TWI461365B - Indium oxide target - Google Patents

Description

Indium oxide target

The present invention relates to an indium oxide-based target from which an amorphous film can be easily produced, and the amorphous film can be easily patterned by weak acid etching, and is easier. The film which is crystallized and further crystallized can produce a transparent conductive film having low electrical resistance and high transmittance.

Since indium oxide-tin oxide (composite oxide of In ₂ O ₃ -SnO ₂ , hereinafter abbreviated as "ITO") has high visible light transmittance and high conductivity, it is widely used as a transparent conductive film as a liquid crystal display. A device or a heat-generating film for preventing condensation of glass, an infrared reflection film, or the like is only difficult to form an amorphous film.

On the other hand, an amorphous indium oxide-zinc oxide (IZO) transparent conductive film is known as an amorphous film, but this film is inferior to the ITO film in transparency and has a slight yellow color.

Then, the applicant of the present invention has previously proposed an amorphous transparent conductive film in which ruthenium is added to an ITO film and formed under a predetermined condition as a transparent conductive film (refer to Patent Document 1), and only high yttrium is added by adding yttrium. The problem of inclination.

[Patent Document 1] Japanese Laid-Open Patent Publication No. 2005-135649 (Application No.)

In view of such circumstances, an object of the present invention is to provide an indium oxide-based target from which an amorphous film can be easily produced, and the amorphous film can be easily patterned by weak acid etching, and can be easily crystallized. Further, the crystallized film can produce a transparent conductive film having low electrical resistance and high transmittance.

The inventors of the present invention have found that the indium oxide-based transparent conductive film to be added is an amorphous film having low resistance and excellent transparency, and can be easily patterned by weak acid etching, as a result of various studies. And the fact that it can be easily crystallized, and the application is made first (Japanese Patent No. 2007-095783).

However, it is known that the film can be added to the amorphous film, not only Ba, but also various similar elements, such as oxygen bond energy in the range of 100 to 350 kJ (kilojoules) / mol (mo The element in the range of the ear is an indium oxide-based target which can be formed into an amorphous film as an additive element, and finally completed the present invention.

The first aspect of the present invention is an indium oxide-based target comprising: an indium oxide and optionally tin, and an indium-containing molar containing an additive element having an oxygen bond energy in the range of 100 to 350 kJ/mol (however, An oxide sintered body of 0.0001 mol or more and 0.10 or less except Ba (钡), Mg (magnesium), and Y (钇).

In such a first state, by containing a predetermined additive element, an amorphous film can be formed.

The second state of the present invention is the indium oxide-based target according to the first aspect, wherein the additive element is selected from the group consisting of Sr (锶), Li (lithium), La (镧), and Ca (calcium). At least one of the indium oxide targets.

In such a second state, if at least one selected from the group consisting of Sr, Li, La, and Ca is contained, an amorphous film can be formed.

In the third aspect of the present invention, the indium oxide-based target described in the first or second state is an indium oxide-based target containing 0 to 0.3 mol of tin with respect to indium 1 molar.

In such a third state, a transparent conductive film containing tin oxide as a main component and tin may be optionally contained.

In the fourth embodiment of the present invention, in the indium oxide-based target according to the second or third aspect, the tin molar ratio y with respect to the indium 1 molar is: the molar of the aforementioned additive element with respect to the indium 1 molar. More than or equal to the value of (-9.3×10 ^-2 Ln(x)−2.1×10 ^-1 ) and (-2.5×10 ^-1 Ln(x)−5.7×10 ^-1 ) A range of indium oxide targets.

In the fourth state, the film can be formed into an amorphous film when the film is formed at a temperature of less than 100 ° C, and then crystallized when it is annealed at 100 ° C to 300 ° C.

In the fifth aspect of the present invention, in the indium oxide-based target according to the second or third aspect, the additive element is Sr, and the molar ratio y of the tin of the indium 1 molar is: relative to the indium 1 The molar ratio of the Sr of the ear is expressed by x (-4.1 × 10 ^-2 Ln (x) - 9.2 × 10 ^-2 ) and (-2.9 × 10 ^-1 Ln (x) - 6.7 × 10 ^- An indium oxide-based target having a value below ¹ ).

In the fifth state, the film can be formed into an amorphous film when the film is formed at a temperature of less than 100 ° C, and then crystallized when the film is annealed at 100 ° C to 300 ° C.

In the sixth aspect of the present invention, in the indium oxide-based target according to the second or third aspect, the additive element is Li, and the molar ratio y of the tin of the indium 1 molar is relative to the indium 1 The molar ratio of Li of Mo is above x (-1.6 × 10 ^-1 Ln(x) - 5.9 × 10 ^-1 ) and (-2.5 × 10 ^-1 Ln(x) - 5.7 × 10 An indium oxide target having a value below ^-1 ).

In such a sixth state, the film can be formed into an amorphous film when formed at a temperature of less than 100 ° C, and then crystallized when it is annealed at 100 ° C to 300 ° C.

In the seventh aspect of the present invention, in the indium oxide-based target according to the second or third aspect, the additive element is La, and the molar ratio y of the tin of the indium 1 molar is relative to the indium 1 The molar ratio of La of Mo is above x (-6.7 × 10 ^-2 Ln(x) - 2.2 × 10 ^-1 ) and (-3.3 × 10 ^-1 Ln(x) - 7.7 × 10 An indium oxide target having a value below ^-1 ).

In the seventh state, the film can be formed into an amorphous film when formed at a temperature of less than 100 ° C, and then crystallized when it is annealed at 100 ° C to 300 ° C.

In the eighth aspect of the present invention, in the indium oxide-based target according to the second or third aspect, the additive element is Ca, and the molar ratio y of the tin of the indium 1 molar is relative to the indium 1 The molar ratio of Ca of Mo is above x (-4.1 × 10 ^-2 Ln(x) - 9.3 × 10 ^-2 ) and (-2.5 × 10 ^-1 Ln(x) - 5.7 × 10 An indium oxide target having a value below ^-1 ).

In such an eighth state, the film can be formed into an amorphous film when it is formed at a temperature of less than 100 ° C, and then crystallized when it is annealed at 100 ° C to 300 ° C.

The ninth aspect of the present invention is an indium oxide-based target comprising an oxide calcined body containing indium oxide and tin and containing at least one additive element selected from the group consisting of Sr, Li, La, and Ca. The indium oxide-based target is characterized in that, when the additive element is Sr, the molar ratio y of the tin of indium 1 molar is expressed by x with respect to the molar ratio of Sr of indium 1 molar a value of (-4.1×10 ^-2 Ln(x)−9.2×10 ⁻² ) or more and a value of (−2.9×10 ⁻¹ Ln(x)−6.7×10 ⁻¹ ) or less; When the element is Li, the molar ratio y of the tin of the indium 1 molar is expressed by x with respect to the molar ratio of Li of the indium 1 molar (-1.6×10 ^-1 Ln(x) a value below -5.9 × 10 ^-1 ) and a value of (-2.5 × 10 ^-1 Ln (x) - 5.7 × 10 ^-1 ) or less; if the aforementioned additive element is La, it is relative to indium 1 mol The molar ratio y of tin is greater than or equal to the value of (-6.7 × 10 ^-2 Ln(x) - 2.2 × 10 ^-1 ) when the molar ratio of La with respect to indium 1 molar is represented by x ( a range of -3.3 × 10 ^-1 Ln(x) - 7.7 × 10 ^-1 ) or less; if the additive element is Ca as described above, the molar ratio y with respect to the tin of indium 1 Mo , below the value of (-4.1×10 ^-2 Ln(x)−9.3×10 ^-2 ) when the molar ratio of Ca with respect to indium 1 molar is represented by x and (-2.5×10 ^-1 Ln An indium oxide-based target having a range of (x) - 5.7 × 10 ^-1 ) or less.

In the ninth aspect, the film can be formed into an amorphous film which is formed when the film is formed at a temperature of less than 100 ° C, and then crystallized when it is annealed at 100 ° C to 300 ° C.

According to a tenth aspect of the present invention, in the indium oxide-based target according to the ninth aspect, the molar ratio y of the tin relative to the indium 1 molar is in the aforementioned additive element with respect to the indium 1 molar. The ear ratio is equal to or greater than the value of (-9.3×10 ^-2 Ln(x)−2.1×10 ^-1 ) and (-2.5×10 ^-1 Ln(x)-5.7×10 ^-1 ) The scope.

In the tenth state, the film can be formed into an amorphous film when formed at a temperature of less than 100 ° C, and then crystallized when it is annealed at 100 ° C to 300 ° C.

According to the present invention, an effect of providing an indium oxide-based target can be achieved, and an amorphous film can be easily produced by adding a film of an additive element having an oxygen bond in the range of 100 to 350 kJ/mol in indium oxide. The crystal film film can be easily patterned by weak acid etching, and can be easily crystallized. Further, the crystallized film is formed into a transparent conductive film having low electrical resistance and high transmittance.

The indium oxide-based target used for forming the indium oxide-based transparent conductive film of the present invention is an oxide containing an indium oxide as a main component and optionally containing tin, and containing an oxide element having an oxygen bond energy in the range of 100 to 350 kJ/mol. The sintered body is not particularly limited as long as it is present as an oxide itself, as a composite oxide, or as a solid solution.

Here, the indium oxide-based target means a target having an indium oxide-based sintered body, and includes a sputtering target used for forming a transparent conductive film by sputtering, and ion plating is also included. (ion plating) A target for ion plating (also referred to as a pellet) used for forming a transparent conductive film.

The addition of an element having an oxygen bond in the range of 100 to 350 kJ/mol is the same as that of the previously applied ruthenium, and has an effect of forming an indium oxide-based transparent conductive film as an amorphous film, and is exemplified by Ba (oxygen bond energy: 138 kJ). /mol), Sr (oxygen bond energy: 134 kJ/mol), Li (oxygen bond energy: 151 kJ/mol), La (oxygen bond energy: 242 kJ/mol), Ca (oxygen bond energy: 134 kJ/mol), Mg ( Oxygen bond energy: 155 kJ/mol), Y (oxygen bond energy: 209 kJ/mol), and the like.

Here, the element having a large oxygen bond energy is a single oxide which is easily vitrified (glass forming element), and when added to an indium oxide transparent conductive film, the bonding strength with oxygen is strong, even in the annealing treatment. After that, the optimum oxygen partial pressure is not changed, and the electrical and optical properties are hardly improved by the annealing treatment, and the oxygen bond energy is in the lower range of 100 to 350 kJ/mol. The element has a small binding force to oxygen, and it is presumed to function as an amorphous film. Here, although Na (oxygen bond energy: 84 kJ/mol) or K (oxygen bond energy: 54 kJ/mol) is low in oxygen bond energy, it is poor in electrical and optical properties when added to an indium oxide-based transparent conductive film. It is not appropriate to influence or damage the environmental resistance (refer to Japan, Nanwu, the temptation of glass - the scientific introduction of amorphous body - Industrial Book (stock), pages 34 to 36).

The content of the added element is preferably in the range of 0.0001 mol or more and 0.10 mol or less with respect to the indium 1 molar. When the amount is less than this, the effect of the addition is not remarkable, and if the amount is more than this, the electric resistance of the transparent conductive film formed tends to increase and the degree of yellowing tends to deteriorate. Here, the content of the additive element in the transparent conductive film formed of the above-described indium oxide-based target is the same as the content in the indium oxide-based target to be used.

Further, the content of tin is in the range of 0 to 0.3 mol with respect to indium 1 molar. The case of containing tin is preferably in the range of 0.001 to 0.3 mol with respect to indium 1 molar. Within this range, the density and mobility of the carrier electrons of the indium oxide-based sputtering target can be appropriately controlled, and the conductivity can be maintained in a favorable range. In addition, when the addition exceeds the above range, the mobility of the carrier electrons of the indium oxide-based sputtering target is lowered, and the conductivity tends to be deteriorated. Here, the tin content in the transparent conductive film formed by the above-described indium oxide sputtering target is the same as the content in the indium oxide sputtering target to be used.

Since such an indium oxide sputtering target has a resistance capable of performing DC magnetron sputtering, sputtering can be performed by inexpensive DC magnetron sputtering, and of course, it can also be used. Frequency magnetic control sputtering device.

By using such an indium oxide-based target, an indium oxide-based transparent conductive film having the same composition can be formed. The composition analysis of such an indium oxide-based transparent conductive film can also be carried out by ICP (inductively coupled plasma) after dissolving the entire film in a single amount. Further, when the film itself is formed into an element structure, a section of a corresponding portion is cut by a FIB (focusing ion beam) or the like as needed, and is attached to an SEM (scanning electron microscope) or a TEM (transmission electron microscope). An elemental analysis device (EDS (Energy Dispersion Spectrometer), WDS (Wavelength Dispersion Spectrometer), Auger electron spectroscopy, etc.) can also be specified.

The indium oxide-based transparent conductive film formed from the indium oxide-based target of the present invention contains a predetermined amount of a predetermined additive element, and may be different depending on the content thereof, but at a room temperature or higher, the crystallization temperature is The film formation is carried out under a low temperature condition, for example, a temperature condition lower than 200 ° C, preferably a condition lower than 150 ° C, more preferably lower than 100 ° C, that is, a film can be formed in an amorphous state. Further, such an amorphous film has an advantage that etching can be performed with a weakly acidic etchant. Here, in the present specification, the etching is included in the patterning step, and is used to produce a predetermined pattern.

Further, the specific resistance of the obtained transparent conductive film varies depending on the type and content of the elements to be added, but the specific resistance is usually 1.0 × 10 ^-4 to 1.0 × 10 ^-3 Ω ‧ cm.

In addition, the crystallization temperature of the film formed using the indium oxide-based target varies depending on the type and content of the additive element contained, and increases as the content increases, for example, at 100 ° C to 300 ° C. The temperature conditions are annealed to crystallize them. Since such a temperature region is used in a usual semiconductor manufacturing process, it can also be crystallized in such a process. Among these temperature ranges, it is preferably crystallized at 100 ° C to 300 ° C, more preferably crystallized at 150 ° C to 250 ° C, and most preferably crystallized at 200 ° C to 250 ° C. Chemical.

Here, the annealing treatment means that heating is performed for a certain period of time at a desired temperature in an atmospheric environment, in an ambient gas, or in a vacuum. A certain period of time generally means from a few minutes to a few hours, but industrially, if the effect is the same, it is preferably a shorter time.

In the transparent conductive film crystallized by the annealing treatment in this manner, the transmittance on the short-wavelength side is improved, and for example, the average transmittance at a wavelength of 400 to 500 nm is 85% or more. Further, there is no problem that the film which is a problem in IZO (indium zinc oxide) is yellowish. Here, in general, the higher the transmittance on the short-wavelength side, the better.

On the other hand, the etching resistance of the crystallized transparent conductive film is improved, so that the weakly acidic etchant capable of etching the amorphous film can no longer be etched. Therefore, the corrosion resistance in the subsequent process or the environmental resistance of the component itself can be improved.

In the present invention, since the content of the additive element in the indium oxide-based target is changed, the crystallization temperature of the film formed by the target film can be set to a desired temperature, so that it can be formed after film formation. In a manner of preventing heat treatment at a temperature higher than the crystallization temperature and maintaining the amorphous state, the film may be formed into a film and patterned, and then heat-treated at a temperature equal to or higher than the temperature at which the crystallization is performed to crystallization. The way to resist etching characteristics.

Here, when the additive element is Sr, an amorphous film is formed when the film is formed at a temperature of less than 100 ° C, and then, when the annealing treatment is performed at 100 ° C to 300 ° C, the composition range of the crystallized film can be formed. The molar ratio y (mole) with respect to the tin of the indium 1 molar is represented by X in the molar ratio of Sr with respect to the indium 1 molar (-4.1 × 10 ^-2 Ln (x) - 9.2 A value of ×10 ^-2 ) is equal to or greater than a value of (-2.9 × 10 ^-1 Ln (x) - 6.7 × 10 ^-1 ).

Further, in such a range, in particular, such as the molar ratio y (mole) with respect to the tin of the indium 1 molar, when the molar ratio of Sr with respect to the indium 1 molar is represented by x ( -8.2 × 10 ^-2 Ln (x) - 1.9 × 10 ^-1 ) In the above range, the annealing treatment temperature does not crystallize when it is less than 200 ° C, and crystallization can be formed by annealing at 200 ° C or higher. Since the range of the film is considered to be more suitable in consideration of a film forming process.

Further, in the above range, if the molar ratio y with respect to the tin of indium 1 mol is 0.15 mol or more and 0.28 mol or less, the film can be formed by annealing at 250 ° C. resistivity of film less than 10 ^-4 Ω‧cm 3.0 ×, whereas those more appropriate.

When the additive element is Li, an amorphous film is formed when the film is formed at 100 ° C or lower, and then, when the annealing treatment is performed at 100 ° C to 300 ° C, the film is formed into a composition range of the crystallized film, which is relative to indium 1 . The molar ratio y (mole) of the tin of the molar is expressed as x in the molar ratio of Li relative to the indium 1 molar (-1.6 × 10 ^-1 Ln (x) - 5.9 × 10 ^-1 The value of the value is equal to or greater than the range of (-2.5 × 10 ^-1 Ln (x) - 5.7 × 10 ^-1 ).

Further, in such a range, in particular, such as the molar ratio y (mole) with respect to the tin of the indium 1 molar, when the molar ratio of Li with respect to the indium 1 molar is represented by x ( -7.0 × 10 ^-2 Ln (x) - 1.6 × 10 ^-1 ) In the above range, the annealing treatment temperature does not crystallize when it is less than 200 ° C, and the film formation can be performed by annealing at 200 ° C or higher. Since the range of the crystallized film is considered, it is more suitable in consideration of the film forming procedure.

Further, in the above range, if the molar ratio y of the tin relative to the indium 1 molar is 0.28 mol or less and the molar ratio x of Li with respect to the indium 1 molar is 0.015 or less, become deg.] C by annealing treatment can 250 forming the resistivity 3.0 × 10 ^-4 Ω‧cm those in the film, while those more appropriate.

When the additive element is La, an amorphous film is formed when the film is formed at 100 ° C or lower, and then, when the annealing treatment is performed at 100 ° C to 300 ° C, the film can be formed into a composition range of the crystallized film, which is relative to indium 1 . The molar ratio y of the tin of the molar is above the value of (-6.7 × 10 ^-2 Ln (x) - 2.2 × 10 ^-1 ) when the molar ratio of La relative to the La of the indium 1 is represented by x Further, the value of (-3.3 × 10 ^-1 Ln (x) - 7.7 × 10 ^-1 ) is not more than the range.

Further, in such a range, in particular, such as the molar ratio y (mole) with respect to the tin of the indium 1 molar, when the molar ratio of La with respect to the indium 1 molar is represented by x ( -8.7 × 10 ^-2 Ln (x) - 2.0 × 10 ^-1 ) In the above range, the annealing treatment temperature does not crystallize when it is less than 200 ° C, and the film formation can be performed by annealing at 200 ° C or higher. Since the range of the crystallized film is considered, it is more suitable in consideration of the film forming process.

Further, in the above range, if the molar ratio y (mole) of tin with respect to indium 1 mol is 0.23 mol or less, the film resistivity after annealing at 250 ° C is obtained. A film of 3.0 × 10 ^-4 Ω ‧ cm or less is more suitable.

When the additive element is Ca, an amorphous film is formed when the film is formed at 100 ° C or lower, and then, when the annealing treatment is performed at 100 ° C to 300 ° C, the film can be formed into a crystallized film composition range, which is relative to indium. The molar ratio y of 1 mole of tin is a value of (-4.1 × 10 ^-2 Ln (x) - 9.3 × 10 ^-2 ) when the molar ratio of Ca with respect to indium 1 molar is represented by x. The range of the above (-2.5 × 10 ^-1 Ln (x) - 5.7 × 10 ^-1 ) is not more than the range.

Further, in such a range, in particular, such as the molar ratio y (mole) with respect to the tin of the indium 1 molar, when the molar ratio of Ca with respect to the indium 1 molar is represented by x ( -8.7 × 10 ^-2 Ln (x) - 2.0 × 10 ^-1 ) In the above range, the annealing treatment temperature does not crystallize when it is less than 200 ° C, and the film formation can be performed by annealing at 200 ° C or higher. Since the range of the crystallized film is considered, it is more suitable in consideration of the film forming process.

Further, in the above range, if the molar ratio y (mole) of tin relative to the indium 1 molar is 0.28 mol or less, the film can be formed into a resistivity after annealing at 250 ° C. It is more suitable for a film of 3.0 × 10 ^-4 Ω ‧ cm or less.

Thus, the predetermined effect can be obtained as a result of adding the added element, but if the added elements are not the same, the range in which the predetermined effect can be obtained is somewhat different, but the range common to the above-mentioned Sr, Li, La, and Ca elements is the same. In the case of film formation at less than 100 ° C, it becomes an amorphous film, and then, when it is annealed at 100 ° C to 300 ° C, it can form a film into a composition range of the crystallized film, which is relative to the tin of indium 1 Mohr ratio y is a value above (-9.3×10 ^-2 Ln(x)-2.1×10 ^-1 ) when the molar ratio of the additive element relative to indium 1 molar is expressed by x and (-2.5 A range of ×10 ^-1 Ln(x) - 5.7 × 10 ^-1 ) or less.

Next, the method for producing the indium oxide-based target of the present invention will be described, but the examples are merely illustrative and the production method is not limited by the examples.

First, as the starting material of the indium oxide-based target of the present invention, an oxide of a constituent element is generally used, but such a monomer, a compound, a composite oxide or the like may be used as a raw material. When a monomer or a compound is used, a procedure which can be made into an oxide is passed in advance.

The method of mixing and molding the raw material powders at a desired blending ratio is not particularly limited, and various wet methods or dry methods known in the art can be employed.

The dry method may, for example, be a cold press method or a hot press method. In the cold pressing method, the mixed powder is filled in a molding die to prepare a molded body and calcined. In the hot press method, the mixed powder is calcined and sintered in a molding die.

In the wet method, for example, a filter molding method is preferably used (refer to Japanese Laid-Open Patent Publication No. Hei 11-286002). Such a filtration molding method is a filtration molding die obtained by dewatering water from a ceramic raw material slurry to obtain a water-insoluble material for a molded body, the molded film having: one or more drainage holes The molding lower mold, the water-passing filter placed on the lower mold for molding, and the molding die frame which is sandwiched from the upper surface by sealing the sealing material for the filter, and The filter molding die having the molding lower mold, the molding die frame, the sealing material, and the filter, and removing the moisture in the slurry only from the filter surface side, can be separately assembled to prepare a slurry obtained by mixing powder, ion-exchanged water, and an organic additive, and injecting the slurry into a filter molding die, and removing the moisture in the slurry from the surface side of the filter to form a molded body The obtained ceramic molded body was dried and degreased, and then calcined.

The calcination temperature of the person formed by cold pressing or hot pressing is preferably 1300 to 1650 ° C, more preferably 1500 to 1650 ° C, and the environment is an atmospheric environment, an oxygen atmosphere, a non-oxidizing environment, or a vacuum environment. On the other hand, in the case of the hot press method, it is preferable to sinter it at around 1200 ° C, and the environment is a non-oxidizing environment or a vacuum environment. Further, after calcination in each method, mechanical processing for molding and processing up to a predetermined size is applied to form a target.

[Examples]

Hereinafter, the present invention will be described on the basis of an embodiment in which a sputtering target is taken as an example, but the present invention is not limited by the embodiment.

(Sputter target manufacturing example 1) (Sr-ITO) (Add Sr ITO, Sr=0.02-Sn=0.1)

In ₂ O ₃ powder, SnO ₂ powder having a purity of >99.99%, and SrCO ₃ powder having a purity of >99.9% were prepared. First, a total amount of 200 g was prepared in an amount of 65.3 wt% of In ₂ O ₃ powder and 34.7 wt% of SrCO ₃ powder, and ball milling was carried out in a dry state, and pre-calcined in the air at 1200 ° C for 3 hours to obtain Sr. In ₂ O ₄ powder.

Next, a total amount of about 1.0 kg (kg) was prepared in a ratio of 2.2% by weight of the above SrIn ₂ O ₄ powder, 86.6 % by weight of In ₂ O ₃ powder, and 11.2% by weight of SnO ₂ powder (the composition of each metal atom was In = 88.0 at. %, Sn = 10.0 at.%, Sr = 2.0 at.%), and this was mixed by ball milling. Then, a PVA (polyvinyl alcohol) aqueous solution was added as a binder, mixed, dried, and cold pressed to obtain a molded body. This molded body was degreased by heating at 600 ° C for 10 hours at 600 ° C in the air, and then calcined at 1550 ° C for 8 hours in an oxygen atmosphere to obtain a sintered body. The calcination conditions are specifically raised at a rate of 200 ° C / hour from room temperature to 800 ° C, and from 400 ° C to 1550 ° C at a rate of 400 ° C / hour, after 8 hours, from 1550 ° C The conditions of cooling to room temperature at a rate of 100 ° C / hour. Then, the sintered body was processed to obtain a target. The density at this time was 7.05 g/cm ³ .

In the same manner, a sputtering target of Sr = 0.00001, Sr = 0.01, and Sr = 0.05 was produced.

Also, in the same manner, a sputtering target having the composition shown in Table 1 was produced.

(Sputter target manufacturing example 2) (Li-ITO) (Adding ITO of Li, Li=0.02-Sn=0.1)

In ₂ O ₃ powder, SnO ₂ powder having a purity of >99.99%, and Li ₂ CO ₃ powder having a purity of >99.9% were prepared.

First, a total amount of 200 g of 72.0% by weight of In ₂ O ₃ powder and 21.0% by weight of Li ₂ CO ₃ powder was prepared, and the mixture was ball-milled in a dry state, and pre-calcined at 1000 ° C for 3 hours in the atmosphere to obtain LiInO ₂ powder. .

Next, a total amount of about 1.0 kg was prepared in a ratio of 2.2% by weight of the above LiInO ₂ powder, 86.8 % by weight of In ₂ O ₃ powder, and 11.0% by weight of SnO ₂ powder (the composition of each metal atom was In = 88.0 at. %, Sn = The target was produced in the same manner as Sr-ITO (Sr = 0.02) except for 10.0 at.% and Li = 2.0 at.%. However, the calcination temperature was 1,450 °C. The density at this time was 6.85 g/cm ³ .

In the same manner, a sputtering target having a composition as shown in Table 2 below was fabricated.

(Sputter target manufacturing example 3) (La-ITO) (Add La ITO, La=0.02-Sn=0.1)

In ₂ O ₃ powder, SnO ₂ powder having a purity of >99.99%, and La ₂ (CO ₃ ) ₃ ‧8H ₂ O powder having a purity of >99.99% were prepared.

First, a total amount of 200 g of 32.6 wt% of In ₂ O ₃ powder and 68.4 wt% of La ₂ (CO ₃ ) ₃ ‧8 H ₂ O powder was prepared, and ball-milling was carried out in a dry state, and pre-calcined at 1200 ° C in the atmosphere. In hours, LaInO ₃ powder was obtained.

Next, a total amount of about 1.0 kg was prepared in a ratio of 4.3% by weight of the above LaInO ₃ powder, 85.0% by weight of In ₂ O ₃ powder, and 10.7% by weight of SnO ₂ powder (the composition of each metal atom was In=88.0 at.%, Sn= The target was produced in the same manner as in the case of Sr-ITO (Sr = 0.02) except for 10.0 at.% and La = 2.0 at.%. The density at this time was 7.04 g/cm ³ .

In the same manner, a sputtering target having a composition as shown in Table 3 below was fabricated.

(Sputter target manufacturing example 4) (Ca-ITO) (Adding ITO of Ca, Ca=0.02-Sn=0.1)

In ₂ O ₃ powder, SnO ₂ powder having a purity of >99.99%, and CaCO ₃ powder having a purity of >99.5% were prepared.

First, 200 g of the total amount of In ₂ O ₃ powder and 26.5% by weight of CaCO ₃ powder were prepared, and the mixture was ball-milled in a dry state, and pre-calcined in the air at 1200 ° C for 3 hours to obtain CaIn ₂ O ₄ powder. .

Next, a total amount of about 1.0 kg was prepared in an amount of 4.8% by weight of the above CaIn ₂ O ₄ powder, 84.3% by weight of In ₂ O ₃ powder, and 10.9% by weight of SnO ₂ powder (the composition of each metal atom was In=88.0 at.%, The target was produced in the same manner as in the case of Sr-ITO (Sr = 0.02) except for Sn = 10.0 at.% and Ca = 2.0 at.%. The density at this time was 6.73 g/cm ³ .

In the same manner, a sputtering target having the composition shown in Table 4 below was fabricated.

(Sputter target reference manufacturing example 1) (Mg-ITO) (Adding ITO of Mg, Mg=0.02-Sn=0.1)

In ₂ O ₃ powder, SnO ₂ powder, and magnesium carbonate powder (MgO content 41.5 wt%) having a purity of >99.99% were prepared.

First, a total amount of 200 g was prepared in an amount of 87.3 wt% of In ₂ O ₃ powder and 12.7% by weight of magnesium hydroxide powder, and the mixture was ball-milled in a dry state, and pre-calcined at 1400 ° C for 3 hours in the atmosphere to obtain MgIn _{2 .} O ₄ powder.

Next, a total amount of about 1.0 kg was prepared in a ratio of 4.6% by weight of the MgIn ₂ O ₄ powder, 84.5 % by weight of the In ₂ O ₃ powder, and 10.9 % by weight of the SnO ₂ powder (the composition of each metal atom was In=88.0 at.%, The target was produced in the same manner as in the case of Sr-ITO (Sr = 0.02) except for Sn = 10.0 at.% and Mg = 2.0 at.%. The density at this time was 7.02 g/cm ³ .

In the same manner, a sputtering target of Mg = 0.05 and Mg = 0.12 was produced.

(Sputter target reference manufacturing example 2) (Y-ITO) (Add ITO of Y, Y=0.02=Sn=0.1)

In ₂ O ₃ powder, SnO ₂ powder having a purity of >99.99%, and Y ₂ (CO ₃ ) ₃ ‧3H ₂ O powder having a purity of >99.99% were prepared.

First, a total amount of 200 g was prepared in an amount of 40.2% by weight of In ₂ O ₃ powder and 59.8 % by weight of Y ₂ (CO ₃ ) ₃ ‧3H ₂ O powder, and ball-milling was carried out in a dry state, and pre-calcined at 1200 ° C in the atmosphere. In an hour, YInO ₃ powder was obtained.

Next, a total amount of about 1.0 kg was prepared in a ratio of 3.6% by weight of the above YInO ₃ powder, 85.6 % by weight of In ₂ O ₃ powder, and 10.8% by weight of SnO ₂ powder (the composition of each metal atom was In = 88.0 at.%, Sn = The target was produced in the same manner as in the case of Sr-ITO (Sr = 0.02) except for 10.0 at.% and Y = 2.0 at.%. The density at this time was 7.02 g/cm ³ .

In the same manner, a sputtering target of Y = 0.05 was fabricated.

(Sputter target reference manufacturing example 3) (B-ITO) (Adding ITO of B, B=0.05, Sn=0.1)

In ₂ O ₃ powder, SnO ₂ powder having a purity of >99.99%, and B ₂ O ₃ powder having a purity of >99.99% were prepared.

In addition to this powder such as In ₂ O ₃ powder by 87.5 wt% ₂ 11.2 wt.% Powder and SnO, B ₂ O ₃ powder, 1.3% by weight of the total amount to prepare 1.0kg ratio (the composition of each metal atom is In = 85.0at.%, The target was produced in the same manner as in the case of Sr-ITO (Sr = 0.02) except for Sn = 10.0 at.% and B = 5.0 at.%. However, the calcination temperature was 1400 °C. The density at this time was 5.01 g/cm ³ .

(Film Forming Examples 1 to 13, Reference Examples 1 to 5, and Comparative Example 1)

The film formation examples 1 to 13, the reference examples 1 to 5, and the comparative examples in which the sputtering target film formed by the above-described method was used were carried out as follows.

In the target produced as described above, the targets having the compositions of the following Table 5 were used as the targets of the film formation examples 1 to 13, the reference examples 1 to 5, and the comparative example 1, as described below. DC magnetron sputtering device, the substrate temperature is set to room temperature (about 20 ° C), and the oxygen partial pressure is changed between 0 and 3.0 sccm (standard cubic centimeters per minute) (equivalent to 0 to 1.1 × 10 ^{- 2} Pa (Pascal)), the transparent conductive films of Film Forming Examples 1 to 13, Reference Examples 1 to 5, and Comparative Example 1 were obtained.

The conditions of the sputtering were as follows, and the thickness was 1200. Membrane.

Target size: Φ=4in. t=6mm

Sputtering method: DC magnetron sputtering

Exhaust device: rotary pump + cryopump

Ultimate vacuum: 5.3 × 10 ^-6 [Pa]

Ar (argon) pressure: 4.0 × 10 ^-1 [Pa]

Oxygen pressure: 0 to 1.1 × 10 ^-2 [Pa]

Water pressure: 5.0×10 ^-6 [Pa]

Substrate temperature: room temperature

Sputtering power: 130W (watt) (power density 1.6W/cm ² )

Use substrate: Corning #1737 (glass for liquid crystal display) t (thickness) = 0.8mm

The electrical resistivity of the film forming the film under each partial pressure of oxygen and the electrical resistivity after annealing of each film at 250 ° C were measured. The results are shown in Figures 1 to 12.

From the results, it is known that in any case, there is an optimum oxygen partial pressure.

Further, in the film formation examples 1 to 9 and the reference examples 1 to 5, the optimum oxygen partial pressure at room temperature film formation was different from the oxygen partial pressure at the time of film formation at the lowest resistivity after annealing at 250 °C. Table 2 shows the optimum partial pressure of oxygen at room temperature and the partial pressure of oxygen at the time of film formation with the lowest resistivity after annealing at 250 °C. From this, it was found that in Film Forming Examples 1 to 9 and Reference Examples 1 to 5, film formation was performed at a partial pressure of oxygen at the time of film formation having the lowest resistivity after annealing at 250 ° C, and then annealing was performed at 250 ° C. The processor can produce the film with the lowest resistance.

On the other hand, in Comparative Example 1 in which the oxygen bond energy was large, an amorphous film was obtained at the time of film formation, but the optimum oxygen partial pressure was not changed by the annealing treatment at 250 ° C, and crystallization was not caused. With respect to the film forming examples 10 to 12 in which the amount of addition was too small, it was found that an amorphous film could not be obtained without changing the optimum oxygen partial pressure. Further, in the film formation example 13 in which the amount of addition was too large, it was found that an amorphous film could be obtained at the time of film formation, and the optimum oxygen partial pressure was changed by annealing at 250 ° C, but it was not crystallized.

In the following Table 6, the optimum oxygen partial pressure change is indicated by ○, and the optimum oxygen partial pressure change is indicated by ×.

(Test Example 1)

In the film formation examples 1 to 13, the reference examples 1 to 5, and the comparative example 1, the transparent conductive film produced by the optimum oxygen partial pressure at the time of film formation at room temperature was cut into a size of 13 mm square, and this was The sample was annealed at 250 ° C for 1 hour in the atmosphere. The film XRD pattern before and after the annealing treatment is shown in Figs. 13 to 19. Further, in Film Forming Examples 1 to 4, Reference Examples 1 to 4, and Comparative Example 1, the crystal state after the film formation at room temperature and the annealing treatment at 250 ° C was performed in the form of amorphous a and crystal by c. And etc. are shown in Table 2.

From the results, it was confirmed that in the case of the film formation examples 1 to 9 and the reference examples 1 to 4 which were formed at room temperature, although the film was formed as an amorphous film, it was crystallized by annealing at 250 ° C for 1 hour. On the other hand, in Comparative Example 1 in which B having a large oxygen-energy bond energy or Film-forming Example 13 and Reference Example 5 having a large amount of addition were added, although the film formation was amorphous, the film was still annealed at 250 ° C. Chemical. Further, in this regard, it was confirmed that the annealing treatment at 300 ° C did not crystallize. Further, in the film formation examples 10 to 12 in which the amount of addition was small, it was confirmed that the film formation was also performed at the time of film formation, and the film was not formed into an amorphous film.

(Test Example 2)

The specific resistance of each of the transparent conductive films formed in the film formation example at the time of film formation at room temperature was ρ (Ω ‧ cm) at the time of film formation by the optimum oxygen partial pressure. Further, the resistivity of the sample after the annealing treatment of Test 1 was also measured. These results are shown in Table 6.

As a result, it was found that in the case of Film Formation Examples 1 to 12, Reference Examples 1 to 4, and Comparative Example 1, the specific resistance was about 10 ^-4 Ω‧cm.

However, it is known that in the film formation examples 13 to 14, the specific resistance is a high resistance of about 10 ^-3 Ω‧cm.

(Test Example 3)

In the film formation examples 1 to 13, the reference examples 1 to 5, and the comparative example 1, the transparent conductive film produced by the optimum oxygen partial pressure at the time of film formation at room temperature was cut into a size of 13 mm square to measure the transmission. spectrum. Further, the transmission spectrum of the film after the annealing treatment of Test Example 1 was also measured in the same manner. These results are shown in Figures 20 to 26. Further, the average transmittances of each of Film Forming Examples 1 to 13, Reference Examples 1 to 5, and Comparative 1 after annealing treatment are shown in Table 6.

From the results, it was found that the transmission spectrum before the film formation annealing treatment was due to the annealing treatment at 250 ° C for 1 hour, and the absorption end migrated to the low wavelength side to improve the tint.

(Test Example 4)

In the film formation examples 1 to 13, the reference examples 1 to 5, and the comparative example 1, the transparent conductive film produced by the optimum oxygen partial pressure at the time of film formation at room temperature was cut into a size of 10 × 50 mm, and ITO was used. -05N (oxalic acid system, manufactured by Kanto Chemical Co., Ltd.) (oxalic acid concentration: 50 g/L) was used as an etching solution, and it was confirmed whether etching was possible at a temperature of 30 °C. Moreover, the sample after the annealing treatment of Test Example 1 was also confirmed in the same manner. These results are shown in Table 6 as etchable as "○" and non-etchable as "X".

As a result, it was found that the amorphous film system can be etched with a weakly acidic etchant, but the film which is crystallized cannot be etched.

(transparent conductive film containing Sr)

Using the target of the composition shown in Table 1 manufactured in the above manner, this was separately mounted on a 4 DC DC magnetron sputtering apparatus, and the substrate temperature was set to room temperature (about 20 ° C) to make the oxygen partial pressure at 0 to Under a change of 3.0 sccm (corresponding to 0 to 1.1 × 10 ^-2 Pa), a transparent conductive film of each composition was obtained.

The conditions of the sputtering were as follows, and the thickness was 1200. Membrane.

Target size: Φ=4in. t=6mm

Sputtering method: DC magnetron sputtering

Exhaust device: rotary pump + cryopump

Reaching vacuum: 5.3×10 ^-5 [Pa]

Ar pressure: 4.0 × 10 ^-1 [Pa]

Oxygen pressure: 0 to 1.1 × 10 ^-2 [Pa]

Water pressure: 5.0×10 ^-5 [Pa]

Substrate temperature: room temperature

Sputtering power: 130W (power density 1.6W/cm ² )

Use substrate: Corning #1737 (glass for liquid crystal display) t=0.8mm

Here, the optimum oxygen partial pressure at room temperature film formation is different from the oxygen partial pressure at the time of film formation after annealing at 250 ° C, but the composition is optimal, and the optimum oxygen partial pressure is No change.

In Table 7 below, the optimum oxygen partial pressure change is indicated by ○, and the optimum oxygen partial pressure change is indicated by ×.

Further, the transparent conductive film produced under the optimum oxygen partial pressure at the time of film formation at each room temperature was cut into a size of 13 mm square, and the samples were annealed at 250 ° C in the atmosphere. In the case of the film formation at room temperature and after annealing at 250 ° C, amorphous form was used as a, and crystal was used as c, and these are shown in Table 7.

Further, the crystallization temperatures of the respective compositions were measured and shown in Table 7. The crystallization temperature is a temperature at which crystallization is performed after film formation at 100 ° C, and if it is not amorphous at the time of film formation at 100 ° C, it is considered to be less than 100 ° C.

Further, the resistivity ρ (Ω‧ cm) of the sample which was annealed and crystallized after the film formation at room temperature was measured at the optimum oxygen partial pressure of each of the formed transparent conductive films. These results are shown in Table 7.

Further, the transparent conductive film produced by the optimum oxygen partial pressure at the time of film formation at room temperature was cut into a size of 13 mm square, and the transmission spectrum was measured on the annealed film. The average transmittance after the annealing treatment is shown in Table 7.

Further, the transparent conductive film which was produced by the optimum partial pressure of oxygen at the time of film formation at room temperature and subjected to annealing treatment to be crystallized was cut into a size of 10 × 50 mm, and ITO-05N (oxalic acid system, Guan Guo) was used. Chemical (stock) (oxalic acid concentration: 50 g/L) was used as an etching solution, and it was confirmed whether etching was performed at a temperature of 30 °C. It is shown in Table 7 by etchable as "○" and non-etchable as "X".

These results are shown in Fig. 28. In the figure, a sample which can be formed into an amorphous film at a film forming temperature of less than 100 ° C and which can be crystallized at 100 ° C to 300 ° C is indicated by ●, and the others are indicated by ▲.

From this result, it is known that if the additive element is Sr, it will become an amorphous film when it is formed at a temperature of less than 100 ° C, and then, when it is annealed at 100 ° C to 300 ° C, the composition range of crystallization will be Mohr ratio y (mole) with respect to indium 1 molar tin, when the molar ratio of Sr with respect to indium 1 molar is represented by x (-4.1 × 10 ^-2 ln(x) - 9.2 The value of ×10 ^-2 ) is not less than the value of (-2.9 × 10 ^-1 ln(x) - 6.7 × 10 ^-1 ).

It is also known that, in this range, in particular, such as the molar ratio y (mole) relative to the tin of indium 1 mole, when the molar ratio of Sr relative to the indium 1 molar is represented by x (-8.2×10 ^-2 ln(x)−1.9×10 ^-1 ) or more, when the annealing treatment temperature is less than 200 ° C, it will not crystallize, and when it is annealed at 200 ° C or higher, it will crystallize. The range is considered to be more suitable when considering the film forming procedure.

Further, it is known that, in the above range, if the molar ratio y with respect to the tin of indium 1 mol is 0.15 mol or more and 0.28 mol or less, the resistivity after annealing at 250 ° C is obtained. It becomes 3.0 × 10 ^-4 Ω ‧ cm or less, and is more suitable.

(transparent conductive film containing Li composition)

Using the target of the composition shown in Table 2 manufactured in the above manner, this was separately mounted on a 4 CD CD magnetron sputtering apparatus, and the substrate temperature was set to room temperature (about 20 ° C) to make the oxygen partial pressure at 0 to Under a change of 3.0 sccm (corresponding to 0 to 1.1 × 10 ^-2 Pa), a transparent conductive film of each composition was obtained.

The conditions of the sputtering were as follows, and the thickness was 1200. Membrane.

Target size: Φ=4in. t=6mm

Sputtering method: DC magnetron sputtering

Exhaust device: rotary pump + cryopump

Reaching vacuum: 5.3×10 ^-5 [Pa]

Ar pressure: 4.0 × 10 ^-1 [Pa]

Oxygen pressure: 0 to 1.1 × 10 ^-2 [Pa]

Water pressure: 5.0×10 ^-5 [Pa]

Substrate temperature: room temperature

Sputtering power: 130W (power density 1.6W/cm ² )

Use substrate: Corning #1737 (glass for liquid crystal display) t=0.8mm

Here, the optimum oxygen partial pressure at room temperature film formation is different from the oxygen partial pressure at the time of film formation at the lowest resistivity after annealing at 250 ° C, but the composition is optimal, and the optimum oxygen partial pressure is No change.

In Table 8 below, the optimum oxygen partial pressure change is indicated by ○, and the optimum oxygen partial pressure change is indicated by ×.

Further, the transparent conductive film produced under the optimum oxygen partial pressure at the time of film formation at each room temperature was cut into a size of 13 mm square, and the samples were annealed at 250 ° C in the atmosphere. In the case of the film formation at room temperature and after annealing at 250 ° C, amorphous form was used as a, and crystal was used as c, and these are shown in Table 8.

Further, the crystallization temperatures of the respective compositions were measured and shown in Table 8. The crystallization temperature is a temperature at which crystallization is performed after film formation at 100 ° C, and if it is not amorphous at the time of film formation at 100 ° C, it is considered to be less than 100 ° C.

Further, the resistivity ρ (Ω‧ cm) of the sample which was annealed and crystallized by the optimum oxygen partial pressure film formation at the time of film formation of each of the transparent conductive films formed at room temperature was measured. These results are shown in Table 8.

Further, the transparent conductive film produced by the optimum oxygen partial pressure at the time of film formation at room temperature was cut into a size of 13 mm square, and the transmission spectrum was measured on the annealed film. The average transmittance after the annealing treatment is shown in Table 8.

Further, the transparent conductive film which was produced by the optimum partial pressure of oxygen at the time of film formation at room temperature and which was crystallized by annealing was cut into a size of 10 × 50 mm, and ITO-0.5N (oxalic acid system, Kanto) was used. Chemical (stock) system (oxalic acid concentration 50 g / L) as an etching solution, the etching rate was measured at a temperature of 30 ° C ( /sec). The results are shown in Table 8.

These results are shown in Fig. 28. In the figure, a sample which can be formed into an amorphous film at a film forming temperature of less than 100 ° C and which can be crystallized at 100 ° C to 300 ° C is indicated by ●, and the others are indicated by ▲.

From this result, it is known that when the additive element is Li, an amorphous film is formed when the film is formed at a temperature of less than 100 ° C, and then, when an annealing treatment is performed at 100 ° C to 300 ° C, a film which is a crystallized film can be formed. The composition range is relative to the molar ratio y (mole) of indium 1 molar tin, which is expressed by x when the molar ratio of Li relative to indium 1 molar is (-1.6 × 10 ^-1 ln ( The value of x) - 5.9 × 10 ^-1 ) is not less than the value of (-2.5 × 10 ^-1 ln(x) - 5.7 × 10 ^-1 ).

It is also known that, in this range, in particular, the molar ratio y (mole) relative to the tin of indium 1 molar is expressed as x in terms of the molar ratio of Li relative to the indium 1 molar. In the range of (-7.0 × 10 ^-2 ln(x) - 1.6 × 10 ^-6 ) or more, the film can be formed so that the annealing temperature does not crystallize when it is less than 200 ° C, and the annealing treatment is performed at 200 ° C or higher. Since the range of the film which will be crystallized is considered to be more suitable in consideration of the film forming process.

Further, it is known that, in the above range, as in the molar ratio y with respect to the indium 1 molar tin, it is 0.28 mol or more, and the molar ratio x of Li with respect to the indium 1 molar is 0.015 or less. The film can be formed into a film having a resistivity of 3.0×10 ^-4 Ω·cm or less after annealing at 250 ° C, and is more suitable.

(transparent conductive film containing La)

The target of the composition shown in Table 3 manufactured in the above manner was used, and each was mounted on a 4 DC DC magnetron sputtering apparatus, and the substrate temperature was set to room temperature (about 20 ° C) to make the oxygen partial pressure at 0 to Under a change of 3.0 sccm (corresponding to 0 to 1.1 × 10 ^-2 Pa), a transparent conductive film of each composition was obtained.

The conditions of the sputtering were as follows, and the thickness was 1200. Membrane.

Target size: Φ=4in. t=6mm

Sputtering method: DC magnetron sputtering

Exhaust device: rotary pump + cryopump

Reaching vacuum: 5.3×10 ^-5 [Pa]

Ar pressure: 4.0 × 10 ^-1 [Pa]

Oxygen pressure: 0 to 1.1 × 10 ^-2 [Pa]

Water pressure: 5.0×10 ^-5 [Pa]

Substrate temperature: room temperature

Sputtering power: 130W (power density 1.6W/cm ² )

Use substrate: Corning #1737 (glass for liquid crystal display) t=0.8mm

Here, the optimum oxygen partial pressure at room temperature film formation is different from the oxygen partial pressure at the time of film formation after annealing at 250 ° C, but the composition is optimal, and the optimum oxygen partial pressure is No change.

In Table 9 below, the optimum oxygen partial pressure change is indicated by ○, and the change of the optimum oxygen partial pressure is indicated by ×.

Further, the transparent conductive film produced under the optimum oxygen partial pressure at the time of film formation at each room temperature was cut into a size of 13 mm square, and the samples were annealed at 250 ° C in the atmosphere. In the case of the film formation at room temperature and after annealing at 250 ° C, the amorphous form was taken as a, and the crystal was used as c, and these are shown in Table 9.

Further, the crystallization temperatures of the respective compositions were measured and shown in Table 9. The crystallization temperature is a temperature at which crystallization is performed after film formation at 100 ° C, and if it is not amorphous at the time of film formation at 100 ° C, it is considered to be less than 100 ° C.

Further, the resistivity ρ (Ω‧ cm) of the sample which was annealed and crystallized by the optimum oxygen partial pressure film formation at the time of film formation of each of the transparent conductive films formed at room temperature was measured. These results are shown in Table 9.

Further, the transparent conductive film produced by the optimum oxygen partial pressure at the time of film formation at room temperature was cut into a size of 13 mm square, and the transmission spectrum was measured on the annealed film. The average transmittance after the annealing treatment is shown in Table 9.

Further, the transparent conductive film which was produced by the optimum partial pressure of oxygen at the time of film formation at room temperature and which was crystallized by annealing was cut into a size of 10 × 50 mm, and ITO-0.5N (oxalic acid system, Kanto) was used. Chemical (stock) system (oxalic acid concentration 50 g / L) as an etching solution, the etching rate was measured at a temperature of 30 ° C ( /sec). The results are shown in Table 9.

These results are shown in Fig. 29. In the figure, a sample which can be formed into an amorphous film at a film forming temperature of less than 100 ° C and which can be crystallized at 100 ° C to 300 ° C is indicated by ●, and the others are indicated by ▲.

From this result, it is known that, in the case where the additive element is La, an amorphous film is formed when the film is formed at a temperature of less than 100 ° C, and then, when an annealing treatment is performed at 100 ° C to 300 ° C, a film which is crystallized can be formed. The composition range is the molar ratio y with respect to the tin of the indium 1 mole, which is represented by x when the molar ratio of La with respect to the indium 1 molar is (-6.7×10 ^-2 ln(x)- A value of 2.2 × 10 ^-1 ) or more and a value of (-3.3 × 10 ^-1 ln(x) - 7.7 × 10 ^-1 ) or less.

It is also known that, in this range, in particular, such as the molar ratio y (mole) with respect to the tin of indium 1 molar, when the molar ratio of La with respect to the indium 1 molar is represented by x In the range of (-8.7 × 10 ^-2 ln(x) - 2.0 × 10 ^-1 ) or more, the film can be formed so that the annealing temperature does not crystallize when it is less than 200 ° C, and the annealing treatment is performed at 200 ° C or higher. Since the range of the film which will be crystallized is considered to be more suitable in consideration of the film forming process.

Further, it is known that, in the above range, if the molar ratio y (mole) relative to the tin of the indium 1 molar is 0.23 mol or less, the film can be formed into an electric resistance after annealing at 250 ° C. The film rate is 3.0 × 10 ^-4 Ω ‧ cm or less, and is more suitable.

(Transparent conductive film containing Ca)

Using the target of the composition shown in Table 4 manufactured in the above manner, this was separately mounted on a 4 DC DC magnetron sputtering apparatus, and the substrate temperature was set to room temperature (about 20 ° C) to make the oxygen partial pressure at 0 to Under the change of 3.0 sccm (corresponding to 0 to 1.1 × 10 ^-2 Pa), a transparent conductive film of each composition was obtained.

The conditions of the sputtering were as follows, and the thickness was 1200. Membrane.

Target size: ψ=4in. t=6mm

Sputtering method: DC magnetron sputtering

Exhaust device: rotary pump + cryopump

Reaching vacuum: 5.3×10 ^-5 [Pa]

Ar pressure: 4.0 × 10 ^-1 [Pa]

Oxygen pressure: 0 to 1.1 × 10 ^-2 [Pa]

Water pressure: 5.0×10 ^-5 [Pa]

Substrate temperature: room temperature

Sputtering power: 130W (power density 1.6W/cm ² )

Use substrate: Corning #1737 (glass for liquid crystal display) t=0.8mm

Here, the optimum oxygen partial pressure at room temperature film formation is different from the oxygen partial pressure at the time of film formation after annealing at 250 ° C, but the composition is optimal, and the optimum oxygen partial pressure is No change.

In Table 10 below, the optimum oxygen partial pressure change is indicated by ○, and the optimum oxygen partial pressure change is indicated by ×.

Further, the transparent conductive film produced under the optimum oxygen partial pressure at the time of film formation at each room temperature was cut into a size of 13 mm square, and the samples were annealed at 250 ° C in the atmosphere. In the case of the film formation at room temperature and after annealing at 250 ° C, the amorphous form was taken as a, and the crystal was used as c, and these are shown in Table 10.

Further, the crystallization temperatures of the respective compositions were measured and shown in Table 10. The crystallization temperature is a temperature at which crystallization is performed after film formation at 100 ° C, and if it is not amorphous at the time of film formation at 100 ° C, it is considered to be less than 100 ° C.

Further, the resistivity ρ (Ω‧ cm) of the sample which was annealed and crystallized by the optimum oxygen partial pressure film formation at the time of film formation of each of the transparent conductive films formed at room temperature was measured. These results are shown in Table 10.

Further, the transparent conductive film produced by the optimum oxygen partial pressure at the time of film formation at room temperature was cut into a size of 13 mm square, and the transmission spectrum of the annealed film was measured. The average transmittance after the annealing treatment is shown in Table 10.

Further, the transparent conductive film which was produced by the optimum partial pressure of oxygen at the time of film formation at room temperature and which was crystallized by annealing was cut into a size of 10 × 50 mm, and ITO-0.5N (oxalic acid system, Kanto) was used. Chemical (stock) system (oxalic acid concentration 50 g / L) as an etching solution, the etching rate was measured at a temperature of 30 ° C ( /sec). The results are shown in Table 10.

These results are shown in Fig. 30. In the figure, a sample which can be formed into an amorphous film at a film forming temperature of less than 100 ° C and which can be crystallized at 100 ° C to 300 ° C is indicated by ●, and the others are indicated by ▲.

From this result, it is known that when the additive element is Ca, an amorphous film is formed when the film is formed at a temperature of less than 100 ° C, and then, when the annealing treatment is performed at 100 ° C to 300 ° C, the film can be crystallized. The composition range of the film is the molar ratio y with respect to the tin of the indium 1 mole, which is expressed by x when the molar ratio of Ca with respect to the indium 1 molar is (-4.1×10 ^-2 ln(x) A value of -9.3 × 10 ^-1 ) or more and a range of (-2.5 × 10 ^-1 ln(x) - 5.7 × 10 ^-1 ) or less.

It is also known that, in this range, in particular, such as the molar ratio y (mole) relative to the tin of indium 1 mole, when the molar ratio of Ca relative to the indium 1 molar is represented by x In the range of (-8.7 × 10 ^-2 ln(x) - 2.0 × 10 ^-1 ) or more, the film can be formed so that the annealing temperature does not crystallize when it is less than 200 ° C, and the annealing treatment is performed at 200 ° C or higher. Since the range of the crystallized film is considered to be more suitable in consideration of the film forming process.

Further, it is known that, in the above range, if the molar ratio y (mole) of tin relative to the indium 1 molar is 0.28 mol or less, the film can be formed into a resistivity after annealing at 250 ° C. A film of 3.0 × 10 ^-4 Ω ‧ cm or less is more suitable.

It is thus known that a predetermined effect can be obtained by adding an additive element. If the added elements are not the same, although the range of the predetermined effects that can be obtained is slightly different, the elements of the above-mentioned Sr, Li, La, and Ca are obtained. In the common range, when it is not formed at 100 ° C, it will become an amorphous film, and then, when it is annealed at 100 ° C to 300 ° C, the film can be formed into a crystallized film, which is relative to indium. The molar ratio y (mole) of 1 molar tin is expressed as x in the molar ratio of the additive element relative to indium 1 molar (-9.3×10 ^-2 ln(X)-2.1×10 The value of ^-1 ) is equal to or greater than the range of (-2.5 × 10 ^-2 ln(x) - 5.7 × 10 ^-1 ).

This result is shown in Fig. 31. In the figure, among all the elements, a film which can be formed into an amorphous film at a film forming temperature of less than 100 ° C and which can be crystallized at 100 ° C to 300 ° C is marked with ●, and others are recorded as ▲ . Further, the sample number is represented only by the number from which the Roman alphabet is removed.

Fig. 1 (a) to (c) are views showing the relationship between the oxygen partial pressure and the specific resistance of the film formation examples 1 to 3 of the present invention.

Fig. 2 (a) and (b) are views showing the relationship between the oxygen partial pressure and the specific resistance of the film formation examples 4 to 5 of the present invention.

Fig. 3 (a) and (b) are views showing the relationship between the oxygen partial pressure and the specific resistance of the film formation examples 6 to 7 of the present invention.

Fig. 4 (a) and (b) are views showing the relationship between the oxygen partial pressure and the specific resistance of the film formation examples 8 to 9 of the present invention.

Fig. 5 (a) and (b) are views showing the relationship between the oxygen partial pressure and the specific resistance of Reference Examples 1 to 2 of the present invention.

Fig. 6 (a) and (b) are views showing the relationship between the oxygen partial pressure and the specific resistance of Reference Examples 3 to 4 of the present invention.

Fig. 7 is a graph showing the relationship between the oxygen partial pressure and the specific resistance of Comparative Example 1 of the present invention.

Fig. 8 is a graph showing the relationship between the partial pressure of oxygen and the specific resistance of Film Formation Example 10 of the present invention.

Fig. 9 is a graph showing the relationship between the oxygen partial pressure and the specific resistance of the film formation example 11 of the present invention.

Fig. 10 is a graph showing the relationship between the partial pressure of oxygen and the specific resistance of Film Formation Example 12 of the present invention.

Fig. 11 is a graph showing the relationship between the oxygen partial pressure and the specific resistance of the film formation example 13 of the present invention.

Fig. 12 is a graph showing the relationship between the oxygen partial pressure and the specific resistance of Reference Example 5 of the present invention.

Fig. 13 (a) to (c) are views showing a pattern of a film XRD (X-ray diffraction) before and after the annealing treatment of the film formation examples 1 to 3 of the present invention.

Fig. 14 (a) and (b) are views showing the XRD pattern of the film before and after the annealing treatment of the film formation examples 4 to 5 of the present invention.

Fig. 15 (a) and (b) are views showing the XRD pattern of the film before and after the annealing treatment of the film formation examples 6 to 7 of the present invention.

Fig. 16 (a) and (b) are views showing the XRD pattern of the film before and after the annealing treatment of the film formation examples 8 to 9 of the present invention.

Fig. 17 (a) and (b) are views showing the XRD pattern of the film before and after the annealing treatment of Reference Examples 1 to 2 of the present invention.

Fig. 18 (a) and (b) are views showing the XRD pattern of the film before and after the annealing treatment of Reference Examples 3 to 4 of the present invention.

Fig. 19 is a view showing the XRD pattern of the film before and after the annealing treatment of Comparative Example 1 of the present invention.

Fig. 20 (a) to (c) are views showing a transmission spectrum before and after the annealing treatment of the film formation examples 1 to 3 of the present invention.

Fig. 21 (a) and (b) are views showing transmission spectra before and after the annealing treatment of the film formation examples 4 to 5 of the present invention.

Fig. 22 (a) and (b) are views showing transmission spectra before and after the annealing treatment of the film formation examples 6 to 7 of the present invention.

Fig. 23 (a) and (b) are views showing transmission spectra before and after the annealing treatment of Test Examples 7 to 8 of the present invention.

Fig. 24 (a) and (b) are views showing transmission spectra before and after annealing treatment of Reference Examples 1 to 2 of the present invention.

Fig. 25 (a) and (b) are views showing transmission spectra before and after annealing treatment of Reference Examples 3 to 4 of the present invention.

Fig. 26 is a view showing the transmission spectrum before and after the annealing treatment of Comparative Example 1 of the present invention.

Fig. 27 is a view showing the results of the Si-containing transparent conductive film of the present invention.

Fig. 28 is a view showing the results of the Li-containing transparent conductive film of the present invention.

Fig. 29 is a view showing the results of the La-containing transparent conductive film of the present invention.

Fig. 30 is a view showing the results of the Ca-containing transparent conductive film of the present invention.

Fig. 31 is a view showing the results of the transparent conductive film containing Sr, Li, La, and Ca of the present invention.

Since the figure in this case is the result data of the test compound, it is not a representative figure of this case. Therefore, there is no designated representative map in this case.

Claims (9)

An indium oxide-based target comprising: an indium oxide and optionally tin, and an additive element having an oxygen bond energy in the range of 100 to 350 kJ/mol with respect to indium 1 molar (however, Ba, Mg, and Y are Except for 0.0001 moles of oxide sintered body of less than 0.10 moles, wherein the molar ratio y of tin relative to indium 1 is based on the molar ratio of the additive element relative to indium 1 molar x represents a range equal to or greater than the value of (-9.3 × 10 ^-2 ln(x) - 2.1 × 10 ^-1 ) and not more than (-2.5 × 10 ^-1 ln(x) - 5.7 × 10 ^-1 ). The indium oxide-based target according to claim 1, wherein the additive element is at least one selected from the group consisting of Sr, Li, La, and Ca. The indium oxide-based target according to the first aspect of the patent application, wherein the indium 1 molar contains 0.3 mol or less of tin. An indium oxide-based target according to the second aspect of the patent application, wherein the indium 1 molar contains 0.3 mol or less of tin. The indium oxide-based target according to any one of the items 2 to 4, wherein the additive element is Sr. The indium oxide-based target according to any one of the items 2 to 4, wherein the additive element is Li. The indium oxide-based target according to any one of the items 2 to 4, wherein the additive element is La. The indium oxide-based target according to any one of the items 2 to 4, wherein the additive element is Ca. An indium oxide-based target comprising: an oxide sintered body containing indium oxide and tin and containing at least one additive element selected from the group consisting of Sr, Li, La, and Ca, characterized in that: When the element is Sr, the molar ratio y of the tin of the indium 1 molar is expressed by x with respect to the molar ratio of the Sr of the indium 1 molar (-9.3×10 ^-2 ln(x) a value of -2.1 × 10 ^-1 ) or more and a value of (-2.5 × 10 ^-1 ln(x) - 5.7 × 10 ^-1 ) or less; if the aforementioned additive element is Li, it is relative to indium 1 mol The molar ratio y of tin is greater than or equal to the value of (-9.3 × 10 ^-2 ln(x) - 2.1 × 10 ^-1 ) when the molar ratio of Li with respect to indium 1 molar is represented by x ( a range of -2.5 × 10 ^-1 ln(x) - 5.7 × 10 ^-1 ) or less; if the additive element is La as described above, the molar ratio y relative to the tin of indium 1 is relative to The molar ratio of La of Indium 1 Mo is higher than the value of (-9.3 × 10 ^-2 ln(x) - 2.1 × 10 ^-1 ) and (-2.5 × 10 ^-1 ln(x) - 5.7 the range of values × 10 ^-1) or less, such as when the additive element is Ca, with respect to the indium tin molar ratio of 1 mole of the y, based mole relative to 1 mole of Ca in the indium The time represented by ^{x (-9.3 × 10 -2 ln (} x) -2.1 × 10 -1) and a range value or values ^{(-2.5 × 10 -1 ln (x} ) -5.7 × 10 -1) of the following .