ 4.1 ⁇ 10 ⁇ 2 Ln (x)
  • the partial pressure of water is 1.0. It becomes an amorphous film under the condition of x10 ⁇ 4 Pa or more and 1.0 ⁇ 10 ⁇ 3 Pa or less, and then crystallizes when annealed at 100 ° C. to 300 ° C., which is more preferable in consideration of the film forming process. .
  • the additional element of Mg for the first time become the amorphous film by a partial pressure below 1.0 ⁇ 10 -4 Pa or 1.0 ⁇ 10 -1 Pa under the conditions of water, then, 100 ° C. ⁇
  • the molar ratio y of tin to 1 mol of indium is expressed by the molar ratio x of Mg to 1 mol of indium ( ⁇ 4.1 ⁇ 10 ⁇ 2 Ln (x) ⁇ 9.3 ⁇ 10 ⁇ 2 ).
  • the molar ratio y of tin to 1 mol of indium is expressed by the molar ratio x of Mg to 1 mol of indium ( ⁇ 4.1 ⁇ 10 ⁇ 2 Ln (x)
  • the partial pressure of water is 1.0. It becomes an amorphous film under the condition of x10 ⁇ 4 Pa or more and 1.0 ⁇ 10 ⁇ 3 Pa or less, and then crystallizes when annealed at 100 ° C. to 300 ° C., which is more preferable in consideration of the film forming process. .
  • an amorphous film is formed only when the partial pressure of water is 1.0 ⁇ 10 ⁇ 4 Pa or more and 1.0 ⁇ 10 ⁇ 1 Pa or less.
  • the composition range that crystallizes when annealed at 300 ° C. is expressed by a molar ratio y of tin to 1 mol of indium and a molar ratio x of Y to 1 mol of indium ( ⁇ 2.5 ⁇ 10 ⁇ 2 Ln (x) ⁇ 5.8 ⁇ 10 ⁇ 2 ).
  • the molar ratio y of tin to 1 mol of indium is represented by the molar ratio x of Y to 1 mol of indium ( ⁇ 2.5 ⁇ 10 ⁇ 2 Ln (x)
  • the partial pressure of water is 1.0. It becomes an amorphous film under the condition of x10 ⁇ 4 Pa or more and 1.0 ⁇ 10 ⁇ 3 Pa or less, and then crystallizes when annealed at 100 ° C. to 300 ° C., which is more preferable in consideration of the film forming process. .
  • the manufacturing method of the sputtering target used in the present invention will be described. However, this is merely an example, and the manufacturing method is not particularly limited.
  • an oxide of a constituent element is generally used, but these simple substances, compounds, complex oxides, and the like may be used as a raw material.
  • a simple substance or a compound it is made to go through a process of making it oxide in advance.
  • the method of mixing and molding these raw material powders at a desired blending ratio is not particularly limited, and various conventionally known wet methods or dry methods can be used.
  • Examples of the dry method include a cold press method and a hot press method.
  • the mixed powder is filled in a mold to produce a molded body and fired.
  • the hot press method the mixed powder is fired and sintered in a mold.
  • a filtration molding method (see JP-A-11-286002) is preferably used.
  • This filtration molding method is a filtration molding die made of a water-insoluble material for obtaining a molded body by draining water from a ceramic raw material slurry under reduced pressure, and a lower molding die having one or more drain holes And a water-permeable filter placed on the molding lower mold, and a molding mold clamped from the upper surface side through a sealing material for sealing the filter, the molding lower mold, Forming mold, sealing material, and filter are assembled so that they can be disassembled respectively.
  • mixed powder, ion-exchanged water and organic Prepare a slurry consisting of additives, inject the slurry into a filtration mold, drain the water in the slurry only from the filter surface side, and produce a molded body. After drying degreasing, and firing.
  • the firing temperature of the one formed by the cold press method or the wet method is preferably 1300 to 1650 ° C., more preferably 1500 to 1650 ° C., and the atmosphere is an air atmosphere, an oxygen atmosphere, a non-oxidizing atmosphere, a vacuum atmosphere, or the like. It is.
  • the hot press method sintering is preferably performed at around 1200 ° C., and the atmosphere is a non-oxidizing atmosphere, a vacuum atmosphere, or the like.
  • molding and a process is given to a predetermined dimension, and it is set as a target.
  • aqueous PVA solution was added as a binder, mixed, dried, and cold pressed to obtain a molded body.
  • This molded body was degreased at 600 ° C. for 10 hours in the air at a temperature increase of 60 ° C./h, and then fired at 1550 ° C. for 8 hours in an oxygen atmosphere to obtain a sintered body.
  • the firing condition is that the temperature is raised from room temperature to 800 ° C. at 200 ° C./h, the temperature is raised from 800 ° C. to 1550 ° C. at 400 ° C./h, held for 8 hours, and then 1550 ° C. to room temperature is 100 ° C. It is a condition of cooling under the condition of / h. Thereafter, this sintered body was processed to obtain a target.
  • In 2 O 3 powder and Li 2 CO 3 powder were prepared, mixed in a ball mill in a dry state, and calcined at 1000 ° C. for 3 hours in the air to obtain LiInO 2 powder.
  • the same as Sr-ITO except that about 1.0 kg of LiInO 2 powder, In 2 O 3 powder and SnO 2 powder were prepared (the composition of each metal atom was as shown in Tables 3 and 4 below).
  • a target was produced. However, the firing temperature is 1450 ° C.
  • (Sputtering target production example 4) (Ca-ITO) Prepare In 2 O 3 powder with a purity of> 99.99%, SnO 2 powder, and CaCO 3 with a purity of> 99.5%.
  • the In 2 O 3 powder and the CaCO 3 powder are mixed in a ball mill in a dry state. Calcination was performed at 1200 ° C. in the air for 3 hours to obtain CaIn 2 O 4 powder.
  • Sr-ITO was used except that about 1.0 kg of CaIn 2 O 4 powder, In 2 O 3 powder and SnO 2 powder were prepared (the composition of each metal atom was as shown in Tables 7 and 8 below). Similarly, a target was produced.
  • the sputtering conditions were as follows, and a film having a thickness of 1200 mm was obtained.
  • Sputtering method DC magnetron sputtering
  • Exhaust device Rotary pump + cryopump Ultimate vacuum: 5.3 ⁇ 10 ⁇ 5 [Pa]
  • Ar pressure 4.0 ⁇ 10 ⁇ 1 [Pa]
  • Substrate used: Corning # 1737 (glass for liquid crystal display) t 0.8 mm
  • the optimal oxygen partial pressure for room temperature film formation and the oxygen partial pressure for film formation with the lowest resistivity after annealing at 250 ° C. were different for all samples.
  • the transparent conductive film formed at the oxygen partial pressure at the time of film formation having the lowest resistivity after annealing at 250 ° C. was cut out to a size of 13 mm square, and these samples were 1 at 250 ° C. in the atmosphere.
  • amorphous is a and crystal is c.
  • the crystallization temperature of each composition was measured and shown in Table 13.
  • the crystallization temperature is a temperature at which the film is crystallized after being deposited at room temperature, and those that do not become amorphous in the film formation at room temperature were set to less than 100 ° C.
  • transparent conductive films formed at the oxygen partial pressure at the time of film formation having the lowest resistivity after annealing at 250 ° C. were cut into 13 mm square sizes, and transmission spectra were measured for the annealed films. .
  • Table 13 shows the average transmittance after annealing.
  • each composition was formed at the oxygen partial pressure at the time of film formation having the lowest resistivity after annealing at 250 ° C., cut into a size of 10 ⁇ 50 mm, and ITO-05N (oxalic acid, Kanto Chemical Co., Ltd.) as an etching solution.
  • Etching rate ( ⁇ / sec) was measured at a temperature of 30 ° C. using an oxalic acid concentration (50 g / L). The results are shown in Table 13.
  • FIGS. 1 and 2 the extent of less than a value of (4.1 ⁇ 10 -2 Ln (x ) -9.3 ⁇ 10 -2), as an amorphous film at a deposition temperature less than 100 ° C.
  • Samples that can be formed and crystallized at 100 to 300 ° C. are indicated by ⁇ , and samples that cannot be formed as an amorphous film are indicated by ⁇ .
  • samples that can be formed as an amorphous film at a film forming temperature of less than 100 ° C. and crystallized at 100 to 300 ° C. are indicated by ⁇ , and others are indicated by ⁇ .
  • the molar ratio y (mol) of tin to 1 mol of indium is represented by the molar ratio x of Sr to 1 mol of indium ( ⁇ 4.1 ⁇ 10 ⁇ 2 Ln (x) ⁇ 9.3).
  • the range of the range not less than the value of ( ⁇ 10 ⁇ 2 ) and not more than the value of ( ⁇ 2.9 ⁇ 10 ⁇ 1 Ln (x) ⁇ 6.7 ⁇ 10 ⁇ 1 )
  • the film can be formed as an amorphous film.
  • the molar ratio y (mol) of tin to 1 mol of indium is represented by the molar ratio x of Sr to 1 mol of indium ( ⁇ 4.1 ⁇ 10 ⁇ 2 Ln).
  • the film is formed at a temperature of less than 100 ° C. and a water pressure of 1.0 ⁇ 10 ⁇ 2 Pa, it becomes an amorphous film, and then 100 Crystallization occurred when annealed at a temperature between 0 ° C and 300 ° C.
  • the molar ratio y (mol) of tin to 1 mol of indium is represented by the molar ratio x of Sr to 1 mol of indium ( ⁇ 1.6 ⁇ 10 ⁇ 2 Ln (x) ⁇ ).
  • the molar ratio y (mol) of tin to 1 mol of indium is expressed by the molar ratio x of Sr to 1 mol of indium ( ⁇ 4.1 ⁇ 10 ⁇ 2 Ln (x) ⁇ 9.3 ⁇ ).
  • amorphous film can be formed at a temperature of less than 100 ° C. if the film is formed under conditions of 4 Pa or more and 1.0 ⁇ 10 ⁇ 3 Pa or less. After the film formation, the crystal is obtained by annealing at 100 ° C. to 300 ° C. It turned out that it becomes a film
  • Li-containing composition transparent conductive film test example 1 Li-containing composition transparent conductive film test example 1
  • the substrate temperature was room temperature (about 20 ° C.)
  • the oxygen partial pressure was between 0 and 3.0 sccm. (Corresponding to 0 to 1.1 ⁇ 10 ⁇ 2 Pa) while obtaining a transparent conductive film of each composition.
  • the sputtering conditions were as follows, and a film having a thickness of 1200 mm was obtained.
  • Sputtering method DC magnetron sputtering
  • Exhaust device Rotary pump + cryopump Ultimate vacuum: 5.3 ⁇ 10 ⁇ 5 [Pa]
  • Ar pressure 4.0 ⁇ 10 ⁇ 1 [Pa]
  • Substrate used: Corning # 1737 (glass for liquid crystal display) t 0.8 mm
  • the optimal oxygen partial pressure for room temperature film formation and the oxygen partial pressure for film formation with the lowest resistivity after annealing at 250 ° C. were different for all samples.
  • transparent conductive films formed at the oxygen partial pressure at the time of film formation having the lowest resistivity after annealing at 250 ° C. were cut into 13 mm square sizes, and these samples were 250 ° C. in the atmosphere.
  • Table 16 the crystal states after annealing at room temperature for 1 hour, after film formation at room temperature and after annealing at 250 ° C. are a for amorphous and c for crystal.
  • the crystallization temperature of each composition was measured and shown in Table 16.
  • the crystallization temperature is a temperature at which the film is crystallized after being deposited at room temperature, and those that do not become amorphous in the film formation at room temperature were set to less than 100 ° C.
  • transparent conductive films formed at the oxygen partial pressure at the time of film formation having the lowest resistivity after annealing at 250 ° C. were cut into 13 mm square sizes, and transmission spectra were measured for the annealed films. .
  • Table 16 shows the average transmittance after annealing.
  • each composition was formed at the oxygen partial pressure at the time of film formation having the lowest resistivity after annealing at 250 ° C., cut into a size of 10 ⁇ 50 mm, and ITO-05N (oxalic acid, Kanto Chemical Co., Ltd.) as an etching solution.
  • Etching rate ( ⁇ / sec) was measured at a temperature of 30 ° C. using an oxalic acid concentration (50 g / L). The results are shown in Table 16.
  • Li-containing composition transparent conductive film test example 2 A transparent conductive film having each composition was obtained under the above-described conditions except that the target having the composition shown in Table 3 manufactured as described above was used and the water pressure was 8.0 ⁇ 10 ⁇ 4 Pa.
  • Li-containing composition transparent conductive film reference example A transparent conductive film having each composition was obtained under the above-described conditions except that the target having the composition shown in Table 4 manufactured as described above was used and the water pressure was 5.0 ⁇ 10 ⁇ 6 Pa.
  • Tables 16 to 18 are shown in FIGS. 4 to 6, respectively.
  • samples that can be formed as an amorphous film at a film forming temperature of less than 100 ° C. and crystallized at 100 to 300 ° C. are indicated by ⁇ , and others are indicated by ⁇ .
  • the molar ratio y (mol) of tin to 1 mol of indium is represented by the molar ratio x of Li to 1 mol of indium ( ⁇ 1.6 ⁇ 10 ⁇ 1 Ln (x) ⁇ 5.9).
  • ⁇ 10 -1) is a value or more and (-2.5 ⁇ 10 -1 Ln (x ) -5.7 ⁇ 10 -1 values less range), as is apparent from FIG. 6, the water pressure Is 5.0 ⁇ 10 ⁇ 6 Pa, which is a range in which an amorphous film can be formed even in the absence of water.
  • the molar ratio y (mol) of tin to 1 mol of indium is expressed by the molar ratio x of Li to 1 mol of indium ( ⁇ 1.6 ⁇ 10 ⁇ 1 Ln).
  • the film is formed at a temperature of less than 100 ° C. and a water pressure of 1.0 ⁇ 10 ⁇ 2 Pa, the film is all amorphous, and thereafter 100 Crystallization occurred when annealed at a temperature between 0 ° C and 300 ° C.
  • the molar ratio y of tin to 1 mol of indium is represented by the molar ratio x of Li to 1 mol of indium ( ⁇ 3.5 ⁇ 10 ⁇ 2 Ln (x) ⁇ 1.6 In the range of less than ⁇ 10 ⁇ 1 ), when the water pressure was 8.0 ⁇ 10 ⁇ 4 Pa, the crystallization temperature was less than 100 ° C., and it was found difficult to form an amorphous film.
  • the molar ratio y of tin to 1 mol of indium is represented by the molar ratio x of Li to 1 mol of indium ( ⁇ 1.6 ⁇ 10 ⁇ 1 Ln (x) ⁇ 5.9 ⁇ 10 ⁇ 1 ) And ( ⁇ 3.5 ⁇ 10 ⁇ 2 Ln (x) ⁇ 1.6 ⁇ 10 ⁇ 1 ) or more is particularly preferable, and the partial pressure of water is 1.0 ⁇ 10 ⁇ 4 Pa or more. If the film is formed under the condition of 1.0 ⁇ 10 ⁇ 3 Pa or less, an amorphous film can be formed at a temperature of less than 100 ° C. After the film is formed, the film can be crystallized by annealing at 100 ° C. to 300 ° C. I found out that
  • La-containing composition transparent conductive film test example 1 (La-containing composition transparent conductive film test example 1) Using the target having the composition shown in Table 5 manufactured as described above, this was mounted on a 4-inch DC magnetron sputtering apparatus, the substrate temperature was room temperature (about 20 ° C.), and the oxygen partial pressure was between 0 and 3.0 sccm. (Corresponding to 0 to 1.1 ⁇ 10 ⁇ 2 Pa) while obtaining a transparent conductive film of each composition.
  • the sputtering conditions were as follows, and a film having a thickness of 1200 mm was obtained.
  • Sputtering method DC magnetron sputtering
  • Exhaust device Rotary pump + cryopump Ultimate vacuum: 5.3 ⁇ 10 ⁇ 5 [Pa]
  • Ar pressure 4.0 ⁇ 10 ⁇ 1 [Pa]
  • Substrate used: Corning # 1737 (glass for liquid crystal display) t 0.8 mm
  • the optimal oxygen partial pressure for room temperature film formation and the oxygen partial pressure for film formation with the lowest resistivity after annealing at 250 ° C. were different for all samples.
  • transparent conductive films formed at the oxygen partial pressure at the time of film formation having the lowest resistivity after annealing at 250 ° C. were cut into 13 mm square sizes, and these samples were 250 ° C. in the atmosphere.
  • Table 19 the crystal states after annealing at room temperature for 1 hour and after annealing at room temperature and after annealing at 250 ° C. are a for amorphous and c for crystal.
  • the crystallization temperature of each composition was measured and shown in Table 19.
  • the crystallization temperature is a temperature at which the film is crystallized after being deposited at room temperature, and those that do not become amorphous in the film formation at room temperature were set to less than 100 ° C.
  • transparent conductive films formed at the oxygen partial pressure at the time of film formation having the lowest resistivity after annealing at 250 ° C. were cut into 13 mm square sizes, and transmission spectra were measured for the annealed films. .
  • Table 19 shows the average transmittance after annealing.
  • each composition was formed at the oxygen partial pressure at the time of film formation having the lowest resistivity after annealing at 250 ° C., cut into a size of 10 ⁇ 50 mm, and ITO-05N (oxalic acid, Kanto Chemical Co., Ltd.) as an etching solution.
  • Etching rate ( ⁇ / sec) was measured at a temperature of 30 ° C. using an oxalic acid concentration (50 g / L). The results are shown in Table 19.
  • an amorphous film is formed at a film formation temperature of less than 100 ° C. within a range of less than ( ⁇ 6.7 ⁇ 10 ⁇ 2 Ln (x) ⁇ 2.2 ⁇ 10 ⁇ 1 ).
  • Samples that can be formed and crystallized at 100 to 300 ° C. are indicated by ⁇ , and samples that cannot be formed as an amorphous film are indicated by ⁇ .
  • the samples that can be formed as an amorphous film at a film forming temperature of less than 100 ° C. and can be crystallized at 100 to 300 ° C. are indicated by ⁇ and the others are indicated by ⁇ .
  • the molar ratio y (mol) of tin to 1 mol of indium is represented by the molar ratio x of La to 1 mol of indium ( ⁇ 6.7 ⁇ 10 ⁇ 2 Ln (x) ⁇ 2.2).
  • the water pressure is within the range of not less than the value of ( ⁇ 10 ⁇ 1 ) and not more than the value of ( ⁇ 3.3 ⁇ 10 ⁇ 1 Ln (x) ⁇ 7.7 ⁇ 10 ⁇ 1 ).
  • Is 5.0 ⁇ 10 ⁇ 6 Pa which is a range in which an amorphous film can be formed even in the absence of water.
  • the additive element is La
  • the molar ratio y (mol) of tin to 1 mol of indium is represented by the molar ratio x of La to 1 mol of indium ( ⁇ 6.7 ⁇ 10 ⁇ 2 Ln).
  • the film when the film is formed at a temperature of less than 100 ° C. and a water pressure of 1.0 ⁇ 10 ⁇ 2 Pa, the film becomes an amorphous film. Crystallization occurred when annealed at a temperature between 0 ° C and 300 ° C.
  • the molar ratio y of tin to 1 mol of indium is represented by the molar ratio x of La to 1 mol of indium ( ⁇ 2.9 ⁇ 10 ⁇ 2 Ln (x) ⁇ 1.3
  • the crystallization temperature was less than 100 ° C., and it was found difficult to form an amorphous film.
  • the molar ratio y of tin to 1 mol of indium is represented by the molar ratio x of La to 1 mol of indium ( ⁇ 6.7 ⁇ 10 ⁇ 2 Ln (x) ⁇ 2.2 ⁇ 10 ⁇ 1 ) And ⁇ 2.9 ⁇ 10 ⁇ 2 Ln (x) ⁇ 1.3 ⁇ 10 ⁇ 1 ) or more is particularly preferable, and the partial pressure of water is 1.0 ⁇ 10 ⁇ 4 Pa or more and 1 If the film is formed under a condition of 0.0 ⁇ 10 ⁇ 3 Pa or less, an amorphous film can be formed at a temperature of less than 100 ° C. After the film formation, a film that can be crystallized by annealing at 100 ° C. to 300 ° C. I found out that
  • the sputtering conditions were as follows, and a film having a thickness of 1200 mm was obtained.
  • Sputtering method DC magnetron sputtering
  • Exhaust device Rotary pump + cryopump Ultimate vacuum: 5.3 ⁇ 10 ⁇ 5 [Pa]
  • Ar pressure 4.0 ⁇ 10 ⁇ 1 [Pa]
  • Substrate used: Corning # 1737 (glass for liquid crystal display) t 0.8 mm
  • the optimal oxygen partial pressure for room temperature film formation and the oxygen partial pressure for film formation with the lowest resistivity after annealing at 250 ° C. were different for all samples.
  • transparent conductive films formed at the oxygen partial pressure at the time of film formation having the lowest resistivity after annealing at 250 ° C. were cut into 13 mm square sizes, and these samples were 250 ° C. in the atmosphere.
  • Table 22 the crystal states after annealing at room temperature for 1 hour and after annealing at room temperature and after annealing at 250 ° C. are a for amorphous and c for crystal.
  • the crystallization temperature of each composition was measured and shown in Table 22.
  • the crystallization temperature is a temperature at which crystallization is performed after film formation at room temperature, and the temperature at which film formation does not become amorphous by film formation at room temperature is set to less than 100 ° C.
  • transparent conductive films formed at the oxygen partial pressure at the time of film formation having the lowest resistivity after annealing at 250 ° C. were cut into 13 mm square sizes, and transmission spectra were measured for the annealed films. .
  • Table 22 shows the average transmittance after annealing.
  • each composition was formed at the oxygen partial pressure at the time of film formation having the lowest resistivity after annealing at 250 ° C., cut into a size of 10 ⁇ 50 mm, and ITO-05N (oxalic acid, Kanto Chemical Co., Ltd.) as an etching solution.
  • Etching rate ( ⁇ / sec) was measured at a temperature of 30 ° C. using an oxalic acid concentration (50 g / L). The results are shown in Table 22.
  • an amorphous film is formed at a film formation temperature of less than 100 ° C. within a range of less than ( ⁇ 6.7 ⁇ 10 ⁇ 2 Ln (x) ⁇ 2.2 ⁇ 10 ⁇ 1 ).
  • Samples that can be formed and crystallized at 100 to 300 ° C. are indicated by ⁇ , and samples that cannot be formed as an amorphous film are indicated by ⁇ .
  • samples that can be formed as an amorphous film at a film forming temperature of less than 100 ° C. and crystallized at 100 to 300 ° C. are indicated by ⁇ , and others are indicated by ⁇ .
  • the molar ratio y (mol) of tin to 1 mol of indium is expressed by the molar ratio x of Ca to 1 mol of indium ( ⁇ 4.1 ⁇ 10 ⁇ 2 Ln (x) ⁇ 9.3).
  • the water pressure is within the range of not less than the value of ⁇ 10 ⁇ 2 ) and not more than the value of ( ⁇ 2.5 ⁇ 10 ⁇ 1 Ln (x) ⁇ 5.7 ⁇ 10 ⁇ 1 ).
  • Is 5.0 ⁇ 10 ⁇ 6 Pa which is a range in which an amorphous film can be formed even in the absence of water.
  • the molar ratio y of tin to 1 mol of indium is expressed by the molar ratio x of Ca to 1 mol of indium ( ⁇ 4.1 ⁇ 10 ⁇ 2 Ln (x) In the range less than the value of ⁇ 9.3 ⁇ 10 ⁇ 2 ), when the film is formed at a temperature of less than 100 ° C. and a water pressure of 1.0 ⁇ 10 ⁇ 2 Pa, it becomes an amorphous film, and thereafter, the film is 100 ° C. to 300 ° C. When it was annealed at 0 ° C., it crystallized.
  • the molar ratio y of tin to 1 mol of indium is represented by the molar ratio x of Ca to 1 mol of indium ( ⁇ 1.6 ⁇ 10 ⁇ 2 Ln (x) ⁇ 3.7).
  • the crystallization temperature was less than 100 ° C., and it was found difficult to form an amorphous film.
  • the molar ratio y of tin to 1 mol of indium is expressed by the molar ratio x of Ca to 1 mol of indium ( ⁇ 4.1 ⁇ 10 ⁇ 2 Ln (x) ⁇ 9.3 ⁇ 10 ⁇ 2 ) And ( ⁇ 1.6 ⁇ 10 ⁇ 2 Ln (x) ⁇ 3.7 ⁇ 10 ⁇ 2 ) or more is particularly preferable, and the partial pressure of water is 1.0 ⁇ 10 ⁇ 4 Pa or more. If the film is formed under the condition of 1.0 ⁇ 10 ⁇ 3 Pa or less, an amorphous film can be formed at a temperature of less than 100 ° C. After the film is formed, the film can be crystallized by annealing at 100 ° C. to 300 ° C. I found out that
  • Mg-containing composition transparent conductive film test example 1 The targets having the composition shown in Table 9 manufactured as described above were used and mounted on a 4-inch DC magnetron sputtering apparatus, the substrate temperature was room temperature (about 20 ° C.), and the oxygen partial pressure was between 0 and 3.0 sccm. (Corresponding to 0 to 1.1 ⁇ 10 ⁇ 2 Pa) while obtaining a transparent conductive film of each composition.
  • the sputtering conditions were as follows, and a film having a thickness of 1200 mm was obtained.
  • Sputtering method DC magnetron sputtering
  • Exhaust device Rotary pump + cryopump Ultimate vacuum: 5.3 ⁇ 10 ⁇ 5 [Pa]
  • Ar pressure 4.0 ⁇ 10 ⁇ 1 [Pa]
  • Substrate used: Corning # 1737 (glass for liquid crystal display) t 0.8 mm
  • the optimal oxygen partial pressure for room temperature film formation and the oxygen partial pressure for film formation with the lowest resistivity after annealing at 250 ° C. were different for all samples.
  • transparent conductive films formed at the oxygen partial pressure at the time of film formation having the lowest resistivity after annealing at 250 ° C. were cut into 13 mm square sizes, and these samples were 250 ° C. in the atmosphere.
  • the crystal state after annealing at room temperature for 1 hour and after film formation at room temperature and after annealing at 250 ° C. is a for amorphous and c for crystal.
  • the crystallization temperature of each composition was measured and shown in Table 25.
  • the crystallization temperature is the temperature at which crystallization occurs after film formation at 100 ° C., and the temperature that does not become amorphous after film formation at 100 ° C. is less than 100 ° C.
  • transparent conductive films formed at the oxygen partial pressure at the time of film formation having the lowest resistivity after annealing at 250 ° C. were cut into 13 mm square sizes, and transmission spectra were measured for the annealed films. .
  • Table 25 shows the average transmittance after annealing.
  • each composition was formed at the oxygen partial pressure at the time of film formation having the lowest resistivity after annealing at 250 ° C., cut into a size of 10 ⁇ 50 mm, and ITO-05N (oxalic acid, Kanto Chemical Co., Ltd.) as an etching solution.
  • Etching rate ( ⁇ / sec) was measured at a temperature of 30 ° C. using an oxalic acid concentration (50 g / L). The results are shown in Table 25.
  • samples that can be formed as an amorphous film at a film forming temperature of less than 100 ° C. and crystallized at 100 to 300 ° C. are indicated by ⁇ , and others are indicated by ⁇ .
  • the molar ratio y (mol) of tin to 1 mol of indium is expressed by the molar ratio x of Mg to 1 mol of indium ( ⁇ 4.1 ⁇ 10 ⁇ 2 Ln (x) ⁇ 9.3).
  • the water pressure is within the range of not less than the value of ( ⁇ 10 ⁇ 2 ) and not more than the value of ( ⁇ 2.5 ⁇ 10 ⁇ 1 Ln (x) ⁇ 5.7 ⁇ 10 ⁇ 1 ) Is 5.0 ⁇ 10 ⁇ 6 Pa, which is a range in which an amorphous film can be formed even in the absence of water.
  • the molar ratio y of tin to 1 mol of indium is expressed by the molar ratio x of Mg to 1 mol of indium ( ⁇ 4.1 ⁇ 10 ⁇ 2 Ln (x) In the range less than the value of ⁇ 9.3 ⁇ 10 ⁇ 2 ), when the film is formed at a temperature of less than 100 ° C. and a water pressure of 1.0 ⁇ 10 ⁇ 2 Pa, it becomes an amorphous film, and thereafter, the film is 100 ° C. to 300 ° C. When it was annealed at 0 ° C., it crystallized.
  • the molar ratio y of tin to 1 mol of indium is represented by the molar ratio x of Mg to 1 mol of indium ( ⁇ 1.6 ⁇ 10 ⁇ 2 Ln (x) ⁇ 3.7).
  • the molar ratio x of Mg to 1 mol of indium ⁇ 1.6 ⁇ 10 ⁇ 2 Ln (x) ⁇ 3.7.
  • the crystallization temperature was less than 100 ° C., and it was found difficult to form an amorphous film.
  • the molar ratio y of tin to 1 mol of indium is expressed by the molar ratio x of Mg to 1 mol of indium ( ⁇ 4.1 ⁇ 10 ⁇ 2 Ln (x) ⁇ 9.3 ⁇ 10 ⁇ 2 ) And ( ⁇ 1.6 ⁇ 10 ⁇ 2 Ln (x) ⁇ 3.7 ⁇ 10 ⁇ 2 ) or more is particularly preferable, and the partial pressure of water is 1.0 ⁇ 10 ⁇ 4 Pa or more. If the film is formed under the condition of 1.0 ⁇ 10 ⁇ 3 Pa or less, an amorphous film can be formed at a temperature of less than 100 ° C. After the film is formed, the film can be crystallized by annealing at 100 ° C. to 300 ° C. I found out that
  • Y-containing composition transparent conductive film test example 1 Using the targets having the composition shown in Table 11 manufactured as described above, these were mounted on a 4-inch DC magnetron sputtering apparatus, the substrate temperature was room temperature (about 20 ° C.), and the oxygen partial pressure was between 0 and 3.0 sccm. (Corresponding to 0 to 1.1 ⁇ 10 ⁇ 2 Pa) while obtaining a transparent conductive film of each composition.
  • the sputtering conditions were as follows, and a film having a thickness of 1200 mm was obtained.
  • Sputtering method DC magnetron sputtering
  • Exhaust device Rotary pump + cryopump Ultimate vacuum: 5.3 ⁇ 10 ⁇ 5 [Pa]
  • Ar pressure 4.0 ⁇ 10 ⁇ 1 [Pa]
  • Substrate used: Corning # 1737 (glass for liquid crystal display) t 0.8 mm
  • the optimal oxygen partial pressure for room temperature film formation and the oxygen partial pressure for film formation with the lowest resistivity after annealing at 250 ° C. were different for all samples.
  • transparent conductive films formed at the oxygen partial pressure at the time of film formation having the lowest resistivity after annealing at 250 ° C. were cut into 13 mm square sizes, and these samples were 250 ° C. in the atmosphere.
  • the crystal states after annealing at room temperature for 1 hour, after film formation at room temperature and after annealing at 250 ° C. are a for amorphous and c for crystal, and these are shown in Table 28.
  • the crystallization temperature of each composition was measured and shown in Table 28.
  • the crystallization temperature is a temperature at which crystallization is performed after film formation at room temperature, and the temperature at which film formation does not become amorphous by film formation at room temperature is set to less than 100 ° C.
  • transparent conductive films formed at the oxygen partial pressure at the time of film formation having the lowest resistivity after annealing at 250 ° C. were cut into 13 mm square sizes, and transmission spectra were measured for the annealed films. .
  • Table 28 shows the average transmittance after annealing.
  • each composition was formed at the oxygen partial pressure at the time of film formation having the lowest resistivity after annealing at 250 ° C., cut into a size of 10 ⁇ 50 mm, and ITO-05N (oxalic acid, Kanto Chemical Co., Ltd.) as an etching solution.
  • Etching rate ( ⁇ / sec) was measured at a temperature of 30 ° C. using an oxalic acid concentration (50 g / L). The results are shown in Table 28.
  • Y-containing composition transparent conductive film test example 2 A transparent conductive film having each composition was obtained under the conditions described above except that the target having the composition shown in Table 11 manufactured as described above was used and the water pressure was 8.0 ⁇ 10 ⁇ 4 Pa.
  • Y-containing composition transparent conductive film reference example A transparent conductive film having each composition was obtained under the above-described conditions except that the target having the composition shown in Table 12 manufactured as described above was used and the water pressure was 5.0 ⁇ 10 ⁇ 6 Pa.
  • Table 28 to Table 30 are shown in FIGS. 16 to 18, respectively.
  • samples that can be formed as an amorphous film at a film forming temperature of less than 100 ° C. and crystallized at 100 to 300 ° C. are indicated by ⁇ , and the others are indicated by ⁇ .
  • the molar ratio y (mol) of tin to 1 mol of indium is represented by the molar ratio x of Y to 1 mol of indium ( ⁇ 2.5 ⁇ 10 ⁇ 2 Ln (x) ⁇ 5.8).
  • ⁇ 10 -2) is a value or more and (-1.0 ⁇ 10 -1 Ln (x ) -5.0 ⁇ 10 -2 and less than or equal to the range of), as is clear from FIG. 18, the water pressure Is 5.0 ⁇ 10 ⁇ 6 Pa, which is a range in which an amorphous film can be formed even in the absence of water.
  • the molar ratio y of tin to 1 mol of indium is represented by the molar ratio x of Y to 1 mol of indium ( ⁇ 2.5 ⁇ 10 ⁇ 2 Ln (x) In the range of less than ⁇ 5.8 ⁇ 10 ⁇ 2 ), when the film is formed at a water pressure of 1.0 ⁇ 10 ⁇ 2 Pa at a temperature of less than 100 ° C., the film becomes an amorphous film. When it was annealed at 0 ° C., it crystallized.
  • the molar ratio y of tin to 1 mol of indium is represented by the molar ratio x of Y to 1 mol of indium ( ⁇ 2.2 ⁇ 10 ⁇ 2 Ln (x) ⁇ 1.5 In the range of less than ⁇ 10 ⁇ 1 ), when the water pressure was 8.0 ⁇ 10 ⁇ 4 Pa, the crystallization temperature was less than 100 ° C., and it was found difficult to form an amorphous film.
  • the molar ratio y of tin to 1 mol of indium is represented by the molar ratio x of Y to 1 mol of indium ( ⁇ 2.5 ⁇ 10 ⁇ 2 Ln (x) ⁇ 5.8 ⁇ 10 ⁇ 2 ) And ( ⁇ 2.2 ⁇ 10 ⁇ 2 Ln (x) ⁇ 1.5 ⁇ 10 ⁇ 1 ) or more is particularly preferable, and the partial pressure of water is 1.0 ⁇ 10 ⁇ 4 Pa or more. If the film is formed under the condition of 1.0 ⁇ 10 ⁇ 3 Pa or less, an amorphous film can be formed at a temperature of less than 100 ° C. After the film is formed, the film can be crystallized by annealing at 100 ° C. to 300 ° C. I found out that
  • TPD Test Example 1 A sputtering target of sample A8 was mounted on a 4-inch DC magnetron sputtering apparatus, the substrate temperature was room temperature (about 20 ° C.), the water pressure during film formation was 0 Pa (referred to as TPD Test Example 1), 8.0 ⁇ 10 ⁇ Transparent conductive films of TPD Test Examples 1 to 3 were obtained under the conditions of 4 Pa (referred to as TPD Test Example 2) and 1.0 ⁇ 10 ⁇ 2 Pa (referred to as TPD Test Example 3).
  • the copper foil sample was also measured as a blank.
  • Measurement condition Measurement atmosphere: 20% O 2 -80% He Gas flow rate: 50ccm Pretreatment: 120 ° C., 30 min keep (to remove water adhering to the sample) Measurement temperature: 120-600 ° C Temperature increase rate: 4 ° C / min
  • H 2 O + ions are detected in the entire measurement temperature range of all the samples, these are considered to be due to the influence of moisture present in the apparatus and in the atmospheric gas. Since such a behavior is always detected even if any sample is measured, it is general to consider these as a baseline and correct the intensity. Accordingly, the baseline correction processing was performed in the same way for the measurement results. The result is shown in FIG.
  • TPD Test Example 1 formed in an atmosphere substantially free of water overlaps with the H 2 O + ion peak of the copper foil sample that is almost blank. From this, it can be said that the sample of TPD Test Example 1 hardly contains hydrogen.
  • TPD Test Examples 2 and 3 in which water was added by increasing the water pressure during film formation, the peak of H 2 O + ions was confirmed not only in the temperature range of 200 to 300 ° C. but also at 300 ° C. or higher. . In particular, in TPD Test Example 3 in which the amount of water added during film formation was large, it was confirmed that there was a large H 2 O + ion peak near 400 ° C.
  • TPD Test Examples 2 and 3 hydrogen was taken into the film and contained by adding water with a hydrogen partial pressure within a predetermined range during film formation.
  • the crystallization temperatures of TPD Test Examples 2 and 3 are 200 ° C. and 300 ° C., respectively, but the peak of H 2 O + ions of these samples is confirmed even at 300 ° C. or higher. It was found that water gas was desorbed even after crystallization.
  • TPD temperature programmed desorption
  • the transparent conductive film according to the present invention is actually mounted on a liquid crystal display device or a heat generation film for preventing condensation of glass, an infrared reflection film, etc., in order to confirm hydrogen present in those films, This is possible by taking out the substrate on which the film is formed and detecting the water gas generated during heating by the TPD method described above.
  • hydrogen present in the film can be analyzed by TOF-SIMS and dynamic SIMS.
  • the sputtering conditions were as follows, and a film having a thickness of 1200 mm was obtained.
  • Sputtering method DC magnetron sputtering
  • Exhaust device Rotary pump + cryopump Ultimate vacuum: 5.3 ⁇ 10 ⁇ 5 [Pa]
  • Ar pressure 4.0 ⁇ 10 ⁇ 1 [Pa]
  • Substrate temperature Room temperature Sputtering power: 130 W (Power density 1.6 W / cm 2 )
  • Table 31 shows (H + ion count number) / (total ion count number), which is a TOF-SIMS analysis result of the deposited sample.
  • H + ions were also detected in the sample of TOF Test Example 1 formed in an atmosphere where the water pressure during film formation was 5.0 ⁇ 10 ⁇ 5 and substantially no water was present. Can be determined as a background. That is, in recent research, it has been reported that H + ions were detected from an indium oxide film formed at a partial pressure lower than the water pressure of TOF Test Example 1 (Jpn. J. Appl. Phys., Vol. 46, No. 28, 2007, pp. L685-L687) From the above, it can be inferred that the detected hydrogen ions have incorporated a small amount of moisture adhering to the substrate during film formation into the film.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Non-Insulated Conductors (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

Disclosed is an electrically conductive transparent film which can be produced in the form of an amorphous film that can be patterned easily by weak acid etching and can be crystallized easily, wherein the crystallized film has a low resistivity and a high transmissivity. The film is produced in the form of an amorphous film using a sputtering target that comprises a sintered oxide material comprising indium oxide and optionally tin, and additionally comprising at least one additive element selected from the group consisting of Sr, Li, La, Ca, Mg and Y, under conditions where the partial pressure of water is 1.0 × 10-4 to 1.0 × 10-1 Pa inclusive.

Description

酸化インジウム系透明導電膜及びその製造方法Indium oxide-based transparent conductive film and method for producing the same
　本発明は、アモルファス膜として成膜でき、そのアモルファス膜は弱酸エッチングにより容易にパターニングでき、さらに容易に結晶化でき、またさらに結晶化した膜は低抵抗で且つ透過率が高い透明導電膜に関する。 The present invention relates to a transparent conductive film that can be formed as an amorphous film, the amorphous film can be easily patterned by weak acid etching, can be crystallized more easily, and the crystallized film has low resistance and high transmittance.
　酸化インジウム－酸化錫（Ｉｎ2Ｏ3－ＳｎＯ2の複合酸化物、以下、「ＩＴＯ」という）膜は、可視光透過性が高く、かつ導電性が高いので透明導電膜として液晶表示装置やガラスの結露防止用発熱膜、赤外線反射膜等に幅広く用いられているが、アモルファスな膜とするのが困難であるという問題がある。 An indium oxide-tin oxide (In 2 O 3 —SnO 2 composite oxide, hereinafter referred to as “ITO”) film has high visible light transmittance and high electrical conductivity, so that it can be used as a transparent conductive film such as a liquid crystal display device or glass. However, it is difficult to obtain an amorphous film.
　一方、アモルファスな膜となるものとして、酸化インジウム－酸化亜鉛（ＩＺＯ）透明導電膜が知られているが、かかる膜はＩＴＯ膜より透明性に劣り、黄色みがかるという問題がある。 On the other hand, an indium oxide-zinc oxide (IZO) transparent conductive film is known as an amorphous film. However, such a film is inferior in transparency to an ITO film and has a problem of yellowing.
　そこで、本出願人は、透明導電膜としてＩＴＯ膜に珪素を添加して所定の条件で成膜したアモルファスな透明導電膜を先に提案した（特許文献１参照）が、珪素を添加すると高抵抗化の傾向があるという問題があった。 Therefore, the present applicant has previously proposed an amorphous transparent conductive film formed by adding silicon to an ITO film under a predetermined condition as a transparent conductive film (see Patent Document 1). There was a problem that there was a tendency to change.
特開２００５－１３５６４９号公報（特許請求の範囲）Japanese Patent Laying-Open No. 2005-135649 (Claims)
　本発明は、このような事情に鑑み、アモルファス膜として成膜でき、そのアモルファス膜は弱酸エッチングにより容易にパターニングでき、さらに容易に結晶化でき、またさらに結晶化した膜は低抵抗で且つ透過率が高い酸化インジウム系透明導電膜及びその製造方法を提供することを課題とする。 In view of such circumstances, the present invention can be formed as an amorphous film, and the amorphous film can be easily patterned by weak acid etching, can be crystallized more easily, and the crystallized film has low resistance and transmittance. It is an object of the present invention to provide an indium oxide-based transparent conductive film and a method for producing the same.
　本発明は上述した課題を解決するために種々検討を重ねた結果、特定の添加元素を添加し且つ水の分圧を１．０×１０-4Ｐａ以上１．０×１０-1Ｐａ以下の条件下で成膜した膜は、広い組成範囲で結晶化温度を、例えば、１００℃以上と上昇させることができ、例えば、１００℃程度の成膜条件でもアモルファスな膜を得ることができることを知見し、完成されたものである。 As a result of various investigations in order to solve the above-mentioned problems, the present invention adds a specific additive element and the partial pressure of water is 1.0 × 10 −4 Pa or more and 1.0 × 10 −1 Pa or less. It has been found that a film formed under conditions can raise the crystallization temperature to, for example, 100 ° C. or higher over a wide composition range, and an amorphous film can be obtained even under film formation conditions of, for example, about 100 ° C. And completed.
　かかる本発明の第１の態様は、酸化インジウムと必要に応じて錫を含有すると共にＳｒ、Ｌｉ、Ｌａ、Ｃａ、Ｍｇ及びＹからなる群から選択される少なくとも一種である添加元素を含有する酸化物焼結体を具備するスパッタリングターゲットを用い、水の分圧が１．０×１０-4Ｐａ以上１．０×１０-1Ｐａ以下の条件下でアモルファス膜として成膜されたものであることを特徴とする透明導電膜にある。 The first aspect of the present invention is an oxidation containing indium oxide and tin as required, and at least one additive element selected from the group consisting of Sr, Li, La, Ca, Mg and Y. The film was formed as an amorphous film using a sputtering target having a sintered body and having a partial pressure of water of 1.0 × 10 −4 Pa to 1.0 × 10 −1 Pa. It is in the transparent conductive film characterized by these.
　かかる第１の態様では、アモルファス膜として成膜されるので、そのアモルファス膜は弱酸エッチングにより容易にパターニングでき、さらに容易に結晶化でき、またさらに結晶化した膜は低抵抗で且つ透過率が高いものである。 In the first aspect, since the film is formed as an amorphous film, the amorphous film can be easily patterned by weak acid etching, can be crystallized more easily, and the crystallized film has low resistance and high transmittance. Is.
　本発明の第２の態様は、第１の態様に記載の透明導電膜において、前記アモルファスな膜が水素を含有することを特徴とする透明導電膜にある。 A second aspect of the present invention is the transparent conductive film according to the first aspect, wherein the amorphous film contains hydrogen.
　かかる第２の態様では、所定の水分圧の条件下で成膜されたものであるので、水素を含有するものとなる。 In the second aspect, since the film is formed under the condition of a predetermined moisture pressure, it contains hydrogen.
　本発明の第３の態様は、第１又は２の態様に記載の透明導電膜において、アモルファス膜を成膜後、アニールすることにより結晶化されたものであることを特徴とする透明導電膜にある。 According to a third aspect of the present invention, there is provided the transparent conductive film according to the first or second aspect, wherein the amorphous conductive film is crystallized by annealing and then crystallized. is there.
　かかる第３の態様では、アモルファスな膜として成膜された後、アニールにより容易に結晶化でき、耐弱酸性を付与することができる。 In such a third aspect, after being formed as an amorphous film, it can be easily crystallized by annealing and imparted weak acid resistance.
　本発明の第４の態様は、第１～３の何れかの態様に記載の透明導電膜において、前記添加元素がストロンチウムであり、膜組成は、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するストロンチウムのモル比ｘで表される（－４．１×１０－２Ｌｎ（ｘ）－９．３×１０－２）の値未満の範囲にあることを特徴とする透明導電膜にある。 According to a fourth aspect of the present invention, in the transparent conductive film according to any one of the first to third aspects, the additive element is strontium, and the film composition is a molar ratio y of tin to 1 mol of indium. Is in the range of less than the value of (−4.1 × 10 −2 Ln (x) −9.3 × 10 −2 ) represented by the molar ratio x of strontium to 1 mol of indium. It is in the conductive film.
　かかる第４の態様では、１００℃未満で成膜した場合にアモルファスな膜となり、その後、１００℃～３００℃でアニールした場合に結晶化することができる。 In such a fourth embodiment, an amorphous film is formed when the film is formed at a temperature lower than 100 ° C., and then the film can be crystallized when annealed at 100 ° C. to 300 ° C.
　本発明の第５の態様は、第１～３の何れかの態様に記載の透明導電膜において、前記添加元素がストロンチウムであり、膜組成は、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するストロンチウムのモル比ｘで表される（－４．１×１０－２Ｌｎ（ｘ）－９．３×１０－２）の値未満であり且つ（－１．６×１０－２Ｌｎ（ｘ）－３．７×１０－２）以上の範囲にあることを特徴とする透明導電膜にある。 According to a fifth aspect of the present invention, in the transparent conductive film according to any one of the first to third aspects, the additive element is strontium, and the film composition is a molar ratio y of tin to 1 mol of indium. Is less than the value of (−4.1 × 10 −2 Ln (x) −9.3 × 10 −2 ) represented by the molar ratio x of strontium to 1 mol of indium and (−1.6 × 10 −2 Ln (x) −3.7 × 10 −2 ) or more.
　かかる第５の態様では、１００℃未満で成膜した場合にアモルファスな膜となり、その後、１００℃～３００℃でアニールした場合に結晶化することができる。 In the fifth aspect, the film is amorphous when formed at a temperature lower than 100 ° C., and can be crystallized when annealed at 100 ° C. to 300 ° C. thereafter.
　本発明の第６の態様は、第１～３の何れかの態様に記載の透明導電膜において、前記添加元素がリチウムであり、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するリチウムのモル比ｘで表される（－１．６×１０－１Ｌｎ（ｘ）－５．９×１０－１）の値未満の範囲にあることを特徴とする透明導電膜にある。 According to a sixth aspect of the present invention, in the transparent conductive film according to any one of the first to third aspects, the additive element is lithium, and the molar ratio y of tin to 1 mol of indium is indium 1 The transparent conductive film is characterized by being in a range less than the value of (−1.6 × 10 −1 Ln (x) −5.9 × 10 −1 ) represented by a molar ratio x of lithium to mole. .
　かかる第６の態様では、１００℃未満で成膜した場合にアモルファスな膜となり、その後、１００℃～３００℃でアニールした場合に結晶化することができる。 In such a sixth aspect, an amorphous film is formed when the film is formed at a temperature lower than 100 ° C., and the film can be crystallized after annealing at 100 ° C. to 300 ° C.
　本発明の第７の態様では、第１～３の何れかの態様に記載の透明導電膜において、前記添加元素がリチウムであり、膜組成は、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するリチウムのモル比ｘで表される（－１．６×１０－１Ｌｎ（ｘ）－５．９×１０－１）の値未満であり且つ（－３．５×１０－２Ｌｎ（ｘ）－１．６×１０－１）以上の範囲にあることを特徴とする透明導電膜にある。 According to a seventh aspect of the present invention, in the transparent conductive film according to any one of the first to third aspects, the additive element is lithium, and the film composition is a molar ratio y of tin to 1 mol of indium. Is less than the value of (−1.6 × 10 −1 Ln (x) −5.9 × 10 −1 ) expressed by the molar ratio x of lithium to 1 mol of indium and (−3.5 × 10 −2 Ln (x) −1.6 × 10 −1 ) or more.
　かかる第７の態様では、１００℃未満で成膜した場合にアモルファスな膜となり、その後、１００℃～３００℃でアニールした場合に結晶化することができる。 In such a seventh aspect, an amorphous film is formed when the film is formed at a temperature lower than 100 ° C., and then the film can be crystallized when annealed at 100 ° C. to 300 ° C.
　本発明の第８の態様は、第１～３の何れかの態様に記載の透明導電膜において、前記添加元素がランタンであり、膜組成は、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するランタンのモル比ｘで表される（－６．７×１０－２Ｌｎ（ｘ）－２．２×１０－１）の値未満の範囲にあることを特徴とする透明導電膜にある。 According to an eighth aspect of the present invention, in the transparent conductive film according to any one of the first to third aspects, the additive element is lanthanum, and the film composition is a molar ratio y of tin to 1 mol of indium. Is in a range of less than the value of (−6.7 × 10 −2 Ln (x) −2.2 × 10 −1 ) represented by the molar ratio x of lanthanum to 1 mol of indium. It is in the conductive film.
　かかる第８の態様では、１００℃未満で成膜した場合にアモルファスな膜となり、その後、１００℃～３００℃でアニールした場合に結晶化することができる。 In the eighth aspect, an amorphous film can be formed when the film is formed at a temperature lower than 100 ° C., and then the film can be crystallized when annealed at 100 ° C. to 300 ° C.
　本発明の第９の態様は、第１～３の何れかの態様に記載の透明導電膜において、前記添加元素がランタンであり、膜組成は、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するランタンのモル比ｘで表される（－６．７×１０－２Ｌｎ（ｘ）－２．２×１０－１）の値未満であり且つ（－２．９×１０－２Ｌｎ（ｘ）－１．３×１０－１）以上の範囲にあることを特徴とする透明導電膜にある。 According to a ninth aspect of the present invention, in the transparent conductive film according to any one of the first to third aspects, the additive element is lanthanum, and the film composition is a molar ratio y of tin to 1 mol of indium. Is less than the value of (−6.7 × 10 −2 Ln (x) −2.2 × 10 −1 ) expressed by the molar ratio x of lanthanum to 1 mol of indium and (−2.9 × 10 −2 Ln (x) −1.3 × 10 −1 ) or more.
　かかる第９の態様では、１００℃未満で成膜した場合にアモルファスな膜となり、その後、１００℃～３００℃でアニールした場合に結晶化することができる。 In the ninth aspect, when the film is formed at a temperature lower than 100 ° C., it becomes an amorphous film, and thereafter, it can be crystallized when annealed at 100 ° C. to 300 ° C.
　本発明の第１０の態様は、第１～３の何れかの態様に記載の透明導電膜において、前記添加元素がカルシウムであり、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するカルシウムのモル比ｘで表される（－４．１×１０－２Ｌｎ（ｘ）－９．３×１０－２）の値未満の範囲にあることを特徴とする透明導電膜にある。 According to a tenth aspect of the present invention, in the transparent conductive film according to any one of the first to third aspects, the additive element is calcium, and the molar ratio y of tin to 1 mol of indium is indium 1 The transparent conductive film is characterized by being in a range of less than a value of (−4.1 × 10 −2 Ln (x) −9.3 × 10 −2 ) represented by a molar ratio of calcium to mole x. .
　かかる第１０の態様では、１００℃未満で成膜した場合にアモルファスな膜となり、その後、１００℃～３００℃でアニールした場合に結晶化することができる。 In such a tenth aspect, an amorphous film is formed when the film is formed at a temperature lower than 100 ° C., and then the film can be crystallized when annealed at 100 ° C. to 300 ° C.
　本発明の第１１の態様は、第１～３の何れかの態様に記載の透明導電膜において、前記添加元素がカルシウムであり、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するカルシウムのモル比ｘで表される（－４．１×１０－２Ｌｎ（ｘ）－９．３×１０－２）の値未満であり且つ（－１．６×１０－２Ｌｎ（ｘ）－３．７×１０－２）以上の範囲にあることを特徴とする透明導電膜にある。 According to an eleventh aspect of the present invention, in the transparent conductive film according to any one of the first to third aspects, the additive element is calcium, and the molar ratio y of tin to 1 mol of indium is indium 1 represented by a molar ratio x of calcium to moles (-4.1 × 10 -2 Ln (x ) -9.3 × 10 -2) less than the value and (-1.6 × 10 -2 Ln ( x) A transparent conductive film characterized by being in the range of −3.7 × 10 −2 ) or more.
　かかる第１１の態様では、１００℃未満で成膜した場合にアモルファスな膜となり、その後、１００℃～３００℃でアニールした場合に結晶化することができる。 In the eleventh aspect, an amorphous film can be formed when the film is formed at a temperature lower than 100 ° C., and then the film can be crystallized when annealed at 100 ° C. to 300 ° C.
　本発明の第１２の態様は、第１～３の何れかの態様に記載の透明導電膜において、前記添加元素がマグネシウムであり、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するマグネシウムのモル比ｘで表される（－４．１×１０－２Ｌｎ（ｘ）－９．３×１０－２）の値未満の範囲にあることを特徴とする透明導電膜にある。 According to a twelfth aspect of the present invention, in the transparent conductive film according to any one of the first to third aspects, the additive element is magnesium, and the molar ratio y of tin to 1 mole of indium is indium 1 The transparent conductive film is characterized by being in a range less than the value of (−4.1 × 10 −2 Ln (x) −9.3 × 10 −2 ) represented by a molar ratio x of magnesium to mol. .
　かかる第１２の態様では、１００℃未満で成膜した場合にアモルファスな膜となり、その後、１００℃～３００℃でアニールした場合に結晶化することができる。 In the twelfth aspect, an amorphous film can be formed when the film is formed at a temperature lower than 100 ° C., and then the film can be crystallized when annealed at 100 ° C. to 300 ° C.
　本発明の第１３の態様は、第１～３の何れかの態様に記載の透明導電膜において、前記添加元素がマグネシウムであり、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するマグネシウムのモル比ｘで表される（－４．１×１０－２Ｌｎ（ｘ）－９．３×１０－２）の値未満であり且つ（－１．６×１０－２Ｌｎ（ｘ）－３．７×１０－２）以上の範囲にあることを特徴とする透明導電膜にある。 According to a thirteenth aspect of the present invention, in the transparent conductive film according to any one of the first to third aspects, the additive element is magnesium, and the molar ratio y of tin to 1 mol of indium is indium 1 Less than the value of (−4.1 × 10 −2 Ln (x) −9.3 × 10 −2 ) expressed by the molar ratio x of magnesium to mol and (−1.6 × 10 −2 Ln ( x) A transparent conductive film characterized by being in the range of −3.7 × 10 −2 ) or more.
　かかる第１３の態様では、１００℃未満で成膜した場合にアモルファスな膜となり、その後、１００℃～３００℃でアニールした場合に結晶化することができる。 In the thirteenth aspect, when the film is formed at a temperature lower than 100 ° C., it becomes an amorphous film, and thereafter, it can be crystallized when annealed at 100 ° C. to 300 ° C.
　本発明の第１４の態様は、第１～３の何れかの態様に記載の透明導電膜において、前記添加元素がイットリウムであり、膜組成は、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するイットリウムのモル比ｘで表される（－２．５×１０－２Ｌｎ（ｘ）－５．８×１０－２）の値未満の範囲にあることを特徴とする透明導電膜にある。 According to a fourteenth aspect of the present invention, in the transparent conductive film according to any one of the first to third aspects, the additive element is yttrium, and the film composition has a molar ratio y of tin to 1 mol of indium. Is in a range less than a value of (−2.5 × 10 −2 Ln (x) −5.8 × 10 −2 ) represented by a molar ratio x of yttrium to 1 mol of indium. It is in the conductive film.
　かかる第１４の態様では、１００℃未満で成膜した場合にアモルファスな膜となり、その後、１００℃～３００℃でアニールした場合に結晶化することができる。 In the fourteenth aspect, an amorphous film is formed when formed at a temperature lower than 100 ° C., and crystallization can be performed when annealed at 100 ° C. to 300 ° C. thereafter.
　本発明の第１５の態様は、第１～３の何れかの態様に記載の透明導電膜において、前記添加元素がイットリウムであり、膜組成は、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するイットリウムのモル比ｘで表される（－２．５×１０－２Ｌｎ（ｘ）－５．８×１０－２）の値未満であり且つ（－２．２×１０－２Ｌｎ（ｘ）－１．５×１０－１）以上の範囲にあることを特徴とする透明導電膜にある。 According to a fifteenth aspect of the present invention, in the transparent conductive film according to any one of the first to third aspects, the additive element is yttrium, and the film composition has a molar ratio y of tin to 1 mol of indium. Is less than the value of (−2.5 × 10 −2 Ln (x) −5.8 × 10 −2 ) expressed by the molar ratio x of yttrium to 1 mol of indium and (−2.2 × 10 −2 Ln (x) −1.5 × 10 −1 ) or more.
　かかる第１５の態様では、１００℃未満で成膜した場合にアモルファスな膜となり、その後、１００℃～３００℃でアニールした場合に結晶化することができる。 In the fifteenth aspect, when the film is formed at a temperature lower than 100 ° C., it becomes an amorphous film, and thereafter, it can be crystallized when annealed at 100 ° C. to 300 ° C.
　本発明の第１６の態様は、酸化インジウムと必要に応じて錫を含有すると共にＳｒ（ストロンチウム）、Ｌｉ（リチウム）、Ｌａ（ランタン）、Ｃａ（カルシウム）、Ｍｇ（マグネシウム）及びＹ（イットリウム）からなる群から選択される少なくとも一種である添加元素を含有する酸化物焼結体を具備するスパッタリングターゲットを用い、１００℃未満、水の分圧が１．０×１０-4Ｐａ以上１．０×１０-1Ｐａ以下の条件下で、アモルファス膜を成膜することを特徴とする透明導電膜の製造方法にある。 The sixteenth aspect of the present invention contains indium oxide and tin as required, and Sr (strontium), Li (lithium), La (lanthanum), Ca (calcium), Mg (magnesium) and Y (yttrium). using a sputtering target comprising an oxide sintered body containing an additive element is at least one selected from the group consisting of less than 100 ° C., the partial pressure of water 1.0 × 10 -4 Pa or more and 1.0 In the method for producing a transparent conductive film, an amorphous film is formed under a condition of × 10 −1 Pa or less.
　かかる第１６の態様では、アモルファス膜として成膜されるので、そのアモルファス膜は弱酸エッチングにより容易にパターニングでき、さらに容易に結晶化でき、またさらに結晶化した膜は低抵抗で且つ透過率が高いものである。 In the sixteenth aspect, since the film is formed as an amorphous film, the amorphous film can be easily patterned by weak acid etching, can be crystallized more easily, and the crystallized film has low resistance and high transmittance. Is.
　本発明の第１７の態様は、第１６の態様に記載の透明導電膜の製造方法において、アモルファス膜を成膜後、１００℃～３００℃でアニールすることにより結晶化して透明導電膜とすることを特徴とする透明導電膜の製造方法にある。 According to a seventeenth aspect of the present invention, in the method for producing a transparent conductive film according to the sixteenth aspect, after forming an amorphous film, it is crystallized by annealing at 100 ° C. to 300 ° C. to obtain a transparent conductive film. A method for producing a transparent conductive film.
　かかる第１７の態様では、１００℃未満で成膜してアモルファスな膜とし、その後、１００℃～３００℃でアニールして結晶化することができ、耐環境性を向上できる。 In the seventeenth aspect, an amorphous film can be formed at a temperature lower than 100 ° C., and then annealed at 100 ° C. to 300 ° C. for crystallization, thereby improving the environmental resistance.
　本発明の第１８の態様は、第１６又は１７の態様に記載の透明導電膜の製造方法において、前記添加元素がストロンチウムであり、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するストロンチウムのモル比ｘで表される（－４．１×１０－２Ｌｎ（ｘ）－９．３×１０－２）の値未満の範囲にある膜組成の膜を成膜することを特徴とする透明導電膜の製造方法にある。 According to an eighteenth aspect of the present invention, in the method for producing a transparent conductive film according to the sixteenth or seventeenth aspect, the additive element is strontium, and the molar ratio y of tin to 1 mol of indium is indium 1 Forming a film having a film composition in a range less than a value of (−4.1 × 10 −2 Ln (x) −9.3 × 10 −2 ) represented by a molar ratio x of strontium to mol. It is in the manufacturing method of the transparent conductive film characterized.
　本発明の第１９の態様は、第１６又は１７の態様に記載の透明導電膜の製造方法において、前記添加元素がストロンチウムであり、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するストロンチウムのモル比ｘで表される（－４．１×１０－２Ｌｎ（ｘ）－９．３×１０－２）の値未満であり且つ（－１．６×１０－２Ｌｎ（ｘ）－３．７×１０－２）以上の範囲にある膜組成の膜を、水の分圧が１．０×１０-4Ｐａ以上１．０×１０-３Ｐａ以下の条件下で成膜することを特徴とする透明導電膜の製造方法にある。 According to a nineteenth aspect of the present invention, in the method for producing a transparent conductive film according to the sixteenth or seventeenth aspect, the additive element is strontium, and the molar ratio y of tin to 1 mol of indium is indium 1 Less than the value of (−4.1 × 10 −2 Ln (x) −9.3 × 10 −2 ) expressed by the molar ratio x of strontium to mole and (−1.6 × 10 −2 Ln ( x) A film having a film composition in the range of −3.7 × 10 −2 ) or higher is formed under conditions where the partial pressure of water is 1.0 × 10 −4 Pa or higher and 1.0 × 10 −3 Pa or lower. It is in the manufacturing method of the transparent conductive film characterized by carrying out a film | membrane.
　本発明の第２０の態様は、第１６又は１７の態様に記載の透明導電膜の製造方法において、前記添加元素がリチウムであり、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するリチウムのモル比ｘで表される（－１．６×１０－１Ｌｎ（ｘ）－５．９×１０－１）の値未満の範囲にある膜組成の膜を成膜することを特徴とする透明導電膜の製造方法にある。 According to a twentieth aspect of the present invention, in the method for producing a transparent conductive film according to the sixteenth or seventeenth aspect, the additive element is lithium, and the molar ratio y of tin to 1 mole of indium is indium 1 Forming a film having a film composition in a range less than a value of (−1.6 × 10 −1 Ln (x) −5.9 × 10 −1 ) represented by a molar ratio x of lithium to mole. It is in the manufacturing method of the transparent conductive film characterized.
　本発明の第２１の態様は、第１６又は１７の態様に記載の透明導電膜の製造方法において、前記添加元素がリチウムであり、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するリチウムのモル比ｘで表される（－１．６×１０－１Ｌｎ（ｘ）－５．９×１０－１）の値未満であり且つ（－３．５×１０－２Ｌｎ（ｘ）－１．６×１０－１）以上の範囲にある膜組成の膜を、水の分圧が１．０×１０-4Ｐａ以上１．０×１０-３Ｐａ以下の条件下で成膜することを特徴とする透明導電膜の製造方法にある。 According to a twenty-first aspect of the present invention, in the method for producing a transparent conductive film according to the sixteenth or seventeenth aspect, the additive element is lithium, and the molar ratio y of tin to 1 mol of indium is indium 1 Less than the value of (−1.6 × 10 −1 Ln (x) −5.9 × 10 −1 ) expressed by the molar ratio x of lithium to mol and (−3.5 × 10 −2 Ln ( x) A film having a film composition in the range of −1.6 × 10 −1 ) or more is formed under a condition where the partial pressure of water is 1.0 × 10 −4 Pa or more and 1.0 × 10 −3 Pa or less. It is in the manufacturing method of the transparent conductive film characterized by carrying out a film | membrane.
　本発明の第２２の態様は、第１６又は１７の態様に記載の透明導電膜の製造方法において、前記添加元素がランタンであり、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するランタンのモル比ｘで表される（－６．７×１０－２Ｌｎ（ｘ）－２．２×１０－１）の値未満の範囲にある膜組成の膜を成膜することを特徴とする透明導電膜の製造方法にある。 According to a twenty-second aspect of the present invention, in the method for producing a transparent conductive film according to the sixteenth or seventeenth aspect, the additive element is lanthanum, and the molar ratio y of tin to 1 mol of indium is indium 1 Forming a film having a film composition in a range less than the value of (−6.7 × 10 −2 Ln (x) −2.2 × 10 −1 ) represented by the molar ratio x of lanthanum to mol. It is in the manufacturing method of the transparent conductive film characterized.
　本発明の第２３の態様は、第１６又は１７の態様に記載の透明導電膜の製造方法において、前記添加元素がランタンであり、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するランタンのモル比ｘで表される（－６．７×１０－２Ｌｎ（ｘ）－２．２×１０－１）の値未満であり且つ（－２．９×１０－２Ｌｎ（ｘ）－１．３×１０－１）以上の範囲にある膜組成の膜を、水の分圧が１．０×１０-4Ｐａ以上１．０×１０-３Ｐａ以下の条件下で成膜することを特徴とする透明導電膜の製造方法にある。 According to a twenty-third aspect of the present invention, in the method for producing a transparent conductive film according to the sixteenth or seventeenth aspect, the additive element is lanthanum, and the molar ratio y of tin to 1 mol of indium is indium 1 It is less than the value of (−6.7 × 10 −2 Ln (x) −2.2 × 10 −1 ) expressed by the molar ratio x of lanthanum to mol and (−2.9 × 10 −2 Ln ( x) A film having a film composition in the range of −1.3 × 10 −1 ) or more is formed under conditions where the partial pressure of water is 1.0 × 10 −4 Pa or more and 1.0 × 10 −3 Pa or less. It is in the manufacturing method of the transparent conductive film characterized by carrying out a film | membrane.
　本発明の第２４の態様は、第１６又は１７の態様に記載の透明導電膜の製造方法において、前記添加元素がカルシウムであり、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するカルシウムのモル比ｘで表される（－４．１×１０－２Ｌｎ（ｘ）－９．３×１０－２）の値未満の範囲にある膜組成の膜を成膜することを特徴とする透明導電膜の製造方法にある。 According to a twenty-fourth aspect of the present invention, in the method for producing a transparent conductive film according to the sixteenth or seventeenth aspect, the additive element is calcium, and the molar ratio y of tin to 1 mol of indium is indium 1 Forming a film having a film composition in a range less than a value of (−4.1 × 10 −2 Ln (x) −9.3 × 10 −2 ) represented by a molar ratio x of calcium to mole. It is in the manufacturing method of the transparent conductive film characterized.
　本発明の第２５の態様は、第１６又は１７の態様に記載の透明導電膜の製造方法において、前記添加元素がカルシウムであり、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するカルシウムのモル比ｘで表される（－４．１×１０－２Ｌｎ（ｘ）－９．３×１０－２）の値未満であり且つ（－１．６×１０－２Ｌｎ（ｘ）－３．７×１０－２）以上の範囲にある膜組成の膜を、水の分圧が１．０×１０-4Ｐａ以上１．０×１０-３Ｐａ以下の条件下で成膜することを特徴とする透明導電膜の製造方法にある。 According to a 25th aspect of the present invention, in the method for producing a transparent conductive film according to the 16th or 17th aspect, the additive element is calcium, and the molar ratio y of tin to 1 mol of indium is indium 1 Less than the value of (−4.1 × 10 −2 Ln (x) −9.3 × 10 −2 ) expressed by the molar ratio x of calcium to mol and (−1.6 × 10 −2 Ln ( x) A film having a film composition in the range of −3.7 × 10 −2 ) or higher is formed under conditions where the partial pressure of water is 1.0 × 10 −4 Pa or higher and 1.0 × 10 −3 Pa or lower. It is in the manufacturing method of the transparent conductive film characterized by carrying out a film | membrane.
　本発明の第２６の態様は、第１６又は１７の態様に記載の透明導電膜の製造方法において、前記添加元素がマグネシウムであり、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するマグネシウムのモル比ｘで表される（－４．１×１０－２Ｌｎ（ｘ）－９．３×１０－２）の値未満の範囲にある膜組成の膜を成膜することを特徴とする透明導電膜の製造方法にある。 According to a twenty-sixth aspect of the present invention, in the method for producing a transparent conductive film according to the sixteenth or seventeenth aspect, the additive element is magnesium, and the molar ratio y of tin to 1 mol of indium is indium 1 to deposit a film of the film composition in the range of less than the value of which is expressed as a molar ratio x of magnesium to molar (-4.1 × 10 -2 Ln (x ) -9.3 × 10 -2) It is in the manufacturing method of the transparent conductive film characterized.
　本発明の第２７の態様は、第１６又は１７の態様に記載の透明導電膜の製造方法において、前記添加元素がマグネシウムであり、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するマグネシウムのモル比ｘで表される（－４．１×１０－２Ｌｎ（ｘ）－９．３×１０－２）の値未満であり且つ（－１．６×１０－２Ｌｎ（ｘ）－３．７×１０－２）以上の範囲にある膜組成の膜を、水の分圧が１．０×１０-4Ｐａ以上１．０×１０-３Ｐａ以下の条件下で成膜することを特徴とする透明導電膜の製造方法にある。 According to a twenty-seventh aspect of the present invention, in the method for producing a transparent conductive film according to the sixteenth or seventeenth aspect, the additive element is magnesium, and the molar ratio y of tin to 1 mol of indium is indium 1 Less than the value of (−4.1 × 10 −2 Ln (x) −9.3 × 10 −2 ) expressed by the molar ratio x of magnesium to mol and (−1.6 × 10 −2 Ln ( x) A film having a film composition in the range of −3.7 × 10 −2 ) or higher is formed under conditions where the partial pressure of water is 1.0 × 10 −4 Pa or higher and 1.0 × 10 −3 Pa or lower. It is in the manufacturing method of the transparent conductive film characterized by carrying out a film | membrane.
　本発明の第２８の態様は、第１６又は１７の態様に記載の透明導電膜の製造方法において、前記添加元素がイットリウムであり、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するイットリウムのモル比ｘで表される（－２．５×１０－２Ｌｎ（ｘ）－５．８×１０－２）の値未満の範囲にある膜組成の膜を成膜することを特徴とする透明導電膜の製造方法にある。 According to a twenty-eighth aspect of the present invention, in the method for manufacturing a transparent conductive film according to the sixteenth or seventeenth aspect, the additive element is yttrium, and the molar ratio y of tin to 1 mol of indium is indium 1 Forming a film having a film composition in a range less than the value of (−2.5 × 10 −2 Ln (x) −5.8 × 10 −2 ) represented by the molar ratio x of yttrium to mol. It is in the manufacturing method of the transparent conductive film characterized.
　本発明の第２９の態様は、第１６又は１７の態様に記載の透明導電膜の製造方法において、前記添加元素がイットリウムであり、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するイットリウムのモル比ｘで表される（－２．５×１０－２Ｌｎ（ｘ）－５．８×１０－２）の値未満であり且つ（－２．２×１０－２Ｌｎ（ｘ）－１．５×１０－１）以上の範囲にある膜組成の膜を、水の分圧が１．０×１０-4Ｐａ以上１．０×１０-３Ｐａ以下の条件下で成膜することを特徴とする透明導電膜の製造方法にある。 According to a twenty-ninth aspect of the present invention, in the method for producing a transparent conductive film according to the sixteenth or seventeenth aspect, the additive element is yttrium, and the molar ratio y of tin to 1 mol of indium is indium 1 Less than the value of (−2.5 × 10 −2 Ln (x) −5.8 × 10 −2 ) expressed by the molar ratio x of yttrium to mol, and (−2.2 × 10 −2 Ln ( x) A film having a film composition in the range of −1.5 × 10 −1 ) or more is formed under a condition where the partial pressure of water is 1.0 × 10 −4 Pa or more and 1.0 × 10 −3 Pa or less. It is in the manufacturing method of the transparent conductive film characterized by carrying out a film | membrane.
　本発明によれば、酸化インジウムに錫及び特定の添加元素を添加した組成とし、水の分圧を１．０×１０-4Ｐａ以上１．０×１０-1Ｐａ以下の条件下で成膜した膜は、比較的容易にアモルファス膜とすることができ、成膜後、弱酸エッチングにより容易にパターニングでき、さらに容易に結晶化でき、またさらに結晶化した膜は低抵抗で且つ透過率が高い透明導電膜を製造することができるという効果を奏する。 According to the present invention, a film is formed under the condition that tin and a specific additive element are added to indium oxide, and the partial pressure of water is 1.0 × 10 −4 Pa or more and 1.0 × 10 −1 Pa or less. The film thus obtained can be made relatively easily an amorphous film, can be easily patterned by weak acid etching after the film formation, can be crystallized more easily, and the crystallized film has low resistance and high transmittance. There exists an effect that a transparent conductive film can be manufactured.
本発明のＳｒ含有組成透明導電膜試験例１の結果を示す図である。It is a figure which shows the result of Sr containing composition transparent conductive film test example 1 of this invention. 本発明のＳｒ含有組成透明導電膜試験例２の結果を示す図である。It is a figure which shows the result of Sr containing composition transparent conductive film test example 2 of this invention. 本発明のＳｒ含有組成透明導電膜参考例の結果を示す図である。It is a figure which shows the result of the Sr containing composition transparent conductive film reference example of this invention. 本発明のＬｉ含有組成透明導電膜試験例１の結果を示す図である。It is a figure which shows the result of the Li containing composition transparent conductive film test example 1 of this invention. 本発明のＬｉ含有組成透明導電膜試験例２の結果を示す図である。It is a figure which shows the result of the Li containing composition transparent conductive film test example 2 of this invention. 本発明のＬｉ含有組成透明導電膜参考例の結果を示す図である。It is a figure which shows the result of the Li containing composition transparent conductive film reference example of this invention. 本発明のＬａ含有組成透明導電膜試験例１の結果を示す図である。It is a figure which shows the result of La containing composition transparent conductive film test example 1 of this invention. 本発明のＬａ含有組成透明導電膜試験例２の結果を示す図である。It is a figure which shows the result of the La containing composition transparent conductive film test example 2 of this invention. 本発明のＬａ含有組成透明導電膜参考例の結果を示す図である。It is a figure which shows the result of the La containing composition transparent conductive film reference example of this invention. 本発明のＣａ含有組成透明導電膜試験例１の結果を示す図である。It is a figure which shows the result of the Ca containing composition transparent conductive film test example 1 of this invention. 本発明のＣａ含有組成透明導電膜試験例２の結果を示す図である。It is a figure which shows the result of the Ca containing composition transparent conductive film test example 2 of this invention. 本発明のＣａ含有組成透明導電膜参考例の結果を示す図である。It is a figure which shows the result of the Ca containing composition transparent conductive film reference example of this invention. 本発明のＭｇ含有組成透明導電膜試験例１の結果を示す図である。It is a figure which shows the result of the Mg containing composition transparent conductive film test example 1 of this invention. 本発明のＭｇ含有組成透明導電膜試験例２の結果を示す図である。It is a figure which shows the result of the Mg containing composition transparent conductive film test example 2 of this invention. 本発明のＭｇ含有組成透明導電膜参考例の結果を示す図である。It is a figure which shows the result of the Mg containing composition transparent conductive film reference example of this invention. 本発明のＹ含有組成透明導電膜試験例１の結果を示す図である。It is a figure which shows the result of the Y containing composition transparent conductive film test example 1 of this invention. 本発明のＹ含有組成透明導電膜試験例２の結果を示す図である。It is a figure which shows the result of the Y containing composition transparent conductive film test example 2 of this invention. 本発明のＹ含有組成透明導電膜参考例の結果を示す図である。It is a figure which shows the result of the Y containing composition transparent conductive film reference example of this invention. 本発明のＴＰＤ水素確認試験の結果を示す図である。It is a figure which shows the result of the TPD hydrogen confirmation test of this invention. 図１９のベースライン補正を行った図である。It is the figure which performed the baseline correction | amendment of FIG.
　本発明の酸化インジウム系透明導電膜を形成するために用いる透明導電膜用スパッタリングターゲットは、酸化インジウムを主体とし、錫を含有するもので、且つＳｒ（ストロンチウム）、Ｌｉ（リチウム）、Ｌａ（ランタン）、Ｃａ（カルシウム）、Ｍｇ（マグネシウム）及びＹ（イットリウム）からなる群から選択される少なくとも一種の特定の添加元素を含有する酸化物焼結体であり、添加元素は、その酸化物のまま、あるいは複合酸化物として、あるいは固溶体として存在していればよく、特に限定されない。 The sputtering target for transparent conductive film used for forming the indium oxide-based transparent conductive film of the present invention is mainly composed of indium oxide and contains tin, and Sr (strontium), Li (lithium), La (lanthanum). ), Ca (calcium), Mg (magnesium), and Y (yttrium), and is an oxide sintered body containing at least one specific additive element selected from the group consisting of Y (yttrium). Alternatively, it may be present as a complex oxide or as a solid solution, and is not particularly limited.
　添加元素の含有量は、水の分圧を１．０×１０-4Ｐａ以上１．０×１０-1Ｐａ以下の条件下で１００℃以下の成膜温度で成膜した膜がアモルファス膜として成膜されるように選定すればよく、添加元素の種類や成膜条件で異なるが、インジウム１モルに対して０．００００１モル以上０．１０モル未満の範囲から選択することができる。 The content of the additive element is such that the film formed at a film forming temperature of 100 ° C. or less under the condition that the partial pressure of water is 1.0 × 10 −4 Pa or more and 1.0 × 10 −1 Pa or less is an amorphous film. What is necessary is just to select so that it may form into a film, Although it changes with the kind of additive element, and film-forming conditions, it can select from the range of 0.00001 mol or more and less than 0.10 mol with respect to 1 mol of indium.
　また、錫の含有量は、インジウム１モルに対して０．００１～０．３モル、好ましくは、０．００５～０．３モルの範囲から選択され、このような範囲で錫を含有するスパッタリングターゲットを用いて成膜されるのが望ましい。この範囲内であれば、スパッタリングターゲットのキャリヤ電子の密度並びに移動度を適切にコントロールして導電性を良好な範囲に保つことができる。また、この範囲を越えて添加すると、スパッタリングターゲットのキャリヤ電子の移動度を低下させると共に導電性を劣化させる方向に働くので好ましくない。 Further, the content of tin is selected from the range of 0.001 to 0.3 mol, preferably 0.005 to 0.3 mol, with respect to 1 mol of indium, and sputtering containing tin in such a range. It is desirable to form a film using a target. Within this range, the density and mobility of carrier electrons in the sputtering target can be appropriately controlled to keep the conductivity in a good range. Further, addition beyond this range is not preferable because the mobility of carrier electrons of the sputtering target is lowered and the conductivity is deteriorated.
　なお、このような特定組成を有するスパッタリングターゲットにより形成された透明導電膜中の添加元素や錫の含有量は、使用したスパッタリングターゲット中の含有量と同一の含有量となる。このような酸化インジウム系透明導電膜の組成分析は、単膜を全量溶解しＩＣＰで分析してもよい。また、膜自体が素子構成をなしている場合などは、必要に応じてＦＩＢ等により該当する部分の断面を切り出し、ＳＥＭやＴＥＭ等に付属している元素分析装置（ＥＤＳやＷＤＳ、オージェ分析など）を用いても特定することが可能である。 In addition, content of the additive element and tin in the transparent conductive film formed with the sputtering target having such a specific composition is the same content as the content in the used sputtering target. For the composition analysis of such an indium oxide-based transparent conductive film, the entire amount of a single film may be dissolved and analyzed by ICP. In addition, when the film itself has an element configuration, if necessary, a cross section of the corresponding part is cut out by FIB or the like, and an element analyzer (EDS, WDS, Auger analysis, etc.) attached to the SEM, TEM, etc. ) Can also be specified.
　かかるスパッタリングターゲットは、ＤＣマグネトロンスパッタリングでスパッタリング可能な程度の抵抗値を有しているので、比較的安価なＤＣマグネトロンスパッタリングでスパッタリング可能であるが、勿論、高周波マグネトロンスパッタリング装置を用いてもよい。 Since such a sputtering target has a resistance value that can be sputtered by DC magnetron sputtering, it can be sputtered by relatively inexpensive DC magnetron sputtering. Of course, a high-frequency magnetron sputtering apparatus may be used.
　このような透明導電膜用スパッタリングターゲットを用い、水の分圧が１．０×１０-4Ｐａ以上１．０×１０-1Ｐａ以下の条件下で成膜したものとすることにより、同一組成で結晶化温度が比較的低いアモルファスの酸化インジウム系透明導電膜が形成できる。また、かかる水の分圧化で成膜した場合、アモルファス膜内に水素が取り込まれる。すなわち、成膜されたアモルファス膜は水素を含有するものとなり、水素を含有するか否かにより、上述した所定の水分圧化で成膜したか、又は実質的に水が存在しない１．０×１０-4Ｐａ未満で成膜したかを確認することができる。 By using such a sputtering target for a transparent conductive film and forming a film under the condition that the partial pressure of water is 1.0 × 10 −4 Pa or more and 1.0 × 10 −1 Pa or less, the same composition is obtained. Thus, an amorphous indium oxide-based transparent conductive film having a relatively low crystallization temperature can be formed. Further, when the film is formed by such partial pressure of water, hydrogen is taken into the amorphous film. That is, the formed amorphous film contains hydrogen. Depending on whether or not hydrogen is contained, the amorphous film is formed at the predetermined moisture pressure described above or substantially 1.0 × without water. It can be confirmed whether or not the film is formed at less than 10 −4 Pa.
　ここで、水の分圧を上述した所定範囲とするためには、成膜チャンバに成膜時に導入する雰囲気ガス（一般的にはＡｒ、必要に応じて酸素を含有したガスであり、例えば、１０-4Ｐａ台の圧力）と共に水蒸気をマスフローコントローラなどを介して導入すればよく、到達真空度が１０-4Ｐａ未満と高真空の場合には、雰囲気ガスの１／１００～１／１０程度の圧力とするのが好ましい。なお、到達真空度が１０-4～１０-3Ｐａ程度と真空度が悪い条件下では、その残留ガスの主成分は、水である。つまり、その到達真空度がほぼ水の分圧に相当するので、水蒸気を特に導入することなく所望の水の分圧の状態を得ることができる。 Here, in order to set the partial pressure of water within the predetermined range described above, an atmospheric gas (generally Ar, a gas containing oxygen as necessary, which is introduced into the film formation chamber during film formation, for example, It is only necessary to introduce water vapor through a mass flow controller or the like with a pressure of the order of 10 −4 Pa, and when the ultimate vacuum is less than 10 −4 Pa and a high vacuum, about 1/100 to 1/10 of the atmospheric gas. Preferably, the pressure is Note that, under the condition that the ultimate degree of vacuum is about 10 −4 to 10 −3 Pa and the degree of vacuum is poor, the main component of the residual gas is water. That is, since the ultimate vacuum corresponds approximately to the partial pressure of water, a desired partial pressure of water can be obtained without particularly introducing water vapor.
　このような本発明の酸化インジウム系透明導電膜は、添加元素が所定量含有されているので、成膜を室温以上で結晶化温度、すなわち、１００℃以上の結晶化温度より低い温度条件で行うことにより、アモルファス状の状態で成膜されるというものである。また、このようなアモルファスな膜は、弱酸性のエッチャントでのエッチングを行うことができるという利点がある。また、このようなエッチングにより残渣がない状態で精細なパターンを形成することができるという効果を奏する。なお、本件明細書では、エッチングは、パターニング工程に含まれるもので、所定のパターンを得るためのものである。 Such an indium oxide-based transparent conductive film according to the present invention contains a predetermined amount of an additive element, so that film formation is performed at room temperature or higher and a crystallization temperature, that is, a temperature condition lower than 100 ° C. or higher. Thus, the film is formed in an amorphous state. Further, such an amorphous film has an advantage that it can be etched with a weakly acidic etchant. In addition, such an etching has an effect that a fine pattern can be formed without any residue. In this specification, the etching is included in the patterning step and is for obtaining a predetermined pattern.
　また、得られる透明導電膜の抵抗率は添加元素や錫の含有量によっても異なるが、抵抗率が１．０×１０-4～１．０×１０-3Ω・ｃｍである。 The resistivity of the transparent conductive film obtained varies depending on the additive element and the tin content, but the resistivity is 1.0 × 10 −4 to 1.0 × 10 −3 Ω · cm.
　さらに、成膜した膜の結晶化温度は含有される添加元素や錫の含有量によって異なり、含有量が上昇するほど上昇するが、１００℃～３００℃の温度条件でアニールすることにより、結晶化させることができる。このような温度領域は通常の半導体製造プロセスで使用されているので、このようなプロセスの中で結晶化させることもできる。なお、この温度範囲の中で、１００℃～３００℃で結晶化するものが好ましく、１５０℃～２５０℃で結晶化するのがさらに好ましく、２００℃～２５０℃で結晶化するものが最も好ましい。 Furthermore, the crystallization temperature of the deposited film varies depending on the content of additive elements and tin contained, and increases as the content increases. By annealing at a temperature of 100 ° C to 300 ° C, the crystallization temperature is increased. Can be made. Since such a temperature region is used in a normal semiconductor manufacturing process, it can be crystallized in such a process. In this temperature range, those that crystallize at 100 ° C. to 300 ° C. are preferred, crystals that crystallize at 150 ° C. to 250 ° C. are more preferred, and those that crystallize at 200 ° C. to 250 ° C. are most preferred.
　ここで、アニールとは、大気中、雰囲気中、真空中などにおいて、所望の温度にて一定時間加熱することをさす。その一定時間とは、一般に数分から数時間程度であるが、工業的には効果が同じであれば短い時間が好まれる。 Here, annealing refers to heating at a desired temperature for a certain period of time in air, atmosphere, or vacuum. The fixed time is generally several minutes to several hours, but a short time is preferred industrially if the effect is the same.
　このようにアニールにより結晶化された後の透明導電膜は、短波長側の透過率が向上し、例えば、波長４００～５００ｎｍの平均透過率が８５％以上となる。また、これによって、ＩＺＯで問題となっているような膜が黄色みがかるという問題もない。なお、一般に短波長側の透過率は、高ければ高い方が好まれる。 Thus, the transparent conductive film after being crystallized by annealing has improved transmittance on the short wavelength side, for example, the average transmittance at a wavelength of 400 to 500 nm is 85% or more. This also eliminates the problem that the film which is a problem in IZO is yellowish. In general, a higher transmittance on the short wavelength side is preferred.
　一方、結晶化された透明導電膜は、エッチング耐性が向上し、アモルファスな膜ではエッチングが可能な弱酸性のエッチャントではエッチングできなくなる。これによって後工程での耐腐食性や、デバイス自体の耐環境性が向上する。 On the other hand, the crystallized transparent conductive film has improved etching resistance and cannot be etched with a weakly acidic etchant that can be etched with an amorphous film. This improves the corrosion resistance in the subsequent process and the environmental resistance of the device itself.
　このように本発明では、添加元素の含有量を変化させることにより、成膜後の結晶化温度を所望の温度に設定できるので、成膜後、結晶化温度以上の温度の熱処理を受けないようにして、アモルファス状態を維持するようにしてもよいし、成膜後パターニングした後、結晶化する温度以上の温度で熱処理して結晶化し、耐エッチング特性を変化させるようにしてもよい。 Thus, in the present invention, by changing the content of the additive element, the crystallization temperature after film formation can be set to a desired temperature, so that heat treatment at a temperature higher than the crystallization temperature is not applied after film formation. Thus, the amorphous state may be maintained, or after patterning after film formation, crystallization may be performed by heat treatment at a temperature equal to or higher than the crystallization temperature to change the etching resistance.
　ここで、アモルファスな膜として成膜できるかどうかは、上述したように成膜される膜の組成における結晶化温度より低い成膜温度で成膜する必要があり、錫や添加元素の含有量が少ない組成ほど結晶化温度が低くなり、錫や添加元素の含有量が多い組成ほど結晶化温度が高くなる傾向となるが、水の分圧を１．０×１０-4Ｐａ以上１．０×１０-1Ｐａ以下の条件下で成膜することにより、各組成の結晶化温度を水の分圧を１．０×１０-4Ｐａ未満で成膜したときと比較して５０～１００℃程度高くすることができる。 Here, whether or not the film can be formed as an amorphous film needs to be formed at a film formation temperature lower than the crystallization temperature in the composition of the film formed as described above, and the content of tin and additive elements is small. less becomes the crystallization temperature as the composition is low, tin and although the crystallization temperature as the composition containing a large amount of the additive element is high tends, 1.0 the partial pressure of water 1.0 × 10 -4 Pa or more × By forming the film under the condition of 10 −1 Pa or less, the crystallization temperature of each composition is about 50 to 100 ° C. as compared with the case where the film is formed with a partial pressure of water of less than 1.0 × 10 −4 Pa. Can be high.
　よって、特に、水の分圧を１．０×１０-4Ｐａ未満で成膜したときに、結晶化温度が１００℃未満、特に室温近くになり、アモルファスな膜を得るための成膜条件がかなり厳しい組成範囲においては、水の分圧を１．０×１０-4Ｐａ以上１．０×１０-1Ｐａ以下の条件下とすることにより、結晶化温度を、例えば、１００℃以上と上昇させることができ、例えば、１００℃程度の成膜条件でもアモルファスな膜を得ることができる。 Therefore, particularly when the film is formed with a partial pressure of water of less than 1.0 × 10 −4 Pa, the crystallization temperature is less than 100 ° C., particularly near room temperature, and the film formation conditions for obtaining an amorphous film are In a fairly severe composition range, the crystallization temperature is increased to, for example, 100 ° C. or higher by setting the partial pressure of water to 1.0 × 10 −4 Pa or more and 1.0 × 10 −1 Pa or less. For example, an amorphous film can be obtained even under film forming conditions of about 100 ° C.
　勿論、添加元素の含有量が比較的高く、水の分圧が１．０×１０-4Ｐａよりも低い通常条件での成膜でも、結晶化温度が１００℃以上のアモルファスな膜が成膜できる組成範囲においては、水の分圧を１．０×１０-4Ｐａ以上１．０×１０-1Ｐａ以下の条件下で成膜することにより、アニールによる結晶化温度が多少上昇するが、アモルファス膜が成膜できることはいうまでもない。 Of course, an amorphous film having a crystallization temperature of 100 ° C. or more is formed even in a film formation under a normal condition in which the content of the additive element is relatively high and the partial pressure of water is lower than 1.0 × 10 −4 Pa. In the composition range where the partial pressure of water is formed under conditions where the partial pressure of water is 1.0 × 10 −4 Pa or more and 1.0 × 10 −1 Pa or less, the crystallization temperature due to annealing slightly increases. Needless to say, an amorphous film can be formed.
　なお、水の分圧が１．０×１０-4Ｐａよりも低いと、上述したような結晶化温度を上昇させる効果が顕著ではなく、一方、水の分圧が上限（１．０×１０-1Ｐａ）よりも大きい場合には、得られる膜はアモルファスであるが、結晶化温度が上昇し、３００℃のアニール条件でも結晶化しないため、比抵抗が低減せず、また、アニールして結晶化したとしても膜の比抵抗が低減せず、５．０×１０-4Ω・ｃｍ以下の結晶化膜が得られがたくなり、好ましくはない。 When the partial pressure of water is lower than 1.0 × 10 −4 Pa, the effect of increasing the crystallization temperature as described above is not remarkable, while the partial pressure of water is the upper limit (1.0 × 10 10 -1 Pa), the resulting film is amorphous, but the crystallization temperature rises, and since it does not crystallize even under 300 ° C. annealing conditions, the specific resistance is not reduced and the film is annealed. Even if it is crystallized, the specific resistance of the film does not decrease, and it becomes difficult to obtain a crystallized film of 5.0 × 10 −4 Ω · cm or less, which is not preferable.
　このような水分圧の条件下で成膜されたアモルファス膜は、水素を含有するものであり、水素の存在は、上述する試験方法で確認することができる。 The amorphous film formed under such a moisture pressure condition contains hydrogen, and the presence of hydrogen can be confirmed by the test method described above.
　ここで、水の分圧が１．０×１０-4Ｐａよりも低い通常条件での成膜した場合、結晶化温度が１００℃以上のアモルファス膜が成膜できない組成範囲においては、水の分圧を１．０×１０-4Ｐａ以上１．０×１０-1Ｐａ以下の条件下とすることにより、アモルファス膜が得られるが、このような組成範囲は添加元素の種類によりことなる。以下、このような組成範囲について説明する。 Here, when the film is formed under a normal condition where the partial pressure of water is lower than 1.0 × 10 −4 Pa, in the composition range where an amorphous film having a crystallization temperature of 100 ° C. or higher cannot be formed, An amorphous film can be obtained by adjusting the pressure to 1.0 × 10 −4 Pa or more and 1.0 × 10 −1 Pa or less, but such a composition range depends on the kind of the additive element. Hereinafter, such a composition range will be described.
　添加元素がＳｒの場合、水の分圧を１．０×１０-4Ｐａ以上１．０×１０-1Ｐａ以下の条件下とすることにより初めてアモルファスな膜となり、その後、１００℃～３００℃でアニールした場合に結晶化する組成範囲は、インジウム１モルに対しての錫のモル比ｙ（モル）が、インジウム１モルに対するＳｒのモル比ｘで表される（－４．１×１０－２Ｌｎ（ｘ）－９．３×１０－２）の値未満の範囲となる。 When the additive element is Sr, an amorphous film is formed only when the partial pressure of water is 1.0 × 10 −4 Pa or more and 1.0 × 10 −1 Pa or less, and thereafter 100 ° C. to 300 ° C. in the composition range of crystallization when annealed, the molar ratio of tin to indium mole y (mol) is represented by the molar ratio x of Sr relative to 1 mol of indium (-4.1 × 10 - 2 Ln (x) −9.3 × 10 −2 ).
　また、このような範囲において、特に、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するＳｒのモル比ｘで表される（－４．１×１０－２Ｌｎ（ｘ）－９．３×１０－２）の値未満であり且つ－１．６×１０－２Ｌｎ（ｘ）－３．７×１０－２）以上の組成範囲では、水の分圧が１．０×１０-4Ｐａ以上１．０×１０-３Ｐａ以下の条件下でアモルファスな膜となり、その後、１００℃～３００℃でアニールした場合に結晶化し、成膜プロセスを考慮するとさらに好ましいものとなる。 Further, in such a range, in particular, the molar ratio y of tin to indium mole, represented by the molar ratio x of Sr relative to 1 mol of indium (-4.1 × 10 -2 Ln (x ) −9.3 × 10 −2 ) and less than −1.6 × 10 −2 Ln (x) −3.7 × 10 −2 ), the partial pressure of water is 1.0 It becomes an amorphous film under the condition of x10 −4 Pa or more and 1.0 × 10 −3 Pa or less, and then crystallizes when annealed at 100 ° C. to 300 ° C., which is more preferable in consideration of the film forming process. .
　添加元素がＬｉの場合、水の分圧を１．０×１０-4Ｐａ以上１．０×１０-1Ｐａ以下の条件下とすることにより初めてアモルファスな膜となり、その後、１００℃～３００℃でアニールした場合に結晶化する組成範囲は、インジウム１モルに対しての錫のモル比ｙ（モル）が、インジウム１モルに対するＬｉのモル比ｘで表される（－１．６×１０－１Ｌｎ（ｘ）－５．９×１０－１）の値未満の範囲となる。 When the additive element is Li, an amorphous film is formed only when the partial pressure of water is 1.0 × 10 −4 Pa or more and 1.0 × 10 −1 Pa or less, and then 100 ° C. to 300 ° C. As for the composition range to be crystallized when annealed at a temperature, the molar ratio y (mol) of tin to 1 mol of indium is represented by the molar ratio x of Li to 1 mol of indium (−1.6 × 10 − 1 Ln (x) −5.9 × 10 −1 ).
　また、このような範囲において、特に、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するＬｉのモル比ｘで表される（－１．６×１０－１Ｌｎ（ｘ）－５．９×１０－１）の値未満であり且つ（－３．５×１０－２Ｌｎ（ｘ）－１．６×１０－１）以上の組成範囲では、水の分圧が１．０×１０-4Ｐａ以上１．０×１０-３Ｐａ以下の条件下でアモルファスな膜となり、その後、１００℃～３００℃でアニールした場合に結晶化し、成膜プロセスを考慮するとさらに好ましいものとなる。 In such a range, in particular, the molar ratio y of tin to 1 mol of indium is represented by the molar ratio x of Li to 1 mol of indium (−1.6 × 10 −1 Ln (x) In the composition range of less than the value of −5.9 × 10 −1 ) and not less than (−3.5 × 10 −2 Ln (x) −1.6 × 10 −1 ), the partial pressure of water is 1. It becomes an amorphous film under conditions of 0 × 10 −4 Pa or more and 1.0 × 10 −3 Pa or less, and then crystallizes when annealed at 100 ° C. to 300 ° C. Become.
　添加元素がＬａの場合には、水の分圧を１．０×１０-4Ｐａ以上１．０×１０-1Ｐａ以下の条件下とすることにより初めてアモルファスな膜となり、その後、１００℃～３００℃でアニールした場合に結晶化する組成範囲は、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するＬａのモル比ｘで表される（－６．７×１０－２Ｌｎ（ｘ）－２．２×１０－１）の値未満の範囲である。 When the additive element is La, an amorphous film is formed only when the partial pressure of water is 1.0 × 10 −4 Pa or more and 1.0 × 10 −1 Pa or less. The composition range that crystallizes when annealed at 300 ° C. is expressed by the molar ratio y of tin to 1 mol of indium expressed as the molar ratio x of La to 1 mol of indium (−6.7 × 10 −2 Ln (x) −2.2 × 10 −1 ).
　また、このような範囲において、特に、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するＬａのモル比ｘで表される（－６．７×１０－２Ｌｎ（ｘ）－２．２×１０－１）の値未満であり且つ－２．９×１０－２Ｌｎ（ｘ）－１．３×１０－１）以上の組成範囲では、水の分圧が１．０×１０-4Ｐａ以上１．０×１０-３Ｐａ以下の条件下でアモルファスな膜となり、その後、１００℃～３００℃でアニールした場合に結晶化し、成膜プロセスを考慮するとさらに好ましいものとなる。 In such a range, in particular, the molar ratio y of tin to 1 mol of indium is represented by the molar ratio x of La to 1 mol of indium (−6.7 × 10 −2 Ln (x) −2.2 × 10 −1 ) and less than −2.9 × 10 −2 Ln (x) −1.3 × 10 −1 ), the partial pressure of water is 1.0. It becomes an amorphous film under the condition of x10 −4 Pa or more and 1.0 × 10 −3 Pa or less, and then crystallizes when annealed at 100 ° C. to 300 ° C., which is more preferable in consideration of the film forming process. .
　添加元素がＣａの場合には、水の分圧を１．０×１０-4Ｐａ以上１．０×１０-1Ｐａ以下の条件下とすることにより初めてアモルファスな膜となり、その後、１００℃～３００℃でアニールした場合に結晶化する組成範囲は、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するＣａのモル比ｘで表される（－４．１×１０－２Ｌｎ（ｘ）－９．３×１０－２）の値未満の範囲である。 When the additional element of Ca, for the first time become the amorphous film by a partial pressure below 1.0 × 10 -4 Pa or 1.0 × 10 -1 Pa under the conditions of water, then, 100 ° C. ~ In the composition range that crystallizes when annealed at 300 ° C., the molar ratio y of tin to 1 mol of indium is expressed by the molar ratio x of Ca to 1 mol of indium (−4.1 × 10 −2 Ln (x) −9.3 × 10 −2 ).
　また、このような範囲において、特に、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するＣａのモル比ｘで表される（－４．１×１０－２Ｌｎ（ｘ）－９．３×１０－２）の値未満であり且つ（－１．６×１０－２Ｌｎ（ｘ）－３．７×１０－２）以上の範囲では、水の分圧が１．０×１０-4Ｐａ以上１．０×１０-３Ｐａ以下の条件下でアモルファスな膜となり、その後、１００℃～３００℃でアニールした場合に結晶化し、成膜プロセスを考慮するとさらに好ましいものとなる。 In such a range, in particular, the molar ratio y of tin to 1 mol of indium is expressed by the molar ratio x of Ca to 1 mol of indium (−4.1 × 10 −2 Ln (x) In the range of less than (−9.3 × 10 −2 ) and (−1.6 × 10 −2 Ln (x) −3.7 × 10 −2 ) or more, the partial pressure of water is 1.0. It becomes an amorphous film under the condition of x10 −4 Pa or more and 1.0 × 10 −3 Pa or less, and then crystallizes when annealed at 100 ° C. to 300 ° C., which is more preferable in consideration of the film forming process. .
　添加元素がＭｇの場合には、水の分圧を１．０×１０-4Ｐａ以上１．０×１０-1Ｐａ以下の条件下とすることにより初めてアモルファスな膜となり、その後、１００℃～３００℃でアニールした場合に結晶化する組成範囲は、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するＭｇのモル比ｘで表される（－４．１×１０－２Ｌｎ（ｘ）－９．３×１０－２）の値未満の範囲である。 When the additional element of Mg, for the first time become the amorphous film by a partial pressure below 1.0 × 10 -4 Pa or 1.0 × 10 -1 Pa under the conditions of water, then, 100 ° C. ~ In the composition range that crystallizes when annealed at 300 ° C., the molar ratio y of tin to 1 mol of indium is expressed by the molar ratio x of Mg to 1 mol of indium (−4.1 × 10 −2 Ln (x) −9.3 × 10 −2 ).
　また、このような範囲において、特に、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するＭｇのモル比ｘで表される（－４．１×１０－２Ｌｎ（ｘ）－９．３×１０－２）の値未満であり且つ（－１．６×１０－２Ｌｎ（ｘ）－３．７×１０－２）以上の範囲では、水の分圧が１．０×１０-4Ｐａ以上１．０×１０-３Ｐａ以下の条件下でアモルファスな膜となり、その後、１００℃～３００℃でアニールした場合に結晶化し、成膜プロセスを考慮するとさらに好ましいものとなる。 In such a range, in particular, the molar ratio y of tin to 1 mol of indium is expressed by the molar ratio x of Mg to 1 mol of indium (−4.1 × 10 −2 Ln (x) In the range of less than (−9.3 × 10 −2 ) and (−1.6 × 10 −2 Ln (x) −3.7 × 10 −2 ) or more, the partial pressure of water is 1.0. It becomes an amorphous film under the condition of x10 −4 Pa or more and 1.0 × 10 −3 Pa or less, and then crystallizes when annealed at 100 ° C. to 300 ° C., which is more preferable in consideration of the film forming process. .
　添加元素がＹの場合には、水の分圧を１．０×１０-4Ｐａ以上１．０×１０-1Ｐａ以下の条件下とすることにより初めてアモルファスな膜となり、その後、１００℃～３００℃でアニールした場合に結晶化する組成範囲は、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するＹのモル比ｘで表される（－２．５×１０－２Ｌｎ（ｘ）－５．８×１０－２）の値未満の範囲である。 When the additive element is Y, an amorphous film is formed only when the partial pressure of water is 1.0 × 10 −4 Pa or more and 1.0 × 10 −1 Pa or less. The composition range that crystallizes when annealed at 300 ° C. is expressed by a molar ratio y of tin to 1 mol of indium and a molar ratio x of Y to 1 mol of indium (−2.5 × 10 −2 Ln (x) −5.8 × 10 −2 ).
　また、このような範囲において、特に、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するＹのモル比ｘで表される（－２．５×１０－２Ｌｎ（ｘ）－５．８×１０－２）の値未満であり且つ（－２．２×１０－２Ｌｎ（ｘ）－１．５×１０－１）以上の範囲では、水の分圧が１．０×１０-4Ｐａ以上１．０×１０-３Ｐａ以下の条件下でアモルファスな膜となり、その後、１００℃～３００℃でアニールした場合に結晶化し、成膜プロセスを考慮するとさらに好ましいものとなる。 In such a range, in particular, the molar ratio y of tin to 1 mol of indium is represented by the molar ratio x of Y to 1 mol of indium (−2.5 × 10 −2 Ln (x) In the range of less than (−5.8 × 10 −2 ) and (−2.2 × 10 −2 Ln (x) −1.5 × 10 −1 ) or more, the partial pressure of water is 1.0. It becomes an amorphous film under the condition of x10 −4 Pa or more and 1.0 × 10 −3 Pa or less, and then crystallizes when annealed at 100 ° C. to 300 ° C., which is more preferable in consideration of the film forming process. .
　次に、本発明で用いるスパッタリングターゲットの製造方法について説明するが、これは単に例示したものであり、製造方法は特に限定されるものではない。 Next, the manufacturing method of the sputtering target used in the present invention will be described. However, this is merely an example, and the manufacturing method is not particularly limited.
　まず、本発明のスパッタリングターゲットを構成する出発原料としては、一般的には構成元素の酸化物を用いるが、これらの単体、化合物、複合酸化物等を原料としてもよい。単体、化合物を使う場合はあらかじめ酸化物にするようなプロセスを通すようにする。 First, as a starting material constituting the sputtering target of the present invention, an oxide of a constituent element is generally used, but these simple substances, compounds, complex oxides, and the like may be used as a raw material. When using a simple substance or a compound, it is made to go through a process of making it oxide in advance.
　これらの原料粉を、所望の配合率で混合し、成形する方法は特に限定されず、従来から公知の各種湿式法又は乾式法を用いることができる。 The method of mixing and molding these raw material powders at a desired blending ratio is not particularly limited, and various conventionally known wet methods or dry methods can be used.
　乾式法としては、コールドプレス（Ｃｏｌｄ　Ｐｒｅｓｓ）法やホットプレス（Ｈｏｔ　Ｐｒｅｓｓ）法等を挙げることができる。コールドプレス法では、混合粉を成形型に充填して成形体を作製し、焼成させる。ホットプレス法では、混合粉を成形型内で焼成、焼結させる。 Examples of the dry method include a cold press method and a hot press method. In the cold press method, the mixed powder is filled in a mold to produce a molded body and fired. In the hot press method, the mixed powder is fired and sintered in a mold.
　湿式法としては、例えば、濾過式成形法（特開平１１－２８６００２号公報参照）を用いるのが好ましい。この濾過式成形法は、セラミックス原料スラリーから水分を減圧排水して成形体を得るための非水溶性材料からなる濾過式成形型であって、１個以上の水抜き孔を有する成形用下型と、この成形用下型の上に載置した通水性を有するフィルターと、このフィルターをシールするためのシール材を介して上面側から挟持する成形用型枠からなり、前記成形用下型、成形用型枠、シール材、およびフィルターが各々分解できるように組立てられており、該フィルター面側からのみスラリー中の水分を減圧排水する濾過式成形型を用い、混合粉、イオン交換水と有機添加剤からなるスラリーを調製し、このスラリーを濾過式成形型に注入し、該フィルター面側からのみスラリー中の水分を減圧排水して成形体を製作し、得られたセラミックス成形体を乾燥脱脂後、焼成する。 As the wet method, for example, a filtration molding method (see JP-A-11-286002) is preferably used. This filtration molding method is a filtration molding die made of a water-insoluble material for obtaining a molded body by draining water from a ceramic raw material slurry under reduced pressure, and a lower molding die having one or more drain holes And a water-permeable filter placed on the molding lower mold, and a molding mold clamped from the upper surface side through a sealing material for sealing the filter, the molding lower mold, Forming mold, sealing material, and filter are assembled so that they can be disassembled respectively. Using a filtration mold that drains water in the slurry under reduced pressure only from the filter surface side, mixed powder, ion-exchanged water and organic Prepare a slurry consisting of additives, inject the slurry into a filtration mold, drain the water in the slurry only from the filter surface side, and produce a molded body. After drying degreasing, and firing.
　コールドプレス法や湿式法で成形したものの焼成温度は、１３００～１６５０℃が好ましく、さらに好ましくは、１５００～１６５０℃であり、その雰囲気は大気雰囲気、酸素雰囲気、非酸化性雰囲気、または真空雰囲気などである。一方、ホットプレス法の場合は、１２００℃付近で焼結させることが好ましく、その雰囲気は、非酸化性雰囲気や真空雰囲気などである。なお、各方法において焼成した後には、所定寸法に成形・加工のための機械加工を施しターゲットとする。 The firing temperature of the one formed by the cold press method or the wet method is preferably 1300 to 1650 ° C., more preferably 1500 to 1650 ° C., and the atmosphere is an air atmosphere, an oxygen atmosphere, a non-oxidizing atmosphere, a vacuum atmosphere, or the like. It is. On the other hand, in the case of the hot press method, sintering is preferably performed at around 1200 ° C., and the atmosphere is a non-oxidizing atmosphere, a vacuum atmosphere, or the like. In addition, after baking in each method, the machining for shaping | molding and a process is given to a predetermined dimension, and it is set as a target.
　以下、本発明を実施例に基づいて説明するが、これに限定されるものではない。 Hereinafter, the present invention will be described based on examples, but is not limited thereto.
　（スパッタリングターゲット製造例１）（Ｓｒ－ＩＴＯ）
　純度＞９９．９９％のＩｎ２Ｏ３粉、ＳｎＯ２粉、および純度＞９９．９％のＳｒＣＯ３粉を用意し、まず、Ｉｎ２Ｏ３粉及び、ＳｒＣＯ３粉を乾燥状態でボールミル混合し、大気中１２００℃で３時間仮焼し、ＳｒＩｎ２Ｏ４粉を得た。次いで上記、ＳｒＩｎ２Ｏ４粉、Ｉｎ２Ｏ３粉およびＳｎＯ２粉を全量約１．０ｋｇ用意し（各金属原子の組成は、下記表１、２に示すものとした）、これをボールミル混合した。その後バインダーとしてＰＶＡ水溶液を添加して混合、乾燥し、コールドプレスして成形体を得た。この成形体を、大気中６００℃で１０時間、６０℃／ｈの昇温で脱脂し、次いで、酸素雰囲気下、１５５０℃で８時間焼成して焼結体を得た。焼成条件は具体的には、室温から８００℃まで２００℃／ｈで昇温し、８００℃から１５５０℃まで４００℃／ｈで昇温し、８時間保持した後、１５５０℃から室温まで１００℃／ｈの条件で冷却という条件である。その後、この焼結体を加工しターゲットを得た。 (Sputtering target production example 1) (Sr-ITO)
Prepare In 2 O 3 powder with purity> 99.99%, SnO 2 powder, and SrCO 3 powder with purity> 99.9%. First, In 2 O 3 powder and SrCO 3 powder are mixed in a ball mill in a dry state. And calcined in the atmosphere at 1200 ° C. for 3 hours to obtain SrIn 2 O 4 powder. Next, about 1.0 kg of the total amount of the above SrIn 2 O 4 powder, In 2 O 3 powder and SnO 2 powder was prepared (the composition of each metal atom was as shown in Tables 1 and 2 below), and this was mixed with a ball mill. did. Thereafter, an aqueous PVA solution was added as a binder, mixed, dried, and cold pressed to obtain a molded body. This molded body was degreased at 600 ° C. for 10 hours in the air at a temperature increase of 60 ° C./h, and then fired at 1550 ° C. for 8 hours in an oxygen atmosphere to obtain a sintered body. Specifically, the firing condition is that the temperature is raised from room temperature to 800 ° C. at 200 ° C./h, the temperature is raised from 800 ° C. to 1550 ° C. at 400 ° C./h, held for 8 hours, and then 1550 ° C. to room temperature is 100 ° C. It is a condition of cooling under the condition of / h. Thereafter, this sintered body was processed to obtain a target.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　（スパッタリングターゲット製造例２）（Ｌｉ－ＩＴＯ）
　純度＞９９．９９％のＩｎ２Ｏ３粉、ＳｎＯ２粉、および純度＞９９．９％のＬｉ２ＣＯ３粉を用意した。 (Sputtering target production example 2) (Li-ITO)
In 2 O 3 powder, SnO 2 powder with a purity> 99.99%, and Li 2 CO 3 powder with a purity> 99.9% were prepared.
　まず、Ｉｎ２Ｏ３粉及びＬｉ２ＣＯ３粉を用意し、乾燥状態でボールミル混合し、大気中１０００℃で３時間仮焼し、ＬｉＩｎＯ２粉を得た。次いで、ＬｉＩｎＯ２粉、Ｉｎ２Ｏ３粉およびＳｎＯ２粉を全量約１．０ｋｇ用意（各金属原子の組成は、下記表３、４に示すものとした）した以外はＳｒ－ＩＴＯと同様にターゲットを作製した。ただし、焼成温度は１４５０℃である。 First, In 2 O 3 powder and Li 2 CO 3 powder were prepared, mixed in a ball mill in a dry state, and calcined at 1000 ° C. for 3 hours in the air to obtain LiInO 2 powder. Next, the same as Sr-ITO except that about 1.0 kg of LiInO 2 powder, In 2 O 3 powder and SnO 2 powder were prepared (the composition of each metal atom was as shown in Tables 3 and 4 below). A target was produced. However, the firing temperature is 1450 ° C.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　（スパッタリングターゲット製造例３）（Ｌａ－ＩＴＯ）
　純度＞９９．９９％のＩｎ２Ｏ３粉、ＳｎＯ２粉、および純度＞９９．９９％のＬａ２（ＣＯ３）３・８Ｈ２Ｏ粉を用意し、まず、Ｉｎ２Ｏ３粉及びＬａ２（ＣＯ３）３・８Ｈ２Ｏ粉を乾燥状態でボールミル混合し、大気中１２００℃で３時間仮焼し、ＬａＩｎＯ３粉を得た。次いで、ＬａＩｎＯ３粉、Ｉｎ２Ｏ３粉およびＳｎＯ２粉を全量約１．０ｋｇ用意（各金属原子の組成は、下記表５、６に示すものとした）した以外はＳｒ－ＩＴＯと同様にターゲットを作製した。 (Sputtering target production example 3) (La-ITO)
Prepare In 2 O 3 powder, SnO 2 powder with purity> 99.99%, and La 2 (CO 3 ) 3 · 8H 2 O powder with purity> 99.99%. First, In 2 O 3 powder and La 2 (CO 3) 3 · 8H 2 O powder was mixed in a ball mill in a dry condition, for three hours and calcined at 1200 ° C. in air to obtain a Laino 3 powder. Next, the same as Sr-ITO except that about 1.0 kg of LaInO 3 powder, In 2 O 3 powder and SnO 2 powder were prepared (the composition of each metal atom was as shown in Tables 5 and 6 below). A target was produced.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　（スパッタリングターゲット製造例４）（Ｃａ－ＩＴＯ）
　純度＞９９．９９％のＩｎ２Ｏ３粉、ＳｎＯ２粉、および純度＞９９．５％のＣａＣＯ３を用意し、まず、Ｉｎ２Ｏ３粉及びＣａＣＯ３粉を乾燥状態でボールミル混合し、大気中１２００℃で３時間仮焼し、ＣａＩｎ２Ｏ４粉を得た。次いで、ＣａＩｎ２Ｏ４粉、Ｉｎ２Ｏ３粉およびＳｎＯ２粉を全量約１．０ｋｇ用意（各金属原子の組成は、下記表７、８に示すものとした）した以外はＳｒ－ＩＴＯと同様にターゲットを作製した。 (Sputtering target production example 4) (Ca-ITO)
Prepare In 2 O 3 powder with a purity of> 99.99%, SnO 2 powder, and CaCO 3 with a purity of> 99.5%. First, the In 2 O 3 powder and the CaCO 3 powder are mixed in a ball mill in a dry state. Calcination was performed at 1200 ° C. in the air for 3 hours to obtain CaIn 2 O 4 powder. Next, Sr-ITO was used except that about 1.0 kg of CaIn 2 O 4 powder, In 2 O 3 powder and SnO 2 powder were prepared (the composition of each metal atom was as shown in Tables 7 and 8 below). Similarly, a target was produced.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
　（スパッタリングターゲット製造例５）（Ｍｇ－ＩＴＯ）
　純度＞９９．９９％のＩｎ２Ｏ３粉、ＳｎＯ２粉、および炭酸水酸化マグネシウム粉（ＭｇＯ含有量４１．５ｗｔ％）を用意し、まず、Ｉｎ２Ｏ３粉及び炭酸水酸化マグネシウム粉を乾燥状態でボールミル混合し、大気中１４００℃で３時間仮焼し、ＭｇＩｎ２Ｏ４粉を得た。次いで、ＭｇＩｎ２Ｏ４粉、Ｉｎ２Ｏ３粉およびＳｎＯ２粉を全量約１．０ｋｇ用意（各金属原子の組成は、下記表９、１０に示すものとした）した以外はＳｒ－ＩＴＯと同様にターゲットを作製した。 (Sputtering target production example 5) (Mg-ITO)
Prepare In 2 O 3 powder, SnO 2 powder, and magnesium carbonate hydroxide powder (MgO content 41.5 wt%) with a purity> 99.99%. First, In 2 O 3 powder and magnesium carbonate hydroxide powder Ball mill mixing was performed in a dry state and calcined at 1400 ° C. in the air for 3 hours to obtain MgIn 2 O 4 powder. Next, Sr-ITO was used except that MgIn 2 O 4 powder, In 2 O 3 powder and SnO 2 powder were prepared in a total amount of about 1.0 kg (the composition of each metal atom was as shown in Tables 9 and 10 below). Similarly, a target was produced.
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
　（スパッタリングターゲット製造例６）（Ｙ－ＩＴＯ）
　純度＞９９．９９％のＩｎ２Ｏ３粉、ＳｎＯ２粉、および純度＞９９．９９％のＹ２（ＣＯ３）３・３Ｈ２Ｏ粉を用意し、まず、Ｉｎ２Ｏ３粉及びＹ２（ＣＯ３）３・３Ｈ２Ｏ粉を乾燥状態でボールミル混合し、大気中１２００℃で３時間仮焼し、ＹＩｎＯ３粉を得た。次いで、ＹＩｎＯ３粉、Ｉｎ２Ｏ３粉およびＳｎＯ２粉を全量約１．０ｋｇ用意（各金属原子の組成は、下記表１１、１２に示すものとした）した以外はＳｒ－ＩＴＯと同様にターゲットを作製した。 (Sputtering target production example 6) (Y-ITO)
Purity> 99.99% In 2 O 3 powder, prepared SnO 2 powder, and purity> 99.99% Y 2 (CO 3) 3 · 3H 2 O powder, firstly, In 2 O 3 powder and Y 2 (CO 3 ) 3 · 3H 2 O powder was mixed in a ball mill in a dry state and calcined at 1200 ° C. in the air for 3 hours to obtain YInO 3 powder. Next, the same as Sr-ITO except that about 1.0 kg of YInO 3 powder, In 2 O 3 powder and SnO 2 powder were prepared (the composition of each metal atom was as shown in Tables 11 and 12 below). A target was produced.
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
　（Ｓｒ含有組成透明導電膜試験例１）
　上述したとおり製造した表１に示す組成のターゲットを用い、これを４インチのＤＣマグネトロンスパッタ装置にそれぞれ装着し、基板温度を室温（約２０℃）、酸素分圧を０～３．０ｓｃｃｍの間で変化させながら（０～１．１×１０-2Ｐａに相当）、各組成の透明導電膜を得た。 (Sr-containing composition transparent conductive film test example 1)
Using the targets having the composition shown in Table 1 manufactured as described above, each was mounted on a 4-inch DC magnetron sputtering apparatus, the substrate temperature was room temperature (about 20 ° C.), and the oxygen partial pressure was between 0 and 3.0 sccm. (Corresponding to 0 to 1.1 × 10 −2 Pa) while obtaining a transparent conductive film of each composition.
　スパッタの条件は、以下の通りとし、厚さ１２００Åの膜を得た。 The sputtering conditions were as follows, and a film having a thickness of 1200 mm was obtained.
　ターゲット寸法　：Φ＝４ｉｎ．　ｔ＝６ｍｍ
　スパッタ方式　：ＤＣマグネトロンスパッタ
　排気装置　：ロータリーポンプ＋クライオポンプ
　到達真空度　：５．３×１０-５［Ｐａ］
　Ａｒ圧力　：４．０×１０-1［Ｐａ］
　酸素圧力：０～１．１×１０-2［Ｐａ］
　水圧力：１．０×１０－２［Ｐａ］
　基板温度：室温
　スパッタ電力　：１３０Ｗ　（電力密度１．６Ｗ／ｃｍ2）
　使用基板　：コーニング＃１７３７（液晶ディスプレイ用ガラス）　ｔ＝０．８ｍｍ Target size: Φ = 4 in. t = 6mm
Sputtering method: DC magnetron sputtering Exhaust device: Rotary pump + cryopump Ultimate vacuum: 5.3 × 10 −5 [Pa]
Ar pressure: 4.0 × 10 −1 [Pa]
Oxygen pressure: 0 to 1.1 × 10 −2 [Pa]
Water pressure: 1.0 × 10 −2 [Pa]
Substrate temperature: Room temperature Sputtering power: 130 W (Power density 1.6 W / cm 2 )
Substrate used: Corning # 1737 (glass for liquid crystal display) t = 0.8 mm
　ここで、全てのサンプルにおいて室温成膜の最適酸素分圧と、２５０℃アニール後に最も抵抗率が低い成膜時の酸素分圧とが異なった。 Here, the optimal oxygen partial pressure for room temperature film formation and the oxygen partial pressure for film formation with the lowest resistivity after annealing at 250 ° C. were different for all samples.
　下記表１３には、最適酸素分圧の変化があったものを○、最適酸素分圧の変化がなかったものを×として示した。 In Table 13 below, the change in the optimum oxygen partial pressure was indicated by ○, and the change in the optimum oxygen partial pressure was indicated by ×.
　各組成について、２５０℃アニール後に最も抵抗率が低い成膜時の酸素分圧で成膜した透明導電膜を、それぞれ１３ｍｍ角の大きさに切り出し、これらのサンプルを大気中にて２５０℃で１時間アニールし、室温成膜時と２５０℃アニール後の結晶状態について、アモルファスはａ、結晶はｃとし、これらを表１３に示した。 For each composition, the transparent conductive film formed at the oxygen partial pressure at the time of film formation having the lowest resistivity after annealing at 250 ° C. was cut out to a size of 13 mm square, and these samples were 1 at 250 ° C. in the atmosphere. Regarding the crystal state after annealing at room temperature and after film formation at room temperature and after annealing at 250 ° C., amorphous is a and crystal is c.
　また、各組成の結晶化温度を測定し、表１３に示した。結晶化温度は室温で成膜した後、結晶化する温度であり、室温成膜でアモルファスとならないものは１００℃未満とした。 Further, the crystallization temperature of each composition was measured and shown in Table 13. The crystallization temperature is a temperature at which the film is crystallized after being deposited at room temperature, and those that do not become amorphous in the film formation at room temperature were set to less than 100 ° C.
　さらに、各組成について、２５０℃アニール後に最も抵抗率が低い成膜時の酸素分圧で成膜し、アニール後のサンプルの抵抗率ρ（Ω・ｃｍ）を測定した。これらの結果を表１３に示す。 Furthermore, for each composition, a film was formed at the oxygen partial pressure at the time of film formation having the lowest resistivity after annealing at 250 ° C., and the resistivity ρ (Ω · cm) of the sample after annealing was measured. These results are shown in Table 13.
　また、各組成について、２５０℃アニール後に最も抵抗率が低い成膜時の酸素分圧で成膜した透明導電膜を、それぞれ１３ｍｍ角の大きさに切り出し、アニール後の膜について透過スペクトルを測定した。アニール後の平均透過率を表１３に示す。 In addition, for each composition, transparent conductive films formed at the oxygen partial pressure at the time of film formation having the lowest resistivity after annealing at 250 ° C. were cut into 13 mm square sizes, and transmission spectra were measured for the annealed films. . Table 13 shows the average transmittance after annealing.
　また、各組成について、２５０℃アニール後に最も抵抗率が低い成膜時の酸素分圧で成膜し、それぞれ１０×５０ｍｍの大きさに切り出し、エッチング液としてＩＴＯ－０５Ｎ（シュウ酸系、関東化学（株）製）（シュウ酸濃度５０ｇ／Ｌ）を用い、温度３０℃で、エッチングレート（Å／ｓｅｃ）を測定した。結果を表１３に示す。 In addition, each composition was formed at the oxygen partial pressure at the time of film formation having the lowest resistivity after annealing at 250 ° C., cut into a size of 10 × 50 mm, and ITO-05N (oxalic acid, Kanto Chemical Co., Ltd.) as an etching solution. Etching rate (Å / sec) was measured at a temperature of 30 ° C. using an oxalic acid concentration (50 g / L). The results are shown in Table 13.
　（Ｓｒ含有組成透明導電膜試験例２）
　上述したとおり製造した表１に示す組成のターゲットを用い、水圧力を８．０×１０－４Ｐａとした以外は、上述した条件で、各組成の透明導電膜を得た。 (Sr-containing composition transparent conductive film test example 2)
Using a target having the composition shown in Table 1 prepared as described above, except that the water pressure and 8.0 × 10 -4 Pa is the conditions described above, to obtain a transparent conductive film of each composition.
　また、上述した通り、最適酸素分圧の変化の有無、結晶化温度、アニール後のサンプルの抵抗率ρ（Ω・ｃｍ）、アニール後の平均透過率、成膜後の透明導電膜のエッチングレート（Å／ｓｅｃ）をそれぞれ求め、表１４に示す。 In addition, as described above, whether or not the optimum oxygen partial pressure is changed, crystallization temperature, resistivity ρ (Ω · cm) of the sample after annealing, average transmittance after annealing, etching rate of the transparent conductive film after film formation (Å / sec) was determined and shown in Table 14.
　（Ｓｒ含有組成透明導電膜参考例）
　上述したとおり製造した表２に示す組成のターゲットを用い、水圧力を５．０×１０－６Ｐａとした以外は、上述した条件で、各組成の透明導電膜を得た。 (Sr-containing composition transparent conductive film reference example)
Using a target having the composition shown in Table 2 prepared as described above, except that the water pressure and 5.0 × 10 -6 Pa is the conditions described above, to obtain a transparent conductive film of each composition.
　また、上述した通り、最適酸素分圧の変化の有無、結晶化温度、アニール後のサンプルの抵抗率ρ（Ω・ｃｍ）、アニール後の平均透過率、成膜後の透明導電膜のエッチングレート（Å／ｓｅｃ）をそれぞれ求め、表１５に示す。 In addition, as described above, whether or not the optimum oxygen partial pressure is changed, crystallization temperature, resistivity ρ (Ω · cm) of the sample after annealing, average transmittance after annealing, etching rate of the transparent conductive film after film formation (Å / sec) was determined and shown in Table 15.
　これら表１３～表１５の結果をそれぞれ図１～図３に示す。 The results of Table 13 to Table 15 are shown in FIGS. 1 to 3, respectively.
　ここで、図１及び図２において、（－４．１×１０－２Ｌｎ（ｘ）－９．３×１０－２）の値未満の範囲で、１００℃未満の成膜温度でアモルファス膜として成膜でき、１００～３００℃で結晶化できるサンプルを●、アモルファス膜として成膜できないものを△で示した。 Here, in FIGS. 1 and 2, - the extent of less than a value of (4.1 × 10 -2 Ln (x ) -9.3 × 10 -2), as an amorphous film at a deposition temperature less than 100 ° C. Samples that can be formed and crystallized at 100 to 300 ° C. are indicated by ●, and samples that cannot be formed as an amorphous film are indicated by Δ.
　また、図３においては、１００℃未満の成膜温度でアモルファス膜として成膜でき、１００～３００℃で結晶化できるサンプルを●、それ以外を▲で示した。 Further, in FIG. 3, samples that can be formed as an amorphous film at a film forming temperature of less than 100 ° C. and crystallized at 100 to 300 ° C. are indicated by ●, and others are indicated by ▲.
　ここで、インジウム１モルに対しての錫のモル比ｙ（モル）が、インジウム１モルに対するＳｒのモル比ｘで表される（－４．１×１０－２Ｌｎ（ｘ）－９．３×１０－２）の値以上であり且つ（－２．９×１０－１Ｌｎ（ｘ）－６．７×１０－１）の値以下の範囲の範囲は、図３から明らかなように、水圧力が５．０×１０－６Ｐａと実質的に水が存在しない状態でもアモルファス膜として成膜できる範囲である。 Here, the molar ratio y (mol) of tin to 1 mol of indium is represented by the molar ratio x of Sr to 1 mol of indium (−4.1 × 10 −2 Ln (x) −9.3). As shown in FIG. 3, the range of the range not less than the value of (× 10 −2 ) and not more than the value of (−2.9 × 10 −1 Ln (x) −6.7 × 10 −1 ) Even when the water pressure is 5.0 × 10 −6 Pa and substantially no water is present, the film can be formed as an amorphous film.
　この結果、添加元素がＳｒの場合、インジウム１モルに対しての錫のモル比ｙ（モル）が、インジウム１モルに対するＳｒのモル比ｘで表される（－４．１×１０－２Ｌｎ（ｘ）－９．３×１０－２）の値未満の範囲では、１００℃未満で、水圧力１．０×１０－２Ｐａで成膜した場合には全てアモルファスな膜となり、その後、１００℃～３００℃でアニールした場合に、結晶化するものであった。 As a result, when the additive element is Sr, the molar ratio y (mol) of tin to 1 mol of indium is represented by the molar ratio x of Sr to 1 mol of indium (−4.1 × 10 −2 Ln). In the range less than the value of (x) −9.3 × 10 −2 ), when the film is formed at a temperature of less than 100 ° C. and a water pressure of 1.0 × 10 −2 Pa, it becomes an amorphous film, and then 100 Crystallization occurred when annealed at a temperature between 0 ° C and 300 ° C.
　また、この中で、インジウム１モルに対しての錫のモル比ｙ（モル）が、インジウム１モルに対するＳｒのモル比ｘで表される（－１．６×１０－２Ｌｎ（ｘ）－３．７×１０－２）未満の範囲では、水圧力を８．０×１０－４Ｐａとした場合、結晶化温度が１００℃未満となり、アモルファス膜として成膜するのは困難であることがわかった。よって、インジウム１モルに対しての錫のモル比ｙ（モル）が、インジウム１モルに対するＳｒのモル比ｘで表される（－４．１×１０－２Ｌｎ（ｘ）－９．３×１０－２）の値未満であり且つ（－１．６×１０－２Ｌｎ（ｘ）－３．７×１０－２）以上の範囲が特に好ましく、水の分圧が１．０×１０-4Ｐａ以上１．０×１０-３Ｐａ以下の条件下で成膜すれば、１００℃未満の温度でアモルファス膜が成膜でき、成膜後は、１００℃～３００℃でアニールすることにより結晶化できる膜となることがわかった。 Further, in this, the molar ratio y (mol) of tin to 1 mol of indium is represented by the molar ratio x of Sr to 1 mol of indium (−1.6 × 10 −2 Ln (x) −). In the range of less than 3.7 × 10 −2 ), when the water pressure is 8.0 × 10 −4 Pa, the crystallization temperature is less than 100 ° C., and it may be difficult to form an amorphous film. all right. Therefore, the molar ratio y (mol) of tin to 1 mol of indium is expressed by the molar ratio x of Sr to 1 mol of indium (−4.1 × 10 −2 Ln (x) −9.3 ×). 10 −2 ) and (−1.6 × 10 −2 Ln (x) −3.7 × 10 −2 ) or more are particularly preferred, and the partial pressure of water is 1.0 × 10 − An amorphous film can be formed at a temperature of less than 100 ° C. if the film is formed under conditions of 4 Pa or more and 1.0 × 10 −3 Pa or less. After the film formation, the crystal is obtained by annealing at 100 ° C. to 300 ° C. It turned out that it becomes a film | membrane which can be converted.
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000015
　（Ｌｉ含有組成透明導電膜試験例１）
　上述したとおり製造した表３に示す組成のターゲットを用い、これを４インチのＤＣマグネトロンスパッタ装置にそれぞれ装着し、基板温度を室温（約２０℃）、酸素分圧を０～３．０ｓｃｃｍの間で変化させながら（０～１．１×１０-2Ｐａに相当）、各組成の透明導電膜を得た。 (Li-containing composition transparent conductive film test example 1)
Using the target having the composition shown in Table 3 manufactured as described above, this was mounted on a 4-inch DC magnetron sputtering apparatus, the substrate temperature was room temperature (about 20 ° C.), and the oxygen partial pressure was between 0 and 3.0 sccm. (Corresponding to 0 to 1.1 × 10 −2 Pa) while obtaining a transparent conductive film of each composition.
　スパッタの条件は、以下の通りとし、厚さ１２００Åの膜を得た。 The sputtering conditions were as follows, and a film having a thickness of 1200 mm was obtained.
　ターゲット寸法　：Φ＝４ｉｎ．　ｔ＝６ｍｍ
　スパッタ方式　：ＤＣマグネトロンスパッタ
　排気装置　：ロータリーポンプ＋クライオポンプ
　到達真空度　：５．３×１０-５［Ｐａ］
　Ａｒ圧力　：４．０×１０-1［Ｐａ］
　酸素圧力：０～１．１×１０-2［Ｐａ］
　水圧力：１．０×１０－２［Ｐａ］
　基板温度：室温
　スパッタ電力　：１３０Ｗ　（電力密度１．６Ｗ／ｃｍ2）
　使用基板　：コーニング＃１７３７（液晶ディスプレイ用ガラス）　ｔ＝０．８ｍｍ Target size: Φ = 4 in. t = 6mm
Sputtering method: DC magnetron sputtering Exhaust device: Rotary pump + cryopump Ultimate vacuum: 5.3 × 10 −5 [Pa]
Ar pressure: 4.0 × 10 −1 [Pa]
Oxygen pressure: 0 to 1.1 × 10 −2 [Pa]
Water pressure: 1.0 × 10 −2 [Pa]
Substrate temperature: Room temperature Sputtering power: 130 W (Power density 1.6 W / cm 2 )
Substrate used: Corning # 1737 (glass for liquid crystal display) t = 0.8 mm
　ここで、全てのサンプルにおいて室温成膜の最適酸素分圧と、２５０℃アニール後に最も抵抗率が低い成膜時の酸素分圧とが異なった。 Here, the optimal oxygen partial pressure for room temperature film formation and the oxygen partial pressure for film formation with the lowest resistivity after annealing at 250 ° C. were different for all samples.
　下記表１６には、最適酸素分圧の変化があったものを○、最適酸素分圧の変化がなかったものを×として示した。 In Table 16 below, the change in the optimum oxygen partial pressure was indicated by ○, and the change in the optimum oxygen partial pressure was indicated by ×.
　また、各組成について、２５０℃アニール後に最も抵抗率が低い成膜時の酸素分圧で成膜した透明導電膜を、それぞれ１３ｍｍ角の大きさに切り出し、これらのサンプルを大気中にて２５０℃で１時間アニールし、室温成膜時と２５０℃アニール後の結晶状態について、アモルファスはａ、結晶はｃとし、これらを表１６に示した。 Further, for each composition, transparent conductive films formed at the oxygen partial pressure at the time of film formation having the lowest resistivity after annealing at 250 ° C. were cut into 13 mm square sizes, and these samples were 250 ° C. in the atmosphere. As shown in Table 16, the crystal states after annealing at room temperature for 1 hour, after film formation at room temperature and after annealing at 250 ° C. are a for amorphous and c for crystal.
　また、各組成の結晶化温度を測定し、表１６に示した。結晶化温度は室温で成膜した後、結晶化する温度であり、室温成膜でアモルファスとならないものは１００℃未満とした。 Further, the crystallization temperature of each composition was measured and shown in Table 16. The crystallization temperature is a temperature at which the film is crystallized after being deposited at room temperature, and those that do not become amorphous in the film formation at room temperature were set to less than 100 ° C.
　さらに、各組成について、２５０℃アニール後に最も抵抗率が低い成膜時の酸素分圧で成膜し、アニール後のサンプルの抵抗率ρ（Ω・ｃｍ）を測定した。これらの結果を表１６に示す。 Furthermore, for each composition, a film was formed at the oxygen partial pressure at the time of film formation having the lowest resistivity after annealing at 250 ° C., and the resistivity ρ (Ω · cm) of the sample after annealing was measured. These results are shown in Table 16.
　また、各組成について、２５０℃アニール後に最も抵抗率が低い成膜時の酸素分圧で成膜した透明導電膜を、それぞれ１３ｍｍ角の大きさに切り出し、アニール後の膜について透過スペクトルを測定した。アニール後の平均透過率を表１６に示す。 In addition, for each composition, transparent conductive films formed at the oxygen partial pressure at the time of film formation having the lowest resistivity after annealing at 250 ° C. were cut into 13 mm square sizes, and transmission spectra were measured for the annealed films. . Table 16 shows the average transmittance after annealing.
　また、各組成について、２５０℃アニール後に最も抵抗率が低い成膜時の酸素分圧で成膜し、それぞれ１０×５０ｍｍの大きさに切り出し、エッチング液としてＩＴＯ－０５Ｎ（シュウ酸系、関東化学（株）製）（シュウ酸濃度５０ｇ／Ｌ）を用い、温度３０℃で、エッチングレート（Å／ｓｅｃ）を測定した。結果を表１６に示す。 In addition, each composition was formed at the oxygen partial pressure at the time of film formation having the lowest resistivity after annealing at 250 ° C., cut into a size of 10 × 50 mm, and ITO-05N (oxalic acid, Kanto Chemical Co., Ltd.) as an etching solution. Etching rate (Å / sec) was measured at a temperature of 30 ° C. using an oxalic acid concentration (50 g / L). The results are shown in Table 16.
　（Ｌｉ含有組成透明導電膜試験例２）
　上述したとおり製造した表３に示す組成のターゲットを用い、水圧力を８．０×１０－４Ｐａとした以外は、上述した条件で、各組成の透明導電膜を得た。 (Li-containing composition transparent conductive film test example 2)
A transparent conductive film having each composition was obtained under the above-described conditions except that the target having the composition shown in Table 3 manufactured as described above was used and the water pressure was 8.0 × 10 −4 Pa.
　また、上述した通り、最適酸素分圧の変化の有無、結晶化温度、アニール後のサンプルの抵抗率ρ（Ω・ｃｍ）、アニール後の平均透過率、成膜後の透明導電膜のエッチングレート（Å／ｓｅｃ）をそれぞれ求め、表１７に示す。 In addition, as described above, whether or not the optimum oxygen partial pressure is changed, crystallization temperature, resistivity ρ (Ω · cm) of the sample after annealing, average transmittance after annealing, etching rate of the transparent conductive film after film formation (Å / sec) was determined and shown in Table 17.
　（Ｌｉ含有組成透明導電膜参考例）
　上述したとおり製造した表４に示す組成のターゲットを用い、水圧力を５．０×１０－６Ｐａとした以外は、上述した条件で、各組成の透明導電膜を得た。 (Li-containing composition transparent conductive film reference example)
A transparent conductive film having each composition was obtained under the above-described conditions except that the target having the composition shown in Table 4 manufactured as described above was used and the water pressure was 5.0 × 10 −6 Pa.
　また、上述した通り、最適酸素分圧の変化の有無、結晶化温度、アニール後のサンプルの抵抗率ρ（Ω・ｃｍ）、アニール後の平均透過率、成膜後の透明導電膜のエッチングレート（Å／ｓｅｃ）をそれぞれ求め、表１８に示す。 In addition, as described above, whether or not the optimum oxygen partial pressure is changed, crystallization temperature, resistivity ρ (Ω · cm) of the sample after annealing, average transmittance after annealing, etching rate of the transparent conductive film after film formation (Å / sec) was determined and shown in Table 18.
　これら表１６～表１８の結果をそれぞれ図４～図６に示す。 The results of Tables 16 to 18 are shown in FIGS. 4 to 6, respectively.
　ここで、図４及び図５において、（－１．６×１０－１Ｌｎ（ｘ）－５．９×１０－１）の値未満の範囲で、１００℃未満の成膜温度でアモルファス膜として成膜でき、１００～３００℃で結晶化できるサンプルを●、アモルファス膜として成膜できないものを△で示した。 Here, in FIGS. 4 and 5, - in the range of less than a value of (1.6 × 10 -1 Ln (x ) -5.9 × 10 -1), as an amorphous film at a deposition temperature less than 100 ° C. Samples that can be formed and crystallized at 100 to 300 ° C. are indicated by ●, and samples that cannot be formed as an amorphous film are indicated by Δ.
　また、図６においては、１００℃未満の成膜温度でアモルファス膜として成膜でき、１００～３００℃で結晶化できるサンプルを●、それ以外を▲で示した。 Further, in FIG. 6, samples that can be formed as an amorphous film at a film forming temperature of less than 100 ° C. and crystallized at 100 to 300 ° C. are indicated by ●, and others are indicated by ▲.
　ここで、インジウム１モルに対しての錫のモル比ｙ（モル）が、インジウム１モルに対するＬｉのモル比ｘで表される（－１．６×１０－１Ｌｎ（ｘ）－５．９×１０－１）の値以上であり且つ（－２．５×１０－１Ｌｎ（ｘ）－５．７×１０－１）の値以下の範囲は、図６から明らかなように、水圧力が５．０×１０－６Ｐａと実質的に水が存在しない状態でもアモルファス膜として成膜できる範囲である。 Here, the molar ratio y (mol) of tin to 1 mol of indium is represented by the molar ratio x of Li to 1 mol of indium (−1.6 × 10 −1 Ln (x) −5.9). × 10 -1) is a value or more and (-2.5 × 10 -1 Ln (x ) -5.7 × 10 -1 values less range), as is apparent from FIG. 6, the water pressure Is 5.0 × 10 −6 Pa, which is a range in which an amorphous film can be formed even in the absence of water.
　この結果、添加元素がＬｉの場合、インジウム１モルに対しての錫のモル比ｙ（モル）が、インジウム１モルに対するＬｉのモル比ｘで表される（－１．６×１０－１Ｌｎ（ｘ）－５．９×１０－１）の値未満の範囲では、１００℃未満で、水圧力１．０×１０－２Ｐａで成膜した場合には全てアモルファスな膜となり、その後、１００℃～３００℃でアニールした場合に、結晶化するものであった。 As a result, when the additive element is Li, the molar ratio y (mol) of tin to 1 mol of indium is expressed by the molar ratio x of Li to 1 mol of indium (−1.6 × 10 −1 Ln). In the range less than the value of (x) −5.9 × 10 −1 ), when the film is formed at a temperature of less than 100 ° C. and a water pressure of 1.0 × 10 −2 Pa, the film is all amorphous, and thereafter 100 Crystallization occurred when annealed at a temperature between 0 ° C and 300 ° C.
　また、この中で、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するＬｉのモル比ｘで表される（－３．５×１０－２Ｌｎ（ｘ）－１．６×１０－１）未満の範囲では、水圧力を８．０×１０－４Ｐａとした場合、結晶化温度が１００℃未満となり、アモルファス膜として成膜するのは困難であることがわかった。よって、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するＬｉのモル比ｘで表される（－１．６×１０－１Ｌｎ（ｘ）－５．９×１０－１）の値未満であり且つ（－３．５×１０－２Ｌｎ（ｘ）－１．６×１０－１）以上の範囲が特に好ましく、水の分圧が１．０×１０-4Ｐａ以上１．０×１０-３Ｐａ以下の条件下で成膜すれば、１００℃未満の温度でアモルファス膜が成膜でき、成膜後は、１００℃～３００℃でアニールすることにより結晶化できる膜となることがわかった。 In this, the molar ratio y of tin to 1 mol of indium is represented by the molar ratio x of Li to 1 mol of indium (−3.5 × 10 −2 Ln (x) −1.6 In the range of less than × 10 −1 ), when the water pressure was 8.0 × 10 −4 Pa, the crystallization temperature was less than 100 ° C., and it was found difficult to form an amorphous film. Therefore, the molar ratio y of tin to 1 mol of indium is represented by the molar ratio x of Li to 1 mol of indium (−1.6 × 10 −1 Ln (x) −5.9 × 10 −1 ) And (−3.5 × 10 −2 Ln (x) −1.6 × 10 −1 ) or more is particularly preferable, and the partial pressure of water is 1.0 × 10 −4 Pa or more. If the film is formed under the condition of 1.0 × 10 −3 Pa or less, an amorphous film can be formed at a temperature of less than 100 ° C. After the film is formed, the film can be crystallized by annealing at 100 ° C. to 300 ° C. I found out that
Figure JPOXMLDOC01-appb-T000016
Figure JPOXMLDOC01-appb-T000016
Figure JPOXMLDOC01-appb-T000017
Figure JPOXMLDOC01-appb-T000017
Figure JPOXMLDOC01-appb-T000018
Figure JPOXMLDOC01-appb-T000018
　（Ｌａ含有組成透明導電膜試験例１）
　上述したとおり製造した表５に示す組成のターゲットを用い、これを４インチのＤＣマグネトロンスパッタ装置にそれぞれ装着し、基板温度を室温（約２０℃）、酸素分圧を０～３．０ｓｃｃｍの間で変化させながら（０～１．１×１０-2Ｐａに相当）、各組成の透明導電膜を得た。 (La-containing composition transparent conductive film test example 1)
Using the target having the composition shown in Table 5 manufactured as described above, this was mounted on a 4-inch DC magnetron sputtering apparatus, the substrate temperature was room temperature (about 20 ° C.), and the oxygen partial pressure was between 0 and 3.0 sccm. (Corresponding to 0 to 1.1 × 10 −2 Pa) while obtaining a transparent conductive film of each composition.
　スパッタの条件は、以下の通りとし、厚さ１２００Åの膜を得た。 The sputtering conditions were as follows, and a film having a thickness of 1200 mm was obtained.
　ターゲット寸法　：Φ＝４ｉｎ．　ｔ＝６ｍｍ
　スパッタ方式　：ＤＣマグネトロンスパッタ
　排気装置　：ロータリーポンプ＋クライオポンプ
　到達真空度　：５．３×１０-５［Ｐａ］
　Ａｒ圧力　：４．０×１０-1［Ｐａ］
　酸素圧力：０～１．１×１０-2［Ｐａ］
　水圧力：１．０×１０－２［Ｐａ］
　基板温度：室温
　スパッタ電力　：１３０Ｗ　（電力密度１．６Ｗ／ｃｍ2）
　使用基板　：コーニング＃１７３７（液晶ディスプレイ用ガラス）　ｔ＝０．８ｍｍ Target size: Φ = 4 in. t = 6mm
Sputtering method: DC magnetron sputtering Exhaust device: Rotary pump + cryopump Ultimate vacuum: 5.3 × 10 −5 [Pa]
Ar pressure: 4.0 × 10 −1 [Pa]
Oxygen pressure: 0 to 1.1 × 10 −2 [Pa]
Water pressure: 1.0 × 10 −2 [Pa]
Substrate temperature: Room temperature Sputtering power: 130 W (Power density 1.6 W / cm 2 )
Substrate used: Corning # 1737 (glass for liquid crystal display) t = 0.8 mm
　ここで、全てのサンプルにおいて室温成膜の最適酸素分圧と、２５０℃アニール後に最も抵抗率が低い成膜時の酸素分圧とが異なった。 Here, the optimal oxygen partial pressure for room temperature film formation and the oxygen partial pressure for film formation with the lowest resistivity after annealing at 250 ° C. were different for all samples.
　下記表１９には、最適酸素分圧の変化があったものを○、最適酸素分圧の変化がなかったものを×として示した。 In Table 19 below, the change in the optimum oxygen partial pressure was indicated by ○, and the change in the optimum oxygen partial pressure was indicated by ×.
　また、各組成について、２５０℃アニール後に最も抵抗率が低い成膜時の酸素分圧で成膜した透明導電膜を、それぞれ１３ｍｍ角の大きさに切り出し、これらのサンプルを大気中にて２５０℃で１時間アニールし、室温成膜時と２５０℃アニール後の結晶状態について、アモルファスはａ、結晶はｃとし、これらを表１９に示した。 Further, for each composition, transparent conductive films formed at the oxygen partial pressure at the time of film formation having the lowest resistivity after annealing at 250 ° C. were cut into 13 mm square sizes, and these samples were 250 ° C. in the atmosphere. As shown in Table 19, the crystal states after annealing at room temperature for 1 hour and after annealing at room temperature and after annealing at 250 ° C. are a for amorphous and c for crystal.
　また、各組成の結晶化温度を測定し、表１９に示した。結晶化温度は室温で成膜した後、結晶化する温度であり、室温成膜でアモルファスとならないものは１００℃未満とした。 Further, the crystallization temperature of each composition was measured and shown in Table 19. The crystallization temperature is a temperature at which the film is crystallized after being deposited at room temperature, and those that do not become amorphous in the film formation at room temperature were set to less than 100 ° C.
　さらに、各組成について、２５０℃アニール後に最も抵抗率が低い成膜時の酸素分圧で成膜し、アニール後のサンプルの抵抗率ρ（Ω・ｃｍ）を測定した。これらの結果を表１９に示す。 Furthermore, for each composition, a film was formed at the oxygen partial pressure at the time of film formation having the lowest resistivity after annealing at 250 ° C., and the resistivity ρ (Ω · cm) of the sample after annealing was measured. These results are shown in Table 19.
　また、各組成について、２５０℃アニール後に最も抵抗率が低い成膜時の酸素分圧で成膜した透明導電膜を、それぞれ１３ｍｍ角の大きさに切り出し、アニール後の膜について透過スペクトルを測定した。アニール後の平均透過率を表１９に示す。 In addition, for each composition, transparent conductive films formed at the oxygen partial pressure at the time of film formation having the lowest resistivity after annealing at 250 ° C. were cut into 13 mm square sizes, and transmission spectra were measured for the annealed films. . Table 19 shows the average transmittance after annealing.
　また、各組成について、２５０℃アニール後に最も抵抗率が低い成膜時の酸素分圧で成膜し、それぞれ１０×５０ｍｍの大きさに切り出し、エッチング液としてＩＴＯ－０５Ｎ（シュウ酸系、関東化学（株）製）（シュウ酸濃度５０ｇ／Ｌ）を用い、温度３０℃で、エッチングレート（Å／ｓｅｃ）を測定した。結果を表１９に示す。 In addition, each composition was formed at the oxygen partial pressure at the time of film formation having the lowest resistivity after annealing at 250 ° C., cut into a size of 10 × 50 mm, and ITO-05N (oxalic acid, Kanto Chemical Co., Ltd.) as an etching solution. Etching rate (Å / sec) was measured at a temperature of 30 ° C. using an oxalic acid concentration (50 g / L). The results are shown in Table 19.
　（Ｌａ含有組成透明導電膜試験例２）
　上述したとおり製造した表５に示す組成のターゲットを用い、水圧力を８．０×１０－４Ｐａとした以外は、上述した条件で、各組成の透明導電膜を得た。 (La containing composition transparent conductive film test example 2)
A transparent conductive film having each composition was obtained under the above-described conditions except that the target having the composition shown in Table 5 produced as described above was used and the water pressure was 8.0 × 10 −4 Pa.
　また、上述した通り、最適酸素分圧の変化の有無、結晶化温度、アニール後のサンプルの抵抗率ρ（Ω・ｃｍ）、アニール後の平均透過率、成膜後の透明導電膜のエッチングレート（Å／ｓｅｃ）をそれぞれ求め、表２０に示す。 In addition, as described above, whether or not the optimum oxygen partial pressure is changed, crystallization temperature, resistivity ρ (Ω · cm) of the sample after annealing, average transmittance after annealing, etching rate of the transparent conductive film after film formation (Å / sec) was determined and shown in Table 20.
　（Ｌａ含有組成透明導電膜参考例）
　上述したとおり製造した表６に示す組成のターゲットを用い、水圧力を５．０×１０－６Ｐａとした以外は、上述した条件で、各組成の透明導電膜を得た。 (La-containing composition transparent conductive film reference example)
A transparent conductive film of each composition was obtained under the above-described conditions except that the target having the composition shown in Table 6 produced as described above was used and the water pressure was 5.0 × 10 −6 Pa.
　また、上述した通り、最適酸素分圧の変化の有無、結晶化温度、アニール後のサンプルの抵抗率ρ（Ω・ｃｍ）、アニール後の平均透過率、成膜後の透明導電膜のエッチングレート（Å／ｓｅｃ）をそれぞれ求め、表２１に示す。 In addition, as described above, whether or not the optimum oxygen partial pressure is changed, crystallization temperature, resistivity ρ (Ω · cm) of the sample after annealing, average transmittance after annealing, etching rate of the transparent conductive film after film formation (Å / sec) was determined and shown in Table 21.
　これら表１９～表２１の結果をそれぞれ図７～図９に示す。 The results of Table 19 to Table 21 are shown in FIGS. 7 to 9, respectively.
　ここで、図７及び図８において、（－６．７×１０－２Ｌｎ（ｘ）－２．２×１０－１）の値未満の範囲で、１００℃未満の成膜温度でアモルファス膜として成膜でき、１００～３００℃で結晶化できるサンプルを●、アモルファス膜として成膜できないものを△で示した。 Here, in FIGS. 7 and 8, an amorphous film is formed at a film formation temperature of less than 100 ° C. within a range of less than (−6.7 × 10 −2 Ln (x) −2.2 × 10 −1 ). Samples that can be formed and crystallized at 100 to 300 ° C. are indicated by ●, and samples that cannot be formed as an amorphous film are indicated by Δ.
　また、図９においては、１００℃未満の成膜温度でアモルファス膜として成膜でき、１００～３００℃で結晶化できるサンプルを●、それ以外を▲で示した。 In FIG. 9, the samples that can be formed as an amorphous film at a film forming temperature of less than 100 ° C. and can be crystallized at 100 to 300 ° C. are indicated by ● and the others are indicated by ▲.
　ここで、インジウム１モルに対しての錫のモル比ｙ（モル）が、インジウム１モルに対するＬａのモル比ｘで表される（－６．７×１０－２Ｌｎ（ｘ）－２．２×１０－１）の値以上であり且つ（－３．３×１０－１Ｌｎ（ｘ）－７．７×１０－１）の値以下の範囲は、図９から明らかなように、水圧力が５．０×１０－６Ｐａと実質的に水が存在しない状態でもアモルファス膜として成膜できる範囲である。 Here, the molar ratio y (mol) of tin to 1 mol of indium is represented by the molar ratio x of La to 1 mol of indium (−6.7 × 10 −2 Ln (x) −2.2). As shown in FIG. 9, the water pressure is within the range of not less than the value of (× 10 −1 ) and not more than the value of (−3.3 × 10 −1 Ln (x) −7.7 × 10 −1 ). Is 5.0 × 10 −6 Pa, which is a range in which an amorphous film can be formed even in the absence of water.
　この結果、添加元素がＬａの場合、インジウム１モルに対しての錫のモル比ｙ（モル）が、インジウム１モルに対するＬａのモル比ｘで表される（－６．７×１０－２Ｌｎ（ｘ）－２．２×１０－１）の値未満の範囲では、１００℃未満で、水圧力１．０×１０－２Ｐａで成膜した場合には全てアモルファスな膜となり、その後、１００℃～３００℃でアニールした場合に、結晶化するものであった。 As a result, when the additive element is La, the molar ratio y (mol) of tin to 1 mol of indium is represented by the molar ratio x of La to 1 mol of indium (−6.7 × 10 −2 Ln). In the range less than the value of (x) −2.2 × 10 −1 ), when the film is formed at a temperature of less than 100 ° C. and a water pressure of 1.0 × 10 −2 Pa, the film becomes an amorphous film. Crystallization occurred when annealed at a temperature between 0 ° C and 300 ° C.
　また、この中で、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するＬａのモル比ｘで表される（－２．９×１０－２Ｌｎ（ｘ）－１．３×１０－１）未満の範囲では、水圧力を８．０×１０－４Ｐａとした場合、結晶化温度が１００℃未満となり、アモルファス膜として成膜するのは困難であることがわかった。よって、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するＬａのモル比ｘで表される（－６．７×１０－２Ｌｎ（ｘ）－２．２×１０－１）の値未満であり且つ－２．９×１０－２Ｌｎ（ｘ）－１．３×１０－１）以上の範囲が特に好ましく、水の分圧が１．０×１０-4Ｐａ以上１．０×１０-３Ｐａ以下の条件下で成膜すれば、１００℃未満の温度でアモルファス膜が成膜でき、成膜後は、１００℃～３００℃でアニールすることにより結晶化できる膜となることがわかった。 In this, the molar ratio y of tin to 1 mol of indium is represented by the molar ratio x of La to 1 mol of indium (−2.9 × 10 −2 Ln (x) −1.3 In the range of less than × 10 −1 ), when the water pressure was 8.0 × 10 −4 Pa, the crystallization temperature was less than 100 ° C., and it was found difficult to form an amorphous film. Therefore, the molar ratio y of tin to 1 mol of indium is represented by the molar ratio x of La to 1 mol of indium (−6.7 × 10 −2 Ln (x) −2.2 × 10 −1 ) And −2.9 × 10 −2 Ln (x) −1.3 × 10 −1 ) or more is particularly preferable, and the partial pressure of water is 1.0 × 10 −4 Pa or more and 1 If the film is formed under a condition of 0.0 × 10 −3 Pa or less, an amorphous film can be formed at a temperature of less than 100 ° C. After the film formation, a film that can be crystallized by annealing at 100 ° C. to 300 ° C. I found out that
Figure JPOXMLDOC01-appb-T000019
Figure JPOXMLDOC01-appb-T000019
Figure JPOXMLDOC01-appb-T000020
Figure JPOXMLDOC01-appb-T000020
Figure JPOXMLDOC01-appb-T000021
Figure JPOXMLDOC01-appb-T000021
　（Ｃａ含有組成透明導電膜試験例１）
　上述したとおり製造した表７に示す組成のターゲットを用い、これを４インチのＤＣマグネトロンスパッタ装置にそれぞれ装着し、基板温度を室温（約２０℃）、酸素分圧を０～３．０ｓｃｃｍの間で変化させながら（０～１．１×１０-2Ｐａに相当）、各組成の透明導電膜を得た。 (Ca-containing composition transparent conductive film test example 1)
Using the target having the composition shown in Table 7 manufactured as described above, this was mounted on a 4-inch DC magnetron sputtering apparatus, the substrate temperature was room temperature (about 20 ° C.), and the oxygen partial pressure was between 0 and 3.0 sccm. (Corresponding to 0 to 1.1 × 10 −2 Pa) while obtaining a transparent conductive film of each composition.
　スパッタの条件は、以下の通りとし、厚さ１２００Åの膜を得た。 The sputtering conditions were as follows, and a film having a thickness of 1200 mm was obtained.
　ターゲット寸法　：Φ＝４ｉｎ．　ｔ＝６ｍｍ
　スパッタ方式　：ＤＣマグネトロンスパッタ
　排気装置　：ロータリーポンプ＋クライオポンプ
　到達真空度　：５．３×１０-５［Ｐａ］
　Ａｒ圧力　：４．０×１０-1［Ｐａ］
　酸素圧力：０～１．１×１０-2［Ｐａ］
　水圧力：１．０×１０－２［Ｐａ］
　基板温度：室温
　スパッタ電力　：１３０Ｗ　（電力密度１．６Ｗ／ｃｍ2）
　使用基板　：コーニング＃１７３７（液晶ディスプレイ用ガラス）　ｔ＝０．８ｍｍ Target size: Φ = 4 in. t = 6mm
Sputtering method: DC magnetron sputtering Exhaust device: Rotary pump + cryopump Ultimate vacuum: 5.3 × 10 −5 [Pa]
Ar pressure: 4.0 × 10 −1 [Pa]
Oxygen pressure: 0 to 1.1 × 10 −2 [Pa]
Water pressure: 1.0 × 10 −2 [Pa]
Substrate temperature: Room temperature Sputtering power: 130 W (Power density 1.6 W / cm 2 )
Substrate used: Corning # 1737 (glass for liquid crystal display) t = 0.8 mm
　ここで、全てのサンプルにおいて室温成膜の最適酸素分圧と、２５０℃アニール後に最も抵抗率が低い成膜時の酸素分圧とが異なった。 Here, the optimal oxygen partial pressure for room temperature film formation and the oxygen partial pressure for film formation with the lowest resistivity after annealing at 250 ° C. were different for all samples.
　下記表２２には、最適酸素分圧の変化があったものを○、最適酸素分圧の変化がなかったものを×として示した。 In Table 22 below, the change in the optimum oxygen partial pressure was indicated by ○, and the change in the optimum oxygen partial pressure was indicated by ×.
　また、各組成について、２５０℃アニール後に最も抵抗率が低い成膜時の酸素分圧で成膜した透明導電膜を、それぞれ１３ｍｍ角の大きさに切り出し、これらのサンプルを大気中にて２５０℃で１時間アニールし、室温成膜時と２５０℃アニール後の結晶状態について、アモルファスはａ、結晶はｃとし、これらを表２２示した。 Further, for each composition, transparent conductive films formed at the oxygen partial pressure at the time of film formation having the lowest resistivity after annealing at 250 ° C. were cut into 13 mm square sizes, and these samples were 250 ° C. in the atmosphere. As shown in Table 22, the crystal states after annealing at room temperature for 1 hour and after annealing at room temperature and after annealing at 250 ° C. are a for amorphous and c for crystal.
　また、各組成の結晶化温度を測定し、表２２に示した。結晶化温度は室温で成膜した後、結晶化する温度であり、室温成膜でアモルファスとならないものは１００℃未満とした。 Further, the crystallization temperature of each composition was measured and shown in Table 22. The crystallization temperature is a temperature at which crystallization is performed after film formation at room temperature, and the temperature at which film formation does not become amorphous by film formation at room temperature is set to less than 100 ° C.
　さらに、各組成について、２５０℃アニール後に最も抵抗率が低い成膜時の酸素分圧で成膜し、アニール後のサンプルの抵抗率ρ（Ω・ｃｍ）を測定した。これらの結果を表２２に示す。 Furthermore, for each composition, a film was formed at the oxygen partial pressure at the time of film formation having the lowest resistivity after annealing at 250 ° C., and the resistivity ρ (Ω · cm) of the sample after annealing was measured. These results are shown in Table 22.
　また、各組成について、２５０℃アニール後に最も抵抗率が低い成膜時の酸素分圧で成膜した透明導電膜を、それぞれ１３ｍｍ角の大きさに切り出し、アニール後の膜について透過スペクトルを測定した。アニール後の平均透過率を表２２に示す。 In addition, for each composition, transparent conductive films formed at the oxygen partial pressure at the time of film formation having the lowest resistivity after annealing at 250 ° C. were cut into 13 mm square sizes, and transmission spectra were measured for the annealed films. . Table 22 shows the average transmittance after annealing.
　また、各組成について、２５０℃アニール後に最も抵抗率が低い成膜時の酸素分圧で成膜し、それぞれ１０×５０ｍｍの大きさに切り出し、エッチング液としてＩＴＯ－０５Ｎ（シュウ酸系、関東化学（株）製）（シュウ酸濃度５０ｇ／Ｌ）を用い、温度３０℃で、エッチングレート（Å／ｓｅｃ）を測定した。結果を表２２に示す。 In addition, each composition was formed at the oxygen partial pressure at the time of film formation having the lowest resistivity after annealing at 250 ° C., cut into a size of 10 × 50 mm, and ITO-05N (oxalic acid, Kanto Chemical Co., Ltd.) as an etching solution. Etching rate (Å / sec) was measured at a temperature of 30 ° C. using an oxalic acid concentration (50 g / L). The results are shown in Table 22.
　（Ｃａ含有組成透明導電膜試験例２）
　上述したとおり製造した表７に示す組成のターゲットを用い、水圧力を８．０×１０－４Ｐａとした以外は、上述した条件で、各組成の透明導電膜を得た。 (Ca-containing composition transparent conductive film test example 2)
A transparent conductive film having each composition was obtained under the above-described conditions except that the target having the composition shown in Table 7 produced as described above was used and the water pressure was 8.0 × 10 −4 Pa.
　また、上述した通り、最適酸素分圧の変化の有無、結晶化温度、アニール後のサンプルの抵抗率ρ（Ω・ｃｍ）、アニール後の平均透過率、成膜後の透明導電膜のエッチングレート（Å／ｓｅｃ）をそれぞれ求め、表２３に示す。 In addition, as described above, whether or not the optimum oxygen partial pressure is changed, crystallization temperature, resistivity ρ (Ω · cm) of the sample after annealing, average transmittance after annealing, etching rate of the transparent conductive film after film formation (Å / sec) was determined and shown in Table 23.
　（Ｃａ含有組成透明導電膜参考例）
　上述したとおり製造した表８に示す組成のターゲットを用い、水圧力を５．０×１０－６Ｐａとした以外は、上述した条件で、各組成の透明導電膜を得た。 (Ca-containing composition transparent conductive film reference example)
A transparent conductive film having each composition was obtained under the above-described conditions except that the target having the composition shown in Table 8 manufactured as described above was used and the water pressure was 5.0 × 10 −6 Pa.
　また、上述した通り、最適酸素分圧の変化の有無、結晶化温度、アニール後のサンプルの抵抗率ρ（Ω・ｃｍ）、アニール後の平均透過率、成膜後の透明導電膜のエッチングレート（Å／ｓｅｃ）をそれぞれ求め、表２４に示す。 In addition, as described above, whether or not the optimum oxygen partial pressure is changed, crystallization temperature, resistivity ρ (Ω · cm) of the sample after annealing, average transmittance after annealing, etching rate of the transparent conductive film after film formation (Å / sec) was determined and shown in Table 24.
　これら表２２～表２４の結果をそれぞれ図１０～図１２に示す。 The results of Table 22 to Table 24 are shown in FIGS. 10 to 12, respectively.
　ここで、図１０及び図１１において、（－６．７×１０－２Ｌｎ（ｘ）－２．２×１０－１）の値未満の範囲で、１００℃未満の成膜温度でアモルファス膜として成膜でき、１００～３００℃で結晶化できるサンプルを●、アモルファス膜として成膜できないものを△で示した。 Here, in FIGS. 10 and 11, an amorphous film is formed at a film formation temperature of less than 100 ° C. within a range of less than (−6.7 × 10 −2 Ln (x) −2.2 × 10 −1 ). Samples that can be formed and crystallized at 100 to 300 ° C. are indicated by ●, and samples that cannot be formed as an amorphous film are indicated by Δ.
　また、図１２においては、１００℃未満の成膜温度でアモルファス膜として成膜でき、１００～３００℃で結晶化できるサンプルを●、それ以外を▲で示した。 Further, in FIG. 12, samples that can be formed as an amorphous film at a film forming temperature of less than 100 ° C. and crystallized at 100 to 300 ° C. are indicated by ●, and others are indicated by ▲.
　ここで、インジウム１モルに対しての錫のモル比ｙ（モル）が、インジウム１モルに対するＣａのモル比ｘで表される（－４．１×１０－２Ｌｎ（ｘ）－９．３×１０－２）の値以上であり且つ（－２．５×１０－１Ｌｎ（ｘ）－５．７×１０－１）の値以下の範囲は、図１２から明らかなように、水圧力が５．０×１０－６Ｐａと実質的に水が存在しない状態でもアモルファス膜として成膜できる範囲である。 Here, the molar ratio y (mol) of tin to 1 mol of indium is expressed by the molar ratio x of Ca to 1 mol of indium (−4.1 × 10 −2 Ln (x) −9.3). As shown in FIG. 12, the water pressure is within the range of not less than the value of × 10 −2 ) and not more than the value of (−2.5 × 10 −1 Ln (x) −5.7 × 10 −1 ). Is 5.0 × 10 −6 Pa, which is a range in which an amorphous film can be formed even in the absence of water.
　この結果、添加元素がＣａの場合、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するＣａのモル比ｘで表される（－４．１×１０－２Ｌｎ（ｘ）－９．３×１０－２）の値未満の範囲では、１００℃未満で、水圧力１．０×１０－２Ｐａで成膜した場合には全てアモルファスな膜となり、その後、１００℃～３００℃でアニールした場合に、結晶化するものであった。 As a result, when the additive element is Ca, the molar ratio y of tin to 1 mol of indium is expressed by the molar ratio x of Ca to 1 mol of indium (−4.1 × 10 −2 Ln (x) In the range less than the value of −9.3 × 10 −2 ), when the film is formed at a temperature of less than 100 ° C. and a water pressure of 1.0 × 10 −2 Pa, it becomes an amorphous film, and thereafter, the film is 100 ° C. to 300 ° C. When it was annealed at 0 ° C., it crystallized.
　また、この中で、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するＣａのモル比ｘで表される（－１．６×１０－２Ｌｎ（ｘ）－３．７×１０－２）未満の範囲では、水圧力を８．０×１０－４Ｐａとした場合、結晶化温度が１００℃未満となり、アモルファス膜として成膜するのは困難であることがわかった。よって、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するＣａのモル比ｘで表される（－４．１×１０－２Ｌｎ（ｘ）－９．３×１０－２）の値未満であり且つ（－１．６×１０－２Ｌｎ（ｘ）－３．７×１０－２）以上の範囲が特に好ましく、水の分圧が１．０×１０-4Ｐａ以上１．０×１０-３Ｐａ以下の条件下で成膜すれば、１００℃未満の温度でアモルファス膜が成膜でき、成膜後は、１００℃～３００℃でアニールすることにより結晶化できる膜となることがわかった。 In this, the molar ratio y of tin to 1 mol of indium is represented by the molar ratio x of Ca to 1 mol of indium (−1.6 × 10 −2 Ln (x) −3.7). In the range of less than × 10 −2 ), when the water pressure was 8.0 × 10 −4 Pa, the crystallization temperature was less than 100 ° C., and it was found difficult to form an amorphous film. Therefore, the molar ratio y of tin to 1 mol of indium is expressed by the molar ratio x of Ca to 1 mol of indium (−4.1 × 10 −2 Ln (x) −9.3 × 10 −2 ) And (−1.6 × 10 −2 Ln (x) −3.7 × 10 −2 ) or more is particularly preferable, and the partial pressure of water is 1.0 × 10 −4 Pa or more. If the film is formed under the condition of 1.0 × 10 −3 Pa or less, an amorphous film can be formed at a temperature of less than 100 ° C. After the film is formed, the film can be crystallized by annealing at 100 ° C. to 300 ° C. I found out that
Figure JPOXMLDOC01-appb-T000022
Figure JPOXMLDOC01-appb-T000022
Figure JPOXMLDOC01-appb-T000023
Figure JPOXMLDOC01-appb-T000023
Figure JPOXMLDOC01-appb-T000024
Figure JPOXMLDOC01-appb-T000024
　（Ｍｇ含有組成透明導電膜試験例１）
　上述したとおり製造した表９に示す組成のターゲットを用い、これを４インチのＤＣマグネトロンスパッタ装置にそれぞれ装着し、基板温度を室温（約２０℃）、酸素分圧を０～３．０ｓｃｃｍの間で変化させながら（０～１．１×１０-2Ｐａに相当）、各組成の透明導電膜を得た。 (Mg-containing composition transparent conductive film test example 1)
The targets having the composition shown in Table 9 manufactured as described above were used and mounted on a 4-inch DC magnetron sputtering apparatus, the substrate temperature was room temperature (about 20 ° C.), and the oxygen partial pressure was between 0 and 3.0 sccm. (Corresponding to 0 to 1.1 × 10 −2 Pa) while obtaining a transparent conductive film of each composition.
　スパッタの条件は、以下の通りとし、厚さ１２００Åの膜を得た。 The sputtering conditions were as follows, and a film having a thickness of 1200 mm was obtained.
　ターゲット寸法　：Φ＝４ｉｎ．　ｔ＝６ｍｍ
　スパッタ方式　：ＤＣマグネトロンスパッタ
　排気装置　：ロータリーポンプ＋クライオポンプ
　到達真空度　：５．３×１０-５［Ｐａ］
　Ａｒ圧力　：４．０×１０-1［Ｐａ］
　酸素圧力：０～１．１×１０-2［Ｐａ］
　水圧力：１．０×１０－２［Ｐａ］
　基板温度：室温
　スパッタ電力　：１３０Ｗ　（電力密度１．６Ｗ／ｃｍ2）
　使用基板　：コーニング＃１７３７（液晶ディスプレイ用ガラス）　ｔ＝０．８ｍｍ Target size: Φ = 4 in. t = 6mm
Sputtering method: DC magnetron sputtering Exhaust device: Rotary pump + cryopump Ultimate vacuum: 5.3 × 10 −5 [Pa]
Ar pressure: 4.0 × 10 −1 [Pa]
Oxygen pressure: 0 to 1.1 × 10 −2 [Pa]
Water pressure: 1.0 × 10 −2 [Pa]
Substrate temperature: Room temperature Sputtering power: 130 W (Power density 1.6 W / cm 2 )
Substrate used: Corning # 1737 (glass for liquid crystal display) t = 0.8 mm
　ここで、全てのサンプルにおいて室温成膜の最適酸素分圧と、２５０℃アニール後に最も抵抗率が低い成膜時の酸素分圧とが異なった。 Here, the optimal oxygen partial pressure for room temperature film formation and the oxygen partial pressure for film formation with the lowest resistivity after annealing at 250 ° C. were different for all samples.
　下記表２５には、最適酸素分圧の変化があったものを○、最適酸素分圧の変化がなかったものを×として示した。 In Table 25 below, the change in the optimum oxygen partial pressure was indicated by ○, and the change in the optimum oxygen partial pressure was indicated by ×.
　また、各組成について、２５０℃アニール後に最も抵抗率が低い成膜時の酸素分圧で成膜した透明導電膜を、それぞれ１３ｍｍ角の大きさに切り出し、これらのサンプルを大気中にて２５０℃で１時間アニールし、室温成膜時と２５０℃アニール後の結晶状態について、アモルファスはａ、結晶はｃとし、これらを表２５に示した。 Further, for each composition, transparent conductive films formed at the oxygen partial pressure at the time of film formation having the lowest resistivity after annealing at 250 ° C. were cut into 13 mm square sizes, and these samples were 250 ° C. in the atmosphere. The crystal state after annealing at room temperature for 1 hour and after film formation at room temperature and after annealing at 250 ° C. is a for amorphous and c for crystal.
　また、各組成の結晶化温度を測定し、表２５に示した。結晶化温度は１００℃で成膜した後、結晶化する温度であり、１００℃成膜でアモルファスとならないものは１００℃未満とした。 Further, the crystallization temperature of each composition was measured and shown in Table 25. The crystallization temperature is the temperature at which crystallization occurs after film formation at 100 ° C., and the temperature that does not become amorphous after film formation at 100 ° C. is less than 100 ° C.
　さらに、各組成について、２５０℃アニール後に最も抵抗率が低い成膜時の酸素分圧で成膜し、アニール後のサンプルの抵抗率ρ（Ω・ｃｍ）を測定した。これらの結果を表２５に示す。 Furthermore, for each composition, a film was formed at the oxygen partial pressure at the time of film formation having the lowest resistivity after annealing at 250 ° C., and the resistivity ρ (Ω · cm) of the sample after annealing was measured. These results are shown in Table 25.
　また、各組成について、２５０℃アニール後に最も抵抗率が低い成膜時の酸素分圧で成膜した透明導電膜を、それぞれ１３ｍｍ角の大きさに切り出し、アニール後の膜について透過スペクトルを測定した。アニール後の平均透過率を表２５に示す。 In addition, for each composition, transparent conductive films formed at the oxygen partial pressure at the time of film formation having the lowest resistivity after annealing at 250 ° C. were cut into 13 mm square sizes, and transmission spectra were measured for the annealed films. . Table 25 shows the average transmittance after annealing.
　また、各組成について、２５０℃アニール後に最も抵抗率が低い成膜時の酸素分圧で成膜し、それぞれ１０×５０ｍｍの大きさに切り出し、エッチング液としてＩＴＯ－０５Ｎ（シュウ酸系、関東化学（株）製）（シュウ酸濃度５０ｇ／Ｌ）を用い、温度３０℃で、エッチングレート（Å／ｓｅｃ）を測定した。結果を表２５に示す。 In addition, each composition was formed at the oxygen partial pressure at the time of film formation having the lowest resistivity after annealing at 250 ° C., cut into a size of 10 × 50 mm, and ITO-05N (oxalic acid, Kanto Chemical Co., Ltd.) as an etching solution. Etching rate (Å / sec) was measured at a temperature of 30 ° C. using an oxalic acid concentration (50 g / L). The results are shown in Table 25.
　（Ｍｇ含有組成透明導電膜試験例２）
　上述したとおり製造した表９に示す組成のターゲットを用い、水圧力を８．０×１０－４Ｐａとした以外は、上述した条件で、各組成の透明導電膜を得た。 (Mg-containing composition transparent conductive film test example 2)
A transparent conductive film having each composition was obtained under the above-described conditions except that the target having the composition shown in Table 9 manufactured as described above was used and the water pressure was 8.0 × 10 −4 Pa.
　また、上述した通り、最適酸素分圧の変化の有無、結晶化温度、アニール後のサンプルの抵抗率ρ（Ω・ｃｍ）、アニール後の平均透過率、成膜後の透明導電膜のエッチングレート（Å／ｓｅｃ）をそれぞれ求め、表２６に示す。 In addition, as described above, whether or not the optimum oxygen partial pressure is changed, crystallization temperature, resistivity ρ (Ω · cm) of the sample after annealing, average transmittance after annealing, etching rate of the transparent conductive film after film formation (Å / sec) was determined and shown in Table 26.
　（Ｍｇ含有組成透明導電膜参考例）
　上述したとおり製造した表１０に示す組成のターゲットを用い、水圧力を５．０×１０－６Ｐａとした以外は、上述した条件で、各組成の透明導電膜を得た。 (Mg-containing composition transparent conductive film reference example)
A transparent conductive film having each composition was obtained under the conditions described above except that the target having the composition shown in Table 10 manufactured as described above was used and the water pressure was 5.0 × 10 −6 Pa.
　また、上述した通り、最適酸素分圧の変化の有無、結晶化温度、アニール後のサンプルの抵抗率ρ（Ω・ｃｍ）、アニール後の平均透過率、成膜後の透明導電膜のエッチングレート（Å／ｓｅｃ）をそれぞれ求め、表２７に示す。 In addition, as described above, whether or not the optimum oxygen partial pressure is changed, crystallization temperature, resistivity ρ (Ω · cm) of the sample after annealing, average transmittance after annealing, etching rate of the transparent conductive film after film formation (Å / sec) was determined and shown in Table 27.
　これら表２５～表２７の結果をそれぞれ図１３～図１５に示す。 The results of Table 25 to Table 27 are shown in FIGS. 13 to 15, respectively.
　ここで、図１３及び図１４において、（－４．１×１０－２Ｌｎ（ｘ）－９．３×１０－２）の値未満の範囲で、１００℃未満の成膜温度でアモルファス膜として成膜でき、１００～３００℃で結晶化できるサンプルを●、アモルファス膜として成膜できないものを△で示した。 Here, in FIGS. 13 and 14, - in the range of less than a value of (4.1 × 10 -2 Ln (x ) -9.3 × 10 -2), as an amorphous film at a deposition temperature less than 100 ° C. Samples that can be formed and crystallized at 100 to 300 ° C. are indicated by ●, and samples that cannot be formed as an amorphous film are indicated by Δ.
　また、図１５においては、１００℃未満の成膜温度でアモルファス膜として成膜でき、１００～３００℃で結晶化できるサンプルを●、それ以外を▲で示した。 Further, in FIG. 15, samples that can be formed as an amorphous film at a film forming temperature of less than 100 ° C. and crystallized at 100 to 300 ° C. are indicated by ●, and others are indicated by ▲.
　ここで、インジウム１モルに対しての錫のモル比ｙ（モル）が、インジウム１モルに対するＭｇのモル比ｘで表される（－４．１×１０－２Ｌｎ（ｘ）－９．３×１０－２）の値以上であり且つ（－２．５×１０－１Ｌｎ（ｘ）－５．７×１０－１）の値以下の範囲は、図１５から明らかなように、水圧力が５．０×１０－６Ｐａと実質的に水が存在しない状態でもアモルファス膜として成膜できる範囲である。 Here, the molar ratio y (mol) of tin to 1 mol of indium is expressed by the molar ratio x of Mg to 1 mol of indium (−4.1 × 10 −2 Ln (x) −9.3). As shown in FIG. 15, the water pressure is within the range of not less than the value of (× 10 −2 ) and not more than the value of (−2.5 × 10 −1 Ln (x) −5.7 × 10 −1 ) Is 5.0 × 10 −6 Pa, which is a range in which an amorphous film can be formed even in the absence of water.
　この結果、添加元素がＭｇの場合、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するＭｇのモル比ｘで表される（－４．１×１０－２Ｌｎ（ｘ）－９．３×１０－２）の値未満の範囲では、１００℃未満で、水圧力１．０×１０－２Ｐａで成膜した場合には全てアモルファスな膜となり、その後、１００℃～３００℃でアニールした場合に、結晶化するものであった。 As a result, when the additive element is Mg, the molar ratio y of tin to 1 mol of indium is expressed by the molar ratio x of Mg to 1 mol of indium (−4.1 × 10 −2 Ln (x) In the range less than the value of −9.3 × 10 −2 ), when the film is formed at a temperature of less than 100 ° C. and a water pressure of 1.0 × 10 −2 Pa, it becomes an amorphous film, and thereafter, the film is 100 ° C. to 300 ° C. When it was annealed at 0 ° C., it crystallized.
　また、この中で、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するＭｇのモル比ｘで表される（－１．６×１０－２Ｌｎ（ｘ）－３．７×１０－２）未満の範囲では、水圧力を８．０×１０－４Ｐａとした場合、結晶化温度が１００℃未満となり、アモルファス膜として成膜するのは困難であることがわかった。よって、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するＭｇのモル比ｘで表される（－４．１×１０－２Ｌｎ（ｘ）－９．３×１０－２）の値未満であり且つ（－１．６×１０－２Ｌｎ（ｘ）－３．７×１０－２）以上の範囲が特に好ましく、水の分圧が１．０×１０-4Ｐａ以上１．０×１０-３Ｐａ以下の条件下で成膜すれば、１００℃未満の温度でアモルファス膜が成膜でき、成膜後は、１００℃～３００℃でアニールすることにより結晶化できる膜となることがわかった。 In this, the molar ratio y of tin to 1 mol of indium is represented by the molar ratio x of Mg to 1 mol of indium (−1.6 × 10 −2 Ln (x) −3.7). In the range of less than × 10 −2 ), when the water pressure was 8.0 × 10 −4 Pa, the crystallization temperature was less than 100 ° C., and it was found difficult to form an amorphous film. Therefore, the molar ratio y of tin to 1 mol of indium is expressed by the molar ratio x of Mg to 1 mol of indium (−4.1 × 10 −2 Ln (x) −9.3 × 10 −2 ) And (−1.6 × 10 −2 Ln (x) −3.7 × 10 −2 ) or more is particularly preferable, and the partial pressure of water is 1.0 × 10 −4 Pa or more. If the film is formed under the condition of 1.0 × 10 −3 Pa or less, an amorphous film can be formed at a temperature of less than 100 ° C. After the film is formed, the film can be crystallized by annealing at 100 ° C. to 300 ° C. I found out that
Figure JPOXMLDOC01-appb-T000025
Figure JPOXMLDOC01-appb-T000025
Figure JPOXMLDOC01-appb-T000026
Figure JPOXMLDOC01-appb-T000026
Figure JPOXMLDOC01-appb-T000027
Figure JPOXMLDOC01-appb-T000027
　（Ｙ含有組成透明導電膜試験例１）
　上述したとおり製造した表１１に示す組成のターゲットを用い、これを４インチのＤＣマグネトロンスパッタ装置にそれぞれ装着し、基板温度を室温（約２０℃）、酸素分圧を０～３．０ｓｃｃｍの間で変化させながら（０～１．１×１０-2Ｐａに相当）、各組成の透明導電膜を得た。 (Y-containing composition transparent conductive film test example 1)
Using the targets having the composition shown in Table 11 manufactured as described above, these were mounted on a 4-inch DC magnetron sputtering apparatus, the substrate temperature was room temperature (about 20 ° C.), and the oxygen partial pressure was between 0 and 3.0 sccm. (Corresponding to 0 to 1.1 × 10 −2 Pa) while obtaining a transparent conductive film of each composition.
　スパッタの条件は、以下の通りとし、厚さ１２００Åの膜を得た。 The sputtering conditions were as follows, and a film having a thickness of 1200 mm was obtained.
　ターゲット寸法　：Φ＝４ｉｎ．　ｔ＝６ｍｍ
　スパッタ方式　：ＤＣマグネトロンスパッタ
　排気装置　：ロータリーポンプ＋クライオポンプ
　到達真空度　：５．３×１０-５［Ｐａ］
　Ａｒ圧力　：４．０×１０-1［Ｐａ］
　酸素圧力：０～１．１×１０-2［Ｐａ］
　水圧力：１．０×１０－２［Ｐａ］
　基板温度：室温
　スパッタ電力　：１３０Ｗ　（電力密度１．６Ｗ／ｃｍ2）
　使用基板　：コーニング＃１７３７（液晶ディスプレイ用ガラス）　ｔ＝０．８ｍｍ Target size: Φ = 4 in. t = 6mm
Sputtering method: DC magnetron sputtering Exhaust device: Rotary pump + cryopump Ultimate vacuum: 5.3 × 10 −5 [Pa]
Ar pressure: 4.0 × 10 −1 [Pa]
Oxygen pressure: 0 to 1.1 × 10 −2 [Pa]
Water pressure: 1.0 × 10 −2 [Pa]
Substrate temperature: Room temperature Sputtering power: 130 W (Power density 1.6 W / cm 2 )
Substrate used: Corning # 1737 (glass for liquid crystal display) t = 0.8 mm
　ここで全てのサンプルにおいて室温成膜の最適酸素分圧と、２５０℃アニール後に最も抵抗率が低い成膜時の酸素分圧とが異なった。 Here, the optimal oxygen partial pressure for room temperature film formation and the oxygen partial pressure for film formation with the lowest resistivity after annealing at 250 ° C. were different for all samples.
　下記表２８には、最適酸素分圧の変化があったものを○、最適酸素分圧の変化がなかったものを×として示した。 In Table 28 below, the change in the optimum oxygen partial pressure was indicated by ○, and the change in the optimum oxygen partial pressure was indicated by ×.
　また、各組成について、２５０℃アニール後に最も抵抗率が低い成膜時の酸素分圧で成膜した透明導電膜を、それぞれ１３ｍｍ角の大きさに切り出し、これらのサンプルを大気中にて２５０℃で１時間アニールし、室温成膜時と２５０℃アニール後の結晶状態について、アモルファスはａ、結晶はｃとし、これらを表２８に示した。 Further, for each composition, transparent conductive films formed at the oxygen partial pressure at the time of film formation having the lowest resistivity after annealing at 250 ° C. were cut into 13 mm square sizes, and these samples were 250 ° C. in the atmosphere. The crystal states after annealing at room temperature for 1 hour, after film formation at room temperature and after annealing at 250 ° C. are a for amorphous and c for crystal, and these are shown in Table 28.
　また、各組成の結晶化温度を測定し、表２８に示した。結晶化温度は室温で成膜した後、結晶化する温度であり、室温成膜でアモルファスとならないものは１００℃未満とした。 Further, the crystallization temperature of each composition was measured and shown in Table 28. The crystallization temperature is a temperature at which crystallization is performed after film formation at room temperature, and the temperature at which film formation does not become amorphous by film formation at room temperature is set to less than 100 ° C.
　さらに、各組成について、２５０℃アニール後に最も抵抗率が低い成膜時の酸素分圧で成膜し、アニール後のサンプルの抵抗率ρ（Ω・ｃｍ）を測定した。これらの結果を表２８に示す。 Furthermore, for each composition, a film was formed at the oxygen partial pressure at the time of film formation having the lowest resistivity after annealing at 250 ° C., and the resistivity ρ (Ω · cm) of the sample after annealing was measured. These results are shown in Table 28.
　また、各組成について、２５０℃アニール後に最も抵抗率が低い成膜時の酸素分圧で成膜した透明導電膜を、それぞれ１３ｍｍ角の大きさに切り出し、アニール後の膜について透過スペクトルを測定した。アニール後の平均透過率を表２８に示す。 In addition, for each composition, transparent conductive films formed at the oxygen partial pressure at the time of film formation having the lowest resistivity after annealing at 250 ° C. were cut into 13 mm square sizes, and transmission spectra were measured for the annealed films. . Table 28 shows the average transmittance after annealing.
　また、各組成について、２５０℃アニール後に最も抵抗率が低い成膜時の酸素分圧で成膜し、それぞれ１０×５０ｍｍの大きさに切り出し、エッチング液としてＩＴＯ－０５Ｎ（シュウ酸系、関東化学（株）製）（シュウ酸濃度５０ｇ／Ｌ）を用い、温度３０℃で、エッチングレート（Å／ｓｅｃ）を測定した。結果を表２８に示す。 In addition, each composition was formed at the oxygen partial pressure at the time of film formation having the lowest resistivity after annealing at 250 ° C., cut into a size of 10 × 50 mm, and ITO-05N (oxalic acid, Kanto Chemical Co., Ltd.) as an etching solution. Etching rate (Å / sec) was measured at a temperature of 30 ° C. using an oxalic acid concentration (50 g / L). The results are shown in Table 28.
　（Ｙ含有組成透明導電膜試験例２）
　上述したとおり製造した表１１に示す組成のターゲットを用い、水圧力を８．０×１０－４Ｐａとした以外は、上述した条件で、各組成の透明導電膜を得た。 (Y-containing composition transparent conductive film test example 2)
A transparent conductive film having each composition was obtained under the conditions described above except that the target having the composition shown in Table 11 manufactured as described above was used and the water pressure was 8.0 × 10 −4 Pa.
　また、上述した通り、最適酸素分圧の変化の有無、結晶化温度、アニール後のサンプルの抵抗率ρ（Ω・ｃｍ）、アニール後の平均透過率、成膜後の透明導電膜のエッチングレート（Å／ｓｅｃ）をそれぞれ求め、表２９に示す。 In addition, as described above, whether or not the optimum oxygen partial pressure is changed, crystallization temperature, resistivity ρ (Ω · cm) of the sample after annealing, average transmittance after annealing, etching rate of the transparent conductive film after film formation (Å / sec) was determined and shown in Table 29.
　（Ｙ含有組成透明導電膜参考例）
　上述したとおり製造した表１２に示す組成のターゲットを用い、水圧力を５．０×１０－６Ｐａとした以外は、上述した条件で、各組成の透明導電膜を得た。 (Y-containing composition transparent conductive film reference example)
A transparent conductive film having each composition was obtained under the above-described conditions except that the target having the composition shown in Table 12 manufactured as described above was used and the water pressure was 5.0 × 10 −6 Pa.
　また、上述した通り、最適酸素分圧の変化の有無、結晶化温度、アニール後のサンプルの抵抗率ρ（Ω・ｃｍ）、アニール後の平均透過率、成膜後の透明導電膜のエッチングレート（Å／ｓｅｃ）をそれぞれ求め、表３０に示す。 In addition, as described above, whether or not the optimum oxygen partial pressure is changed, crystallization temperature, resistivity ρ (Ω · cm) of the sample after annealing, average transmittance after annealing, etching rate of the transparent conductive film after film formation (Å / sec) was determined and shown in Table 30.
　これら表２８～表３０の結果をそれぞれ図１６～図１８に示す。 The results of Table 28 to Table 30 are shown in FIGS. 16 to 18, respectively.
　ここで、図１６及び図１７において、（－２．５×１０－２Ｌｎ（ｘ）－５．８×１０－２）の値未満の範囲で、１００℃未満の成膜温度でアモルファス膜として成膜でき、１００～３００℃で結晶化できるサンプルを●、アモルファス膜として成膜できないものを△で示した。 Here, in FIGS. 16 and 17, - in the range of less than a value of (2.5 × 10 -2 Ln (x ) -5.8 × 10 -2), as an amorphous film at a deposition temperature less than 100 ° C. Samples that can be formed and crystallized at 100 to 300 ° C. are indicated by ●, and samples that cannot be formed as an amorphous film are indicated by Δ.
　また、図１８においては、１００℃未満の成膜温度でアモルファス膜として成膜でき、１００～３００℃で結晶化できるサンプルを●、それ以外を▲で示した。 In FIG. 18, samples that can be formed as an amorphous film at a film forming temperature of less than 100 ° C. and crystallized at 100 to 300 ° C. are indicated by ●, and the others are indicated by ▲.
　ここで、インジウム１モルに対しての錫のモル比ｙ（モル）が、インジウム１モルに対するＹのモル比ｘで表される（－２．５×１０－２Ｌｎ（ｘ）－５．８×１０－２）の値以上であり且つ（－１．０×１０－１Ｌｎ（ｘ）－５．０×１０－２）の値以下の範囲は、図１８から明らかなように、水圧力が５．０×１０－６Ｐａと実質的に水が存在しない状態でもアモルファス膜として成膜できる範囲である。 Here, the molar ratio y (mol) of tin to 1 mol of indium is represented by the molar ratio x of Y to 1 mol of indium (−2.5 × 10 −2 Ln (x) −5.8). × 10 -2) is a value or more and (-1.0 × 10 -1 Ln (x ) -5.0 × 10 -2 and less than or equal to the range of), as is clear from FIG. 18, the water pressure Is 5.0 × 10 −6 Pa, which is a range in which an amorphous film can be formed even in the absence of water.
　この結果、添加元素がＹの場合、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するＹのモル比ｘで表される（－２．５×１０－２Ｌｎ（ｘ）－５．８×１０－２）の値未満の範囲では、１００℃未満で、水圧力１．０×１０－２Ｐａで成膜した場合には全てアモルファスな膜となり、その後、１００℃～３００℃でアニールした場合に、結晶化するものであった。 As a result, when the additive element is Y, the molar ratio y of tin to 1 mol of indium is represented by the molar ratio x of Y to 1 mol of indium (−2.5 × 10 −2 Ln (x) In the range of less than −5.8 × 10 −2 ), when the film is formed at a water pressure of 1.0 × 10 −2 Pa at a temperature of less than 100 ° C., the film becomes an amorphous film. When it was annealed at 0 ° C., it crystallized.
　また、この中で、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するＹのモル比ｘで表される（－２．２×１０－２Ｌｎ（ｘ）－１．５×１０－１）未満の範囲では、水圧力を８．０×１０－４Ｐａとした場合、結晶化温度が１００℃未満となり、アモルファス膜として成膜するのは困難であることがわかった。よって、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するＹのモル比ｘで表される（－２．５×１０－２Ｌｎ（ｘ）－５．８×１０－２）の値未満であり且つ（－２．２×１０－２Ｌｎ（ｘ）－１．５×１０－１）以上の範囲が特に好ましく、水の分圧が１．０×１０-4Ｐａ以上１．０×１０-３Ｐａ以下の条件下で成膜すれば、１００℃未満の温度でアモルファス膜が成膜でき、成膜後は、１００℃～３００℃でアニールすることにより結晶化できる膜となることがわかった。 In this, the molar ratio y of tin to 1 mol of indium is represented by the molar ratio x of Y to 1 mol of indium (−2.2 × 10 −2 Ln (x) −1.5 In the range of less than × 10 −1 ), when the water pressure was 8.0 × 10 −4 Pa, the crystallization temperature was less than 100 ° C., and it was found difficult to form an amorphous film. Therefore, the molar ratio y of tin to 1 mol of indium is represented by the molar ratio x of Y to 1 mol of indium (−2.5 × 10 −2 Ln (x) −5.8 × 10 −2 ) And (−2.2 × 10 −2 Ln (x) −1.5 × 10 −1 ) or more is particularly preferable, and the partial pressure of water is 1.0 × 10 −4 Pa or more. If the film is formed under the condition of 1.0 × 10 −3 Pa or less, an amorphous film can be formed at a temperature of less than 100 ° C. After the film is formed, the film can be crystallized by annealing at 100 ° C. to 300 ° C. I found out that
Figure JPOXMLDOC01-appb-T000028
Figure JPOXMLDOC01-appb-T000028
Figure JPOXMLDOC01-appb-T000029
Figure JPOXMLDOC01-appb-T000029
Figure JPOXMLDOC01-appb-T000030
Figure JPOXMLDOC01-appb-T000030
（水素存在確認試験）
　成膜されたアモルファス膜内に含有される水素は、アニールによる結晶化に伴い、膜内もしくは雰囲気中の酸素と結びつき、水ガスとして脱離するとの推測に基づき、昇温脱離法（ＴＰＤ）で加熱時に発生する水ガスの検出を行うことにより、膜内に水素が含有されていることを確認した。 (Hydrogen presence confirmation test)
Based on the assumption that hydrogen contained in the deposited amorphous film is combined with oxygen in the film or in the atmosphere as it is crystallized by annealing, and desorbed as water gas, temperature programmed desorption (TPD) It was confirmed that hydrogen was contained in the film by detecting water gas generated during heating at.
　以下、Ｓｒ添加ＩＴＯであるＡ８を試験試料とした確認試験を示す。
　４インチのＤＣマグネトロンスパッタ装置にサンプルＡ８のスパッタリングターゲットをそれぞれ装着し、基板温度を室温（約２０℃）、成膜時の水分圧０Ｐａ（ＴＰＤ試験例１とする）、８．０×１０－４Ｐａ（ＴＰＤ試験例２とする）及び１．０×１０－２Ｐａ（ＴＰＤ試験例３とする）条件でＴＰＤ試験例１～３の透明導電膜を得た。 Hereinafter, a confirmation test using A8 as Sr-added ITO as a test sample will be shown.
A sputtering target of sample A8 was mounted on a 4-inch DC magnetron sputtering apparatus, the substrate temperature was room temperature (about 20 ° C.), the water pressure during film formation was 0 Pa (referred to as TPD Test Example 1), 8.0 × 10 − Transparent conductive films of TPD Test Examples 1 to 3 were obtained under the conditions of 4 Pa (referred to as TPD Test Example 2) and 1.0 × 10 −2 Pa (referred to as TPD Test Example 3).
　スパッタの条件は、以下の通りとし、厚さ１．８μｍの膜を得た。
　ターゲット寸法　：Φ＝４ｉｎ．　ｔ＝６ｍｍ
　スパッタ方式　　：ＤＣマグネトロンスパッタ
　排気装置　　　　：ロータリーポンプ＋クライオポンプ
　到達真空度　　　：５．０×１０－５［Ｐａ］
　Ａｒ圧力　　　　：４．０×１０－１［Ｐａ］
　酸素圧力　　　　：０［Ｐａ］
　水圧力　　　　　：０、８．０×１０－４、１．０×１０－２［Ｐａ］
　基板温度　　　　：室温
　スパッタ電力　　：１３０Ｗ　（電力密度１．６Ｗ　／　ｃｍ２）
　使用基板　　　　：電解銅箔ｔ　＝　１５μｍ The sputtering conditions were as follows, and a film having a thickness of 1.8 μm was obtained.
Target size: Φ = 4 in. t = 6mm
Sputtering method: DC magnetron sputtering Exhaust device: Rotary pump + cryopump Ultimate vacuum: 5.0 × 10 −5 [Pa]
Ar pressure: 4.0 × 10 −1 [Pa]
Oxygen pressure: 0 [Pa]
Water pressure: 0, 8.0 × 10 −4 , 1.0 × 10 −2 [Pa]
Substrate temperature: Room temperature Sputtering power: 130 W (Power density 1.6 W / cm 2 )
Substrate used: electrolytic copper foil t = 15 μm
　ここで、各条件で成膜した試料の結晶状態を薄膜ＸＲＤで分析したところ、ＴＰＤ試験例１では結晶化、ＴＰＤ試験例２及び３ではアモルファスとなっていることが確認された。 Here, when the crystal state of the sample formed under each condition was analyzed by thin film XRD, it was confirmed that the sample was crystallized in TPD Test Example 1 and amorphous in TPD Test Examples 2 and 3.
　各膜試料に存在する水素は、ＴＰＤ（日本ベル製）により以下に示す測定条件で、加熱時に発生する水ガスを、四重極式質量分析装置（ＱＭＳ）にて質量数（ｍ／ｅ）＝１８のフラグメントイオン（Ｈ２Ｏ＋）の強度を比較することで確認した。なお、基板である銅箔内に含まれる水ガスの脱離挙動についても調べるため、ブランクとして銅箔試料の測定も行った。 Hydrogen present in each membrane sample is measured by the following conditions using TPD (manufactured by Nippon Bell), and water gas generated during heating is converted into a mass number (m / e) using a quadrupole mass spectrometer (QMS). = 18 fragment ions was confirmed by comparing the intensity of the (H 2 O +). In addition, in order to investigate also about the desorption | desorption behavior of the water gas contained in the copper foil which is a board | substrate, the copper foil sample was also measured as a blank.
［測定条件］
　測定雰囲気　　：２０％Ｏ２－８０％Ｈｅ
　ガス流量　　　：５０ｃｃｍ
　前処理　　　　：１２０℃、３０ｍｉｎキープ（試料に付着した水分を除去するため）
　測定温度　　　：１２０～６００℃
　昇温速度　　　：４℃／ｍｉｎ [Measurement condition]
Measurement atmosphere: 20% O 2 -80% He
Gas flow rate: 50ccm
Pretreatment: 120 ° C., 30 min keep (to remove water adhering to the sample)
Measurement temperature: 120-600 ° C
Temperature increase rate: 4 ° C / min
　図１９には各膜試料及びブランクである銅箔試料の前処理後１２０～６００℃における質量数（ｍ／ｅ）＝１８のフラグメントイオン（Ｈ２Ｏ＋）の強度変化を示す。全ての試料の全測定温度範囲でＨ２Ｏ＋イオンが検出されているが、これらは装置内や雰囲気ガスに存在する水分の影響であると考えられる。このような挙動は、あらゆる試料を測定しても常に検出されることから、これらをベースラインとして考え、強度補正するのが一般的である。そこで本測定結果においても同様に、ベースライン補正処理を行った。その結果を図２０に示す。 FIG. 19 shows changes in the intensity of fragment ions (H 2 O + ) having a mass number (m / e) = 18 at 120 to 600 ° C. after pretreatment of each film sample and a blank copper foil sample. Although H 2 O + ions are detected in the entire measurement temperature range of all the samples, these are considered to be due to the influence of moisture present in the apparatus and in the atmospheric gas. Since such a behavior is always detected even if any sample is measured, it is general to consider these as a baseline and correct the intensity. Accordingly, the baseline correction processing was performed in the same way for the measurement results. The result is shown in FIG.
　まず、ブランクである銅箔試料では、２００～３００℃において僅かであるがＨ２Ｏ＋イオンのピークが認められた。これは銅箔試料に含有している水分が脱離したものであると考えられる。また実質的に水が存在しない雰囲気下で成膜したＴＰＤ試験例１は、ほぼブランクである銅箔試料のＨ２Ｏ＋イオンのピークと重なっている。このことから、ＴＰＤ試験例１の試料内にはほとんど水素は含有していないと言える。一方、成膜時の水分圧を上昇させて水を添加したＴＰＤ試験例２及び３では２００～３００℃の温度範囲にとどまらず、３００℃以上においてもＨ２Ｏ＋イオンのピークが確認された。特に成膜時の水の添加量が多いＴＰＤ試験例３では、４００℃付近に大きなＨ２Ｏ＋イオンのピークがあるのが確認された。 First, in the blank copper foil sample, a slight H 2 O + ion peak was observed at 200 to 300 ° C. This is considered that the moisture contained in the copper foil sample is detached. In addition, TPD Test Example 1 formed in an atmosphere substantially free of water overlaps with the H 2 O + ion peak of the copper foil sample that is almost blank. From this, it can be said that the sample of TPD Test Example 1 hardly contains hydrogen. On the other hand, in TPD Test Examples 2 and 3 in which water was added by increasing the water pressure during film formation, the peak of H 2 O + ions was confirmed not only in the temperature range of 200 to 300 ° C. but also at 300 ° C. or higher. . In particular, in TPD Test Example 3 in which the amount of water added during film formation was large, it was confirmed that there was a large H 2 O + ion peak near 400 ° C.
　以上の結果により、ＴＰＤ試験例２及び３から、成膜時に水素分圧を所定範囲として水を添加することで、膜内に水素が取り込まれ、水素が含有されることが分かった。また、ＴＰＤ試験例２及び３の結晶化温度はそれぞれ２００℃及び３００℃であるが、これらの試料のＨ２Ｏ＋イオンのピークは３００℃以上でも確認されていることから、これらの試料は結晶化後も水ガスが脱離していることが分かった。 From the above results, it was found from TPD Test Examples 2 and 3 that hydrogen was taken into the film and contained by adding water with a hydrogen partial pressure within a predetermined range during film formation. In addition, the crystallization temperatures of TPD Test Examples 2 and 3 are 200 ° C. and 300 ° C., respectively, but the peak of H 2 O + ions of these samples is confirmed even at 300 ° C. or higher. It was found that water gas was desorbed even after crystallization.
　なお、最近の研究では、スパッタ法及び電子ビーム蒸着にて成膜されたＩＴＯ膜内に含有する微量な水分について、昇温脱離法（ＴＰＤ：Temperature Programmed Desorption）を用いて定量化を行っている報告例もある（J. Therm. Anal. Calori., 69 (2002) 1021-1029. ）。従って、膜内水素の存在を確認するために、ＴＰＤを用いて、脱離する水ガスを検出する手法は非常に有用であると言える。なお、同種の方法である昇温脱離ガス分析法（ＴＤＳ：Thermal Desorption Spectroscopy）も有用であると言える。 In recent research, a small amount of water contained in an ITO film formed by sputtering and electron beam evaporation has been quantified using a temperature programmed desorption (TPD) method. There are some reports (J. Therm. Anal. Calori., 69 (2002) 1021-1029.). Therefore, in order to confirm the presence of hydrogen in the membrane, it can be said that a technique of detecting desorbed water gas using TPD is very useful. In addition, it can be said that the temperature desorption gas analysis method (TDS: Thermal Desorption Spectroscopy) which is the same kind of method is also useful.
　また、以上の測定結果は添加元素がＳｒの場合であるが、他の添加元素（Ｌｉ、Ｌａ、Ｃａ、Ｍｇ、Ｙ）は、酸素結合エネルギーが１００～３５０ｋＪ／ｍｏｌの範囲にある点で共通するので、他の添加元素（Ｌｉ、Ｌａ、Ｃａ、Ｍｇ、Ｙ）の場合も、成膜時の水分圧を制御することで、膜内に水分が取り込まれることによる水素量を変化させることができることは明らかであり、水分圧を所定範囲として成膜されたアモルファス膜には同様に水素が含有されていることが明らかである。 The above measurement results are for the case where the additive element is Sr, but the other additive elements (Li, La, Ca, Mg, Y) are common in that the oxygen binding energy is in the range of 100 to 350 kJ / mol. Therefore, in the case of other additive elements (Li, La, Ca, Mg, Y), the amount of hydrogen due to moisture being taken into the film can be changed by controlling the water pressure during film formation. It is clear that this can be done, and it is clear that the amorphous film formed with the moisture pressure in the predetermined range similarly contains hydrogen.
　なお、本発明による透明導電膜が、実際に液晶表示装置やガラスの結露防止用発熱膜、赤外線反射膜等に搭載されている場合、それらの膜内に存在する水素を確認するためには、成膜されている基板を取り出し、上述したＴＰＤ法により、加熱時に発生する水ガスを検出することで可能である。 In addition, when the transparent conductive film according to the present invention is actually mounted on a liquid crystal display device or a heat generation film for preventing condensation of glass, an infrared reflection film, etc., in order to confirm hydrogen present in those films, This is possible by taking out the substrate on which the film is formed and detecting the water gas generated during heating by the TPD method described above.
　また、膜内に存在する水素の直接的な確認及び定量のためには、Ｋｏｉｄｅらの報告例（Jpn. J. Appl. Phys., 46, No. 28(2007) L685-L687）にある水素前方散乱法（ＨＦＳ）を用いると可能である。 In addition, for direct confirmation and quantification of hydrogen present in the membrane, the hydrogen in the report of Koide et al. (Jpn. J. Appl. Phys., 46, No. 28 (2007) L685-L687) It is possible to use the forward scattering method (HFS).
　さらに、ＴＯＦ－ＳＩＭＳ及びダイナミックＳＩＭＳでも、膜内に存在する水素を分析可能である。 Furthermore, hydrogen present in the film can be analyzed by TOF-SIMS and dynamic SIMS.
　以下に参考例として、Ｂａ添加ＩＴＯ膜についてではあるが、ＴＯＦ－ＳＩＭＳによって膜内に含有された水素を確認した試験を示す。 As a reference example, a test for confirming hydrogen contained in a film by TOF-SIMS is shown below as a Ba-added ITO film.
（参考試験例）
　４インチのＤＣマグネトロンスパッタ装置に、Ｉｎ１モルに対して、Ｓｎ０．０５モル、Ｂａ０．０５モル含有するＢａ－ＩＴＯスパッタリングターゲットをそれぞれ装着し、基板温度を室温（約２０℃）、水の分圧を５．０×１０－５Ｐａ（ＴＯＦ試験例１とする）、５．０×１０－３Ｐａ（ＴＯＦ試験例２とする）及び１．０×１０－２Ｐａ（ＴＯＦ試験例３とする）、の３条件でＴＯＦ試験例１～３の透明導電膜を得た。 (Reference test example)
A Ba-ITO sputtering target containing 0.05 mol of Sn and 0.05 mol of Ba with respect to 1 mol of In was mounted on a 4-inch DC magnetron sputtering apparatus, the substrate temperature was room temperature (about 20 ° C), and the partial pressure of water Of 5.0 × 10 −5 Pa (referred to as TOF Test Example 1), 5.0 × 10 −3 Pa (referred to as TOF Test Example 2), and 1.0 × 10 −2 Pa (referred to as TOF Test Example 3) The transparent conductive films of TOF Test Examples 1 to 3 were obtained under the following three conditions.
　スパッタの条件は、以下の通りとし、厚さ１２００Åの膜を得た。 The sputtering conditions were as follows, and a film having a thickness of 1200 mm was obtained.
　ターゲット寸法　：Φ＝４ｉｎ．　ｔ＝６ｍｍ
　スパッタ方式　　：ＤＣマグネトロンスパッタ
　排気装置　　　　：ロータリーポンプ＋クライオポンプ
　到達真空度　　　：５．３×１０－5［Ｐａ］
　Ａｒ圧力　　　　：４．０×１０－１［Ｐａ］
　酸素圧力　　　　：０［Ｐａ］
　水圧力　　　　　：５．０×１０－５、５．０×１０－３、１．０×１０－２［Ｐａ］
　基板温度　　　　：室温
　スパッタ電力　　：１３０Ｗ　（電力密度１．６Ｗ／ｃｍ２）
　使用基板　：コーニング＃１７３７（液晶ディスプレイ用ガラス）　ｔ＝０．８ｍｍ Target size: Φ = 4 in. t = 6mm
Sputtering method: DC magnetron sputtering Exhaust device: Rotary pump + cryopump Ultimate vacuum: 5.3 × 10 −5 [Pa]
Ar pressure: 4.0 × 10 −1 [Pa]
Oxygen pressure: 0 [Pa]
Water pressure: 5.0 × 10 −5 , 5.0 × 10 −3 , 1.0 × 10 −2 [Pa]
Substrate temperature: Room temperature Sputtering power: 130 W (Power density 1.6 W / cm 2 )
Substrate used: Corning # 1737 (glass for liquid crystal display) t = 0.8 mm
　ここで、各条件において成膜した試料の結晶状態を薄膜ＸＲＤで分析したところ、ＴＯＦ試験例２、３ではアモルファス、ＴＯＦ試験例１では結晶化していることが確認された。 Here, when the crystal state of the sample formed under each condition was analyzed by the thin film XRD, it was confirmed that the TOF Test Examples 2 and 3 were amorphous and the TOF Test Example 1 was crystallized.
　また、各膜内の水素の存在については、飛行時間型二次イオン質量分析法（ＴＯＦ－ＳＩＭＳ、ＵＬＶＡＣ　ＰＨＩ社製　ＴＲＩＦＴ　ＩＶ）を用い、各試料について、以下に示す測定条件により、検出される（Ｈ＋イオン数）／（全イオン数）を比較することで確認した。 In addition, the presence of hydrogen in each membrane is detected using the time-of-flight secondary ion mass spectrometry method (TOF-SIMS, TRIFT IV manufactured by ULVAC PHI) for each sample under the measurement conditions shown below. This was confirmed by comparing (H + number of ions) / (total number of ions).
［測定条件］
　一次イオン：　Ａｕ＋
　加速電圧：　３０ｋＶ
　スキャン条件：　ラスタースキャン（２００×２００μｍ） [Measurement condition]
Primary ion: Au +
Accelerating voltage: 30 kV
Scan conditions: Raster scan (200 × 200 μm)
　表３１は、成膜した試料のＴＯＦ－ＳＩＭＳ分析結果である、（Ｈ＋イオンのカウント数）／（全イオンのカウント数）を示す。 Table 31 shows (H + ion count number) / (total ion count number), which is a TOF-SIMS analysis result of the deposited sample.
　ここで、成膜時の水分圧が５．０×１０－５と実質的に水が存在しない雰囲気下で成膜したＴＯＦ試験例１の試料においてもＨ＋イオンが検出されているが、これはバックラウンドとして判断することができる。すなわち、最近の研究において、ＴＯＦ試験例１の水分圧よりも低い分圧で成膜した酸化インジウム膜からＨ＋イオンが検出されたことが報告されている（Jpn.J.Appl.Phys.,Vol.46,No.28,2007,pp.L685-L687）ことからすると、検出された水素イオンは成膜時に基板に付着した僅かな水分が膜内に取り込まれたものと推測できる。よって、実質的に水が存在しない雰囲気下である水分圧が５．０×１０－５以下の雰囲気で成膜したサンプルの（Ｈ＋イオン数）／（全イオン数）である７．７５×１０－４を基準値とし、これより増えた（Ｈ＋イオン数）／（全イオン数）を膜に含有される水素イオンとすることができる。 Here, H + ions were also detected in the sample of TOF Test Example 1 formed in an atmosphere where the water pressure during film formation was 5.0 × 10 −5 and substantially no water was present. Can be determined as a background. That is, in recent research, it has been reported that H + ions were detected from an indium oxide film formed at a partial pressure lower than the water pressure of TOF Test Example 1 (Jpn. J. Appl. Phys., Vol. 46, No. 28, 2007, pp. L685-L687) From the above, it can be inferred that the detected hydrogen ions have incorporated a small amount of moisture adhering to the substrate during film formation into the film. Therefore, 7.75 × which is (H + number of ions) / (total number of ions) of a sample formed in an atmosphere having a water pressure of 5.0 × 10 −5 or less under an atmosphere where water is not substantially present. 10 −4 is used as a reference value, and (H + number of ions) / (total number of ions) increased from this can be used as hydrogen ions contained in the film.
　よって、ＴＯＦ試験例２及び３の（Ｈ＋イオンのカウント数）／（全イオンのカウント数）を比較すると、成膜時の水分圧が大きくなるに従って大きくなっていることが分かる。従って、ＴＯＦ試験例２および３のように、成膜時の水分圧をコントロールすることで、膜内に水分が取り込まれることによる水素量を変化をさせることができることが確認できた。なお、膜内に取り込まれた水素は、膜内の原子のダングリングボンド（未結合手）と水素終端されることで、膜の結晶化を阻害する効果を有すると推測される。 Therefore, comparing (H + ion count number) / (total ion count number) in TOF Test Examples 2 and 3, it can be seen that the water pressure during film formation increases as the water pressure increases. Therefore, as in TOF Test Examples 2 and 3, it was confirmed that by controlling the water pressure during film formation, the amount of hydrogen due to moisture being taken into the film can be changed. Note that hydrogen taken into the film is presumed to have an effect of inhibiting the crystallization of the film by being terminated with dangling bonds (unbonded hands) of atoms in the film.
Figure JPOXMLDOC01-appb-T000031
Figure JPOXMLDOC01-appb-T000031

Claims (29)

  1. 酸化インジウムと必要に応じて錫を含有すると共にＳｒ（ストロンチウム）、Ｌｉ（リチウム）、Ｌａ（ランタン）、Ｃａ（カルシウム）、Ｍｇ（マグネシウム）及びＹ（イットリウム）からなる群から選択される少なくとも一種である添加元素を含有する酸化物焼結体を具備するスパッタリングターゲットを用い、水の分圧が１．０×１０-4Ｐａ以上１．０×１０-1Ｐａ以下の条件下でアモルファス膜として成膜されたものであることを特徴とする透明導電膜。 At least one selected from the group consisting of indium oxide and tin as required and Sr (strontium), Li (lithium), La (lanthanum), Ca (calcium), Mg (magnesium), and Y (yttrium) As an amorphous film under a condition where the partial pressure of water is 1.0 × 10 −4 Pa or more and 1.0 × 10 −1 Pa or less using a sputtering target including an oxide sintered body containing the additive element A transparent conductive film characterized by being formed.
  2. 請求項１に記載の透明導電膜において、前記アモルファスな膜が水素を含有することを特徴とする透明導電膜。 2. The transparent conductive film according to claim 1, wherein the amorphous film contains hydrogen.
  3. 請求項１又は２に記載の透明導電膜において、アモルファス膜を成膜後、アニールすることにより結晶化されたものであることを特徴とする透明導電膜。 3. The transparent conductive film according to claim 1, wherein the transparent conductive film is crystallized by annealing after forming an amorphous film.
  4. 請求項１～３の何れか１項に記載の透明導電膜において、前記添加元素がストロンチウムであり、膜組成は、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するストロンチウムのモル比ｘで表される（－４．１×１０－２Ｌｎ（ｘ）－９．３×１０－２）の値未満の範囲にあることを特徴とする透明導電膜。 4. The transparent conductive film according to claim 1, wherein the additive element is strontium, and the film composition is such that the molar ratio y of tin to 1 mol of indium is strontium to 1 mol of indium. A transparent conductive film characterized by being in a range less than the value (−4.1 × 10 −2 Ln (x) −9.3 × 10 −2 ) represented by a molar ratio x.
  5. 請求項１～３の何れか１項に記載の透明導電膜において、前記添加元素がストロンチウムであり、膜組成は、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するストロンチウムのモル比ｘで表される（－４．１×１０－２Ｌｎ（ｘ）－９．３×１０－２）の値未満であり且つ（－１．６×１０－２Ｌｎ（ｘ）－３．７×１０－２）以上の範囲にあることを特徴とする透明導電膜。 4. The transparent conductive film according to claim 1, wherein the additive element is strontium, and the film composition is such that the molar ratio y of tin to 1 mol of indium is strontium to 1 mol of indium. Less than the value (−4.1 × 10 −2 Ln (x) −9.3 × 10 −2 ) represented by the molar ratio x and (−1.6 × 10 −2 Ln (x) −3) 7 × 10 −2 ) or more of the transparent conductive film.
  6. 請求項１～３の何れか１項に記載の透明導電膜において、前記添加元素がリチウムであり、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するリチウムのモル比ｘで表される（－１．６×１０－１Ｌｎ（ｘ）－５．９×１０－１）の値未満の範囲にあることを特徴とする透明導電膜。 The transparent conductive film according to any one of claims 1 to 3, wherein the additional element is lithium, and a molar ratio y of tin to 1 mol of indium is a molar ratio x of lithium to 1 mol of indium. A transparent conductive film characterized by being in a range less than a value represented by (−1.6 × 10 −1 Ln (x) −5.9 × 10 −1 ).
  7. 請求項１～３の何れか１項に記載の透明導電膜において、前記添加元素がリチウムであり、膜組成は、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するリチウムのモル比ｘで表される（－１．６×１０－１Ｌｎ（ｘ）－５．９×１０－１）の値未満であり且つ（－３．５×１０－２Ｌｎ（ｘ）－１．６×１０－１）以上の範囲にあることを特徴とする透明導電膜。 The transparent conductive film according to any one of claims 1 to 3, wherein the additive element is lithium, and the film composition is such that the molar ratio y of tin to 1 mol of indium is such that the molar ratio of lithium to 1 mol of indium is lithium. Less than the value (−1.6 × 10 −1 Ln (x) −5.9 × 10 −1 ) represented by the molar ratio x and (−3.5 × 10 −2 Ln (x) −1) A transparent conductive film characterized by being in the range of 6 × 10 −1 ) or more.
  8. 請求項１～３の何れか１項に記載の透明導電膜において、前記添加元素がランタンであり、膜組成は、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するランタンのモル比ｘで表される（－６．７×１０－２Ｌｎ（ｘ）－２．２×１０－１）の値未満の範囲にあることを特徴とする透明導電膜。 The transparent conductive film according to any one of claims 1 to 3, wherein the additive element is lanthanum, and the film composition is such that the molar ratio y of tin to 1 mol of indium is lanthanum to 1 mol of indium. A transparent conductive film characterized by being in a range less than a value represented by a molar ratio x (−6.7 × 10 −2 Ln (x) −2.2 × 10 −1 ).
  9. 請求項１～３の何れか１項に記載の透明導電膜において、前記添加元素がランタンであり、膜組成は、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するランタンのモル比ｘで表される（－６．７×１０－２Ｌｎ（ｘ）－２．２×１０－１）の値未満であり且つ（－２．９×１０－２Ｌｎ（ｘ）－１．３×１０－１）以上の範囲にあることを特徴とする透明導電膜。 The transparent conductive film according to any one of claims 1 to 3, wherein the additive element is lanthanum, and the film composition is such that the molar ratio y of tin to 1 mol of indium is lanthanum to 1 mol of indium. Less than the value of (−6.7 × 10 −2 Ln (x) −2.2 × 10 −1 ) and (−2.9 × 10 −2 Ln (x) −1) represented by the molar ratio x A transparent conductive film characterized by being in a range of 3 × 10 −1 ) or more.
  10. 請求項１～３の何れか１項に記載の透明導電膜において、前記添加元素がカルシウムであり、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するカルシウムのモル比ｘで表される（－４．１×１０－２Ｌｎ（ｘ）－９．３×１０－２）の値未満の範囲にあることを特徴とする透明導電膜。 The transparent conductive film according to any one of claims 1 to 3, wherein the additional element is calcium, and a molar ratio y of tin to 1 mol of indium is a molar ratio x of calcium to 1 mol of indium. A transparent conductive film characterized by being in a range less than a value represented by (−4.1 × 10 −2 Ln (x) −9.3 × 10 −2 ).
  11. 請求項１～３の何れか１項に記載の透明導電膜において、前記添加元素がカルシウムであり、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するカルシウムのモル比ｘで表される（－４．１×１０－２Ｌｎ（ｘ）－９．３×１０－２）の値未満であり且つ（－１．６×１０－２Ｌｎ（ｘ）－３．７×１０－２）以上の範囲にあることを特徴とする透明導電膜。 The transparent conductive film according to any one of claims 1 to 3, wherein the additional element is calcium, and a molar ratio y of tin to 1 mol of indium is a molar ratio x of calcium to 1 mol of indium. Less than the value of (−4.1 × 10 −2 Ln (x) −9.3 × 10 −2 ) and (−1.6 × 10 −2 Ln (x) −3.7 × 10) -2 ) A transparent conductive film characterized by being in the above range.
  12. 請求項１～３の何れか１項に記載の透明導電膜において、前記添加元素がマグネシウムであり、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するマグネシウムのモル比ｘで表される（－４．１×１０－２Ｌｎ（ｘ）－９．３×１０－２）の値未満の範囲にあることを特徴とする透明導電膜。 The transparent conductive film according to any one of claims 1 to 3, wherein the additional element is magnesium, and a molar ratio y of tin to 1 mol of indium is a molar ratio x of magnesium to 1 mol of indium. A transparent conductive film characterized by being in a range less than a value represented by (−4.1 × 10 −2 Ln (x) −9.3 × 10 −2 ).
  13. 請求項１～３の何れか１項に記載の透明導電膜において、前記添加元素がマグネシウムであり、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するマグネシウムのモル比ｘで表される（－４．１×１０－２Ｌｎ（ｘ）－９．３×１０－２）の値未満であり且つ（－１．６×１０－２Ｌｎ（ｘ）－３．７×１０－２）以上の範囲にあることを特徴とする透明導電膜。 The transparent conductive film according to any one of claims 1 to 3, wherein the additional element is magnesium, and a molar ratio y of tin to 1 mol of indium is a molar ratio x of magnesium to 1 mol of indium. Less than the value of (−4.1 × 10 −2 Ln (x) −9.3 × 10 −2 ) and (−1.6 × 10 −2 Ln (x) −3.7 × 10) -2 ) A transparent conductive film characterized by being in the above range.
  14. 請求項１～３の何れか１項に記載の透明導電膜において、前記添加元素がイットリウムであり、膜組成は、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するイットリウムのモル比ｘで表される（－２．５×１０－２Ｌｎ（ｘ）－５．８×１０－２）の値未満の範囲にあることを特徴とする透明導電膜。 The transparent conductive film according to any one of claims 1 to 3, wherein the additive element is yttrium, and the film composition is such that the molar ratio y of tin to 1 mol of indium is yttrium of 1 mol of indium. A transparent conductive film characterized by being in a range less than the value (−2.5 × 10 −2 Ln (x) −5.8 × 10 −2 ) represented by a molar ratio x.
  15. 請求項１～３の何れか１項に記載の透明導電膜において、前記添加元素がイットリウムであり、膜組成は、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するイットリウムのモル比ｘで表される（－２．５×１０－２Ｌｎ（ｘ）－５．８×１０－２）の値未満であり且つ（－２．２×１０－２Ｌｎ（ｘ）－１．５×１０－１）以上の範囲にあることを特徴とする透明導電膜。 The transparent conductive film according to any one of claims 1 to 3, wherein the additive element is yttrium, and the film composition is such that the molar ratio y of tin to 1 mol of indium is yttrium of 1 mol of indium. Less than the value (−2.5 × 10 −2 Ln (x) −5.8 × 10 −2 ) represented by the molar ratio x and (−2.2 × 10 −2 Ln (x) −1) A transparent conductive film characterized by being in the range of 5 × 10 −1 ) or more.
  16. 酸化インジウムと必要に応じて錫を含有すると共にＳｒ（ストロンチウム）、Ｌｉ（リチウム）、Ｌａ（ランタン）、Ｃａ（カルシウム）、Ｍｇ（マグネシウム）及びＹ（イットリウム）からなる群から選択される少なくとも一種である添加元素を含有する酸化物焼結体を具備するスパッタリングターゲットを用い、１００℃未満、水の分圧が１．０×１０-4Ｐａ以上１．０×１０-1Ｐａ以下の条件下で、アモルファス膜を成膜することを特徴とする透明導電膜の製造方法。 At least one selected from the group consisting of indium oxide and tin as required and Sr (strontium), Li (lithium), La (lanthanum), Ca (calcium), Mg (magnesium), and Y (yttrium) Using a sputtering target including an oxide sintered body containing an additive element of less than 100 ° C. and a water partial pressure of 1.0 × 10 −4 Pa or more and 1.0 × 10 −1 Pa or less. A method for producing a transparent conductive film, comprising forming an amorphous film.
  17. 請求項１６に記載の透明導電膜の製造方法において、アモルファス膜を成膜後、１００℃～３００℃でアニールすることにより結晶化して透明導電膜とすることを特徴とする透明導電膜の製造方法。 17. The method for producing a transparent conductive film according to claim 16, wherein after forming the amorphous film, the film is crystallized by annealing at 100 ° C. to 300 ° C. to form a transparent conductive film. .
  18. 請求項１６又は１７に記載の透明導電膜の製造方法において、前記添加元素がストロンチウムであり、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するストロンチウムのモル比ｘで表される（－４．１×１０－２Ｌｎ（ｘ）－９．３×１０－２）の値未満の範囲にある膜組成の膜を成膜することを特徴とする透明導電膜の製造方法。 18. The method for producing a transparent conductive film according to claim 16, wherein the additional element is strontium, and a molar ratio y of tin to 1 mol of indium is represented by a molar ratio x of strontium to 1 mol of indium. (-4.1 × 10 −2 Ln (x) −9.3 × 10 −2 )
  19. 請求項１６又は１７に記載の透明導電膜の製造方法において、前記添加元素がストロンチウムであり、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するストロンチウムのモル比ｘで表される（－４．１×１０－２Ｌｎ（ｘ）－９．３×１０－２）の値未満であり且つ（－１．６×１０－２Ｌｎ（ｘ）－３．７×１０－２）以上の範囲にある膜組成の膜を、水の分圧が１．０×１０-4Ｐａ以上１．０×１０-３Ｐａ以下の条件下で成膜することを特徴とする透明導電膜の製造方法。 18. The method for producing a transparent conductive film according to claim 16, wherein the additional element is strontium, and a molar ratio y of tin to 1 mol of indium is represented by a molar ratio x of strontium to 1 mol of indium. (−4.1 × 10 −2 Ln (x) −9.3 × 10 −2 ) and (−1.6 × 10 −2 Ln (x) −3.7 × 10 −2 ) ) A transparent conductive film characterized in that a film having a film composition in the above range is formed under conditions where the partial pressure of water is 1.0 × 10 −4 Pa or more and 1.0 × 10 −3 Pa or less. Manufacturing method.
  20. 請求項１６又は１７に記載の透明導電膜の製造方法において、前記添加元素がリチウムであり、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するリチウムのモル比ｘで表される（－１．６×１０－１Ｌｎ（ｘ）－５．９×１０－１）の値未満の範囲にある膜組成の膜を成膜することを特徴とする透明導電膜の製造方法。 The method for producing a transparent conductive film according to claim 16 or 17, wherein the additional element is lithium, and a molar ratio y of tin to 1 mol of indium is represented by a molar ratio x of lithium to 1 mol of indium. (-1.6 × 10 −1 Ln (x) −5.9 × 10 −1 )
  21. 請求項１６又は１７に記載の透明導電膜の製造方法において、前記添加元素がリチウムであり、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するリチウムのモル比ｘで表される（－１．６×１０－１Ｌｎ（ｘ）－５．９×１０－１）の値未満であり且つ（－３．５×１０－２Ｌｎ（ｘ）－１．６×１０－１）以上の範囲にある膜組成の膜を、水の分圧が１．０×１０-4Ｐａ以上１．０×１０-３Ｐａ以下の条件下で成膜することを特徴とする透明導電膜の製造方法。 The method for producing a transparent conductive film according to claim 16 or 17, wherein the additional element is lithium, and a molar ratio y of tin to 1 mol of indium is represented by a molar ratio x of lithium to 1 mol of indium. (−1.6 × 10 −1 Ln (x) −5.9 × 10 −1 ) and (−3.5 × 10 −2 Ln (x) −1.6 × 10 −1 ) ) A transparent conductive film characterized in that a film having a film composition in the above range is formed under conditions where the partial pressure of water is 1.0 × 10 −4 Pa or more and 1.0 × 10 −3 Pa or less. Manufacturing method.
  22. 請求項１６又は１７に記載の透明導電膜の製造方法において、前記添加元素がランタンであり、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するランタンのモル比ｘで表される（－６．７×１０－２Ｌｎ（ｘ）－２．２×１０－１）の値未満の範囲にある膜組成の膜を成膜することを特徴とする透明導電膜の製造方法。 18. The method for producing a transparent conductive film according to claim 16, wherein the additive element is lanthanum, and a molar ratio y of tin to 1 mol of indium is represented by a molar ratio x of lanthanum to 1 mol of indium. (−6.7 × 10 −2 Ln (x) −2.2 × 10 −1 ) A film having a film composition in a range less than the value of (−6.7 × 10 −2 Ln (x) −2.2 × 10 −1 ) is formed.
  23. 請求項１６又は１７に記載の透明導電膜の製造方法において、前記添加元素がランタンであり、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するランタンのモル比ｘで表される（－６．７×１０－２Ｌｎ（ｘ）－２．２×１０－１）の値未満であり且つ（－２．９×１０－２Ｌｎ（ｘ）－１．３×１０－１）以上の範囲にある膜組成の膜を、水の分圧が１．０×１０-4Ｐａ以上１．０×１０-３Ｐａ以下の条件下で成膜することを特徴とする透明導電膜の製造方法。 18. The method for producing a transparent conductive film according to claim 16, wherein the additive element is lanthanum, and a molar ratio y of tin to 1 mol of indium is represented by a molar ratio x of lanthanum to 1 mol of indium. (−6.7 × 10 −2 Ln (x) −2.2 × 10 −1 ) and (−2.9 × 10 −2 Ln (x) −1.3 × 10 −1 ) ) A transparent conductive film characterized in that a film having a film composition in the above range is formed under conditions where the partial pressure of water is 1.0 × 10 −4 Pa or more and 1.0 × 10 −3 Pa or less. Manufacturing method.
  24. 請求項１６又は１７に記載の透明導電膜の製造方法において、前記添加元素がカルシウムであり、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するカルシウムのモル比ｘで表される（－４．１×１０－２Ｌｎ（ｘ）－９．３×１０－２）の値未満の範囲にある膜組成の膜を成膜することを特徴とする透明導電膜の製造方法。 The method for producing a transparent conductive film according to claim 16 or 17, wherein the additional element is calcium, and a molar ratio y of tin to 1 mol of indium is expressed by a molar ratio x of calcium to 1 mol of indium. (-4.1 × 10 −2 Ln (x) −9.3 × 10 −2 )
  25. 請求項１６又は１７に記載の透明導電膜の製造方法において、前記添加元素がカルシウムであり、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するカルシウムのモル比ｘで表される（－４．１×１０－２Ｌｎ（ｘ）－９．３×１０－２）の値未満であり且つ（－１．６×１０－２Ｌｎ（ｘ）－３．７×１０－２）以上の範囲にある膜組成の膜を、水の分圧が１．０×１０-4Ｐａ以上１．０×１０-３Ｐａ以下の条件下で成膜することを特徴とする透明導電膜の製造方法。 The method for producing a transparent conductive film according to claim 16 or 17, wherein the additional element is calcium, and a molar ratio y of tin to 1 mol of indium is expressed by a molar ratio x of calcium to 1 mol of indium. (−4.1 × 10 −2 Ln (x) −9.3 × 10 −2 ) and (−1.6 × 10 −2 Ln (x) −3.7 × 10 −2 ) ) A transparent conductive film characterized in that a film having a film composition in the above range is formed under conditions where the partial pressure of water is 1.0 × 10 −4 Pa or more and 1.0 × 10 −3 Pa or less. Manufacturing method.
  26. 請求項１６又は１７に記載の透明導電膜の製造方法において、前記添加元素がマグネシウムであり、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するマグネシウムのモル比ｘで表される（－４．１×１０－２Ｌｎ（ｘ）－９．３×１０－２）の値未満の範囲にある膜組成の膜を成膜することを特徴とする透明導電膜の製造方法。 The method for producing a transparent conductive film according to claim 16 or 17, wherein the additive element is magnesium, and a molar ratio y of tin to 1 mol of indium is expressed by a molar ratio x of magnesium to 1 mol of indium. (-4.1 × 10 −2 Ln (x) −9.3 × 10 −2 )
  27. 請求項１６又は１７に記載の透明導電膜の製造方法において、前記添加元素がマグネシウムであり、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するマグネシウムのモル比ｘで表される（－４．１×１０－２Ｌｎ（ｘ）－９．３×１０－２）の値未満であり且つ（－１．６×１０－２Ｌｎ（ｘ）－３．７×１０－２）以上の範囲にある膜組成の膜を、水の分圧が１．０×１０-4Ｐａ以上１．０×１０-３Ｐａ以下の条件下で成膜することを特徴とする透明導電膜の製造方法。 The method for producing a transparent conductive film according to claim 16 or 17, wherein the additive element is magnesium, and a molar ratio y of tin to 1 mol of indium is expressed by a molar ratio x of magnesium to 1 mol of indium. (−4.1 × 10 −2 Ln (x) −9.3 × 10 −2 ) and (−1.6 × 10 −2 Ln (x) −3.7 × 10 −2 ) ) A transparent conductive film characterized in that a film having a film composition in the above range is formed under conditions where the partial pressure of water is 1.0 × 10 −4 Pa or more and 1.0 × 10 −3 Pa or less. Manufacturing method.
  28. 請求項１６又は１７に記載の透明導電膜の製造方法において、前記添加元素がイットリウムであり、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するイットリウムのモル比ｘで表される（－２．５×１０－２Ｌｎ（ｘ）－５．８×１０－２）の値未満の範囲にある膜組成の膜を成膜することを特徴とする透明導電膜の製造方法。 18. The method for producing a transparent conductive film according to claim 16, wherein the additional element is yttrium, and a molar ratio y of tin to 1 mol of indium is represented by a molar ratio x of yttrium to 1 mol of indium. (−2.5 × 10 −2 Ln (x) −5.8 × 10 −2 )
  29. 請求項１６又は１７に記載の透明導電膜の製造方法において、前記添加元素がイットリウムであり、インジウム１モルに対しての錫のモル比ｙが、インジウム１モルに対するイットリウムのモル比ｘで表される（－２．５×１０－２Ｌｎ（ｘ）－５．８×１０－２）の値未満であり且つ（－２．２×１０－２Ｌｎ（ｘ）－１．５×１０－１）以上の範囲にある膜組成の膜を、水の分圧が１．０×１０-4Ｐａ以上１．０×１０-３Ｐａ以下の条件下で成膜することを特徴とする透明導電膜の製造方法。 18. The method for producing a transparent conductive film according to claim 16, wherein the additional element is yttrium, and a molar ratio y of tin to 1 mol of indium is represented by a molar ratio x of yttrium to 1 mol of indium. (−2.5 × 10 −2 Ln (x) −5.8 × 10 −2 ) and (−2.2 × 10 −2 Ln (x) −1.5 × 10 −1 ) ) A transparent conductive film characterized in that a film having a film composition in the above range is formed under conditions where the partial pressure of water is 1.0 × 10 −4 Pa or more and 1.0 × 10 −3 Pa or less. Manufacturing method.
PCT/JP2010/056195 2009-04-08 2010-04-06 Indium oxide-based electrically conductive transparent film, and process for production thereof WO2010116981A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2009-094444 2009-04-08
JP2009094444 2009-04-08

Publications (1)

Publication Number Publication Date
WO2010116981A1 true WO2010116981A1 (en) 2010-10-14

Family

ID=42936264

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2010/056195 WO2010116981A1 (en) 2009-04-08 2010-04-06 Indium oxide-based electrically conductive transparent film, and process for production thereof

Country Status (1)

Country Link
WO (1) WO2010116981A1 (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06290641A (en) * 1993-03-30 1994-10-18 Asahi Glass Co Ltd Noncrystal transparent conductive membrane
JPH09161542A (en) * 1995-12-07 1997-06-20 Idemitsu Kosan Co Ltd Transparent conductive laminate and touch panel using the same
JP2003105532A (en) * 2001-06-26 2003-04-09 Mitsui Mining & Smelting Co Ltd Sputtering target for highly resistant transparent conductive film, and manufacturing method of highly resistant transparent conductive film
JP2004149883A (en) * 2002-10-31 2004-05-27 Mitsui Mining & Smelting Co Ltd Sputtering target for high resistance transparent conductive film, and manufacturing method of high resistance transparent conductive film
JP2007291521A (en) * 2006-03-31 2007-11-08 Mitsui Mining & Smelting Co Ltd Sputtering target and method for manufacturing oxide sintered body

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06290641A (en) * 1993-03-30 1994-10-18 Asahi Glass Co Ltd Noncrystal transparent conductive membrane
JPH09161542A (en) * 1995-12-07 1997-06-20 Idemitsu Kosan Co Ltd Transparent conductive laminate and touch panel using the same
JP2003105532A (en) * 2001-06-26 2003-04-09 Mitsui Mining & Smelting Co Ltd Sputtering target for highly resistant transparent conductive film, and manufacturing method of highly resistant transparent conductive film
JP2004149883A (en) * 2002-10-31 2004-05-27 Mitsui Mining & Smelting Co Ltd Sputtering target for high resistance transparent conductive film, and manufacturing method of high resistance transparent conductive film
JP2007291521A (en) * 2006-03-31 2007-11-08 Mitsui Mining & Smelting Co Ltd Sputtering target and method for manufacturing oxide sintered body

Similar Documents

Publication Publication Date Title
JPWO2009044891A1 (en) Indium oxide-based transparent conductive film and method for producing the same
US10000842B2 (en) Oxide sintered body, sputtering target, and oxide semiconductor thin film obtained using sputtering target
JP4043044B2 (en) Indium oxide-based transparent conductive film and method for producing the same
US20110011731A1 (en) Process for producing indium oxide-type transparent electroconductive film
TWI544097B (en) An oxide sintered body, a target for sputtering, and an oxide semiconductor thin film obtained by using the same
KR100945196B1 (en) Sputtering target and method for producing sintered oxide
JPWO2009044896A1 (en) Method for producing indium oxide-based transparent conductive film
WO2010116981A1 (en) Indium oxide-based electrically conductive transparent film, and process for production thereof
JPWO2009044898A1 (en) Indium oxide-based transparent conductive film and method for producing the same
CN103774098A (en) Thin film with stannous oxide texture and preparation method thereof
CN103103479B (en) Method for preparing p-type zinc oxide film through sulfur and nitrogen co-doping
JPWO2009044897A1 (en) Indium oxide-based transparent conductive film and method for producing the same
Im et al. Structural and electrical properties of Al and B co-doped Zno thin films
CN102586746A (en) Preparation method of delafossite type copper aluminum oxide infrared transparent conductive film
WO2013140838A1 (en) SINTERED In-Ga-Zn-O-BASED OXIDE COMPACT AND METHOD FOR PRODUCING SAME, SPUTTERING TARGET, AND OXIDE SEMICONDUCTOR FILM
JP2022007853A (en) Barium silicified laminated board
KR20110133814A (en) Transparent p type srcu2o2 semiconductor composition and a method for preparing the same

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10761680

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10761680

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP