TW200927657A - Indium oxide target - Google Patents

Abstract

This invention provides a sputtering target having a sintered oxide which contains indium, and optional tin, and an additive element (excluding Ba, Mg, and Y) which has an oxygen bonding energy in the range of 100-350kJ/mol, the additive element being in the amount of from 0. 0001 mole or more to less than 0. 10 mole with respect to 1 mole of the indium.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an indium oxide-based dry film from which an amorphous film can be easily produced, and the amorphous film can be etched by a weak acid (weak acid) Etching is easy to perform patterning, and it is easy to crystallize, and a film which is crystallized can be used to produce a transparent conductive film having a low electrical resistance and a good transmittance. [Prior Art] ο ; Indium oxide tin oxide (composite oxide of In2〇3_Sn〇2, hereinafter referred to as ιτο) film can be 'g earth&, head> Dao Shi, first teeth, and conductive It is high in nature, so it is used as a liquid crystal display to prevent the glass from being exposed or to prevent the glass from being exposed. However, it is difficult to form an amorphous film. (10)) The problem of transparent indium-oxidation is yellow. The film is inferior to the transparency of the TM film, and there is a kind of film in the film: 2: 2, please as a transparent conductive film and previously proposed a conductive film (refer to the special text H pre-forms under the amorphous _ transparent To the problem.) $ Adding Shi Xi and becoming a high-resistance tilting range. [Patent Document 丨] Japanese Special Report 5 Yun 49 No. 49 (4) Please Patent [Invention] [The subject to be solved by the invention] In view of this situation, An object of the present invention is to provide an indium oxide system 320650 3 200927657 = an amorphous acid etching can be easily obtained from the dry film, and a non-Japanese-shaped film can be patterned by weak crystallization. It is easy to crystallize 'again, [to solve the problem of _^=(4) resistance, and the high-transmission day-transfer film. ο : It is known that the amorphous amorphous amine-based transparent conductive film which is excellent in the results of various researches is low-resistance, transparent and can accommodate "! and can be easily patterned by weak _ , _783) The fact of deuteration, and the first application (Japan's special painting -,,,:, and know, can be formed into the addition of such an amorphous film, not only 疋a, there are still various similar An element, such as an element capable of forming a film as an amorphous film, with an oxygen bond energy (a element of 1,0 to 350 kJ (kJ)/m〇1 (mole)) The indium system finally completes the present invention. The first state of the invention is indium oxide, characterized by having indium oxide and tin as needed, and _丨莫耳 contains oxygen bond energy of 0 to 350 kJ. Adding elements in the range of /mol (except for this (lock), ah) 蒌._mol or more _ below the oxide gargle. In this first state, 'by containing predetermined additive elements, The film can be formed into an amorphous film. The second state of the invention is based on the oxidized marriage system described in the first state, and the added element The element is an indium oxide-based target selected from the group consisting of Sr (Ming), Li (Li), La (Y), and Ca (Calcium). 320650 4 200927657 In this second state, if The group of 5 small ^ s啕 invites self-chemical, 1^, 1^, 匚 & group, and the eve-type, can form a film into an amorphous film. Indium month, brother 3 state is in the first The oxidation system described in the first or second state is required to form a film of bismuth oxide with respect to the copper oxide containing tin bismuth to 0.3 m of indium oxide. Transparent conductive film. 铟 Indium-based second or third state of oxidized Moir Mo tin tbyu for indium 1 (;) 21 ^ ) - 2^1xl 〇) ^ ^ ^ - L ^ (-2.5 xl〇-lLn(x)_5.7xl〇-1) 0^ The following target is an indium oxide-based target. In this fourth form, p + can be formed into A韭曰^~, and the film formation is: Less than loot: When the film is formed, it becomes a non-Japanese B-shaped film, and then, when it is annealed at 1 G (rc to C.C), the film can be crystallized. The fifth state of U is the second or In the indium oxide-based dry liquid described in the third state, the addition is divided into RIE and the halogen is Sr, and the phase is The molar ratio y of the tin of indium 1 is: relative to the molar ratio of Sr of indium! Mohr to the surface (-4. lxl〇-2Ln(x)~Q?νΐη'^ΛΑ ^ 〇 Indium oxide-based target having a value equal to or greater than the value of (-2.9χ1〇-1η(χ)-.7x10). In the fifth state, the film can be formed to be less than 1 〇 (rC When the film is crystallizable, the sixth state of the present invention is the oxidation of 320650 200927657 in the second or third state, and the former element is Li, and is relative to indium. The molar ratio y ' of the moir tin is greater than the value of -1. 6x10-lLn(x)-5. 9x10-1 when the molar ratio of u relative to the indium i molar is expressed by χ And an indium oxide-based target having a range of (2. 5χ1 (1) -5. 7x10' or less). In such a sixth state, the film can be formed into a film that is less than 1 〇{Γ(: when formed into a film, it can be an amorphous film, and then, when it is annealed at 1 〇〇 to 3 〇〇乞, it can be In the indium oxide-based dryness described in the second or third aspect, the additive element is La, and the molar ratio y with respect to the tin of the indium 1 mol, It is greater than the value of (~6·7xl〇2Ln(x)—2·2χ1〇_1) when the molar ratio of La relative to the indium of Mo is above 且 and (UxliTLnU) -7.7x10—〇 Indium oxide-based target in the range below the value. In the seventh state, the film can be formed into an amorphous film which is formed when the film is not filled with loot, and can be crystallized during the annealing treatment of (10). The eighth aspect of the present invention is the indium oxide-based dry material according to the second or third aspect, wherein the additive element is C;a, and the molar ratio of indium to moir tin is y. Is a value equal to or greater than the value of (-4·1χ1〇1η(1)_9·3χ1〇-2) when the molar ratio of Ca of indium oxime is represented by x and (i) the value below (1) to 5.7x1 ο1) Indium oxide targetIn such an eighth state, the film can be formed into a film which can be crystallized when it is not subjected to film formation by c, and then becomes an amorphous film after annealing treatment from 1 to the next. The ninth state of the present invention is a type of indium oxide-free, which is characterized in that it contains 320650 6 200927657 having indium oxide and tin, and contains at least one kind of additive element selected from the group consisting of Sr, Li, La, and ^. The oxidized marriage target of the oxidized 16 cannon is characterized by: /' If the additive element is Sr, the molar ratio y relative to the tin of indium i mole is in Sr relative to the indium i molar. The molar ratio is expressed by the meaning of (-4. 1x10 2Ln(x)-9· 2xlG.2) and the range below (2. 9xl()_lLn(1) - 6. 7xl0_1); ❹ as described above When the additive element is Li, the molar ratio 7' of the tin relative to the indium 1 molar is expressed as -1 (-1. 6X10 1η(χ)-5. 9x10-) ^ T ^ (_2 5xl 〇 - Ln (x) - 5. 7x10 ) The value below the range; as the above added element is "hour, then relative to the molar ratio of 锢 1 Mo tin y, The value of _ Ln 〇〇 2· 2 χ 〇 〇 〇 且 且 相对 相对 相对 相对 相对 相对 La La La La La La La La La La La La La La La La La La La La La La La La La La La La La La La La La La La La La The range of 1; when Mg plus element is Ca, it is relative to indium (4) 5·7χ10-1)^^τ^ιι^α^^〇( 2,5x10 Ln(x)~ The following film can be formed into the following film: when not fully processed: = amorphous The film 'then, then in the lorc to the lower annealed target, the inversion of the indium oxide type as shown in the ninth aspect is relative to the indium 1 苴:g: and ΛΑ & The molar ratio is greater than the value of the above-mentioned additive element with respect to the indium 1 320650 7 200927657 ear, and is represented by x 9 3χ1〇'η (the value of the magical - 2. 1x10 且 and above (_2. 5xl〇 -iLn(x)_5· The range below 7χ1〇〇. In this 10th state, the film can be formed into an amorphous film when film formation is less than 1〇〇〇c, and then it is loot to 30 (film which can be crystallized when annealing under TC. ' [Effect of the invention]

For example, according to the present invention, an effect of providing an indium oxide-based target can be exerted, and an amorphous film can be easily produced by adding a film of an element having an oxygen bond in the range of 100 to 350 kJ/mol. On the other hand, the amorphous film system can be easily patterned by a weak acid (tetra), and can be easily crystallized. The crystallized film is formed into a transparent conductive film having low electrical resistance and high transmittance. [Embodiment] The oxidation 1 and ' used for forming the indium oxide-based transparent conductive film of the present invention are those in which indium oxide is mainly used, and tin is contained, and the hair can be contained in the range of just 350 kJ/mQl. Adding elemental oxide or 1It plus 7" is similar to a Weixiang shirt, or as a pure oxide oxide, as a money (4), and a residue (4). In this case, the indium oxide is a smear. It is a sintered body having an indium oxide sintered body (the ink is splashed by the 4th (four) material (4).

In addition to (4) and (4), Plat includes a sheet-like element (4) et) used for forming a transparent conductive film by ion plating Cic lnS). Ionizing electricity is also known as "320650 8 200927657" The addition of an oxygen bond in the range of 100 to 350 kJ/mol is the same as that of the previously applied bismuth, and has an effect of making an indium oxide transparent conductive film into an amorphous film. It can be exemplified by Ba (oxygen bond energy: 138 kJ/mol), Sr (oxygen bond energy: 134 kJ/mol), Li (oxygen bond energy: 151 kJ/mol), and 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. ❹ 〇 , , , , , , , , , , , , , , , , , , , , , 容易 容易 容易 容易 容易 容易 容易 容易 容易 容易 容易 容易 容易 容易 容易 容易 容易 容易 容易 容易 容易 容易 容易 容易 容易 容易 容易 容易After the annealing treatment, the optimum oxygen partial pressure does not change, and the electro-optical properties are hardly improved by the annealing treatment. · Health &quot; and the oxygen bond is at 1〇〇 to 35 The element of the lower range of 〇kJ/m〇1 is smaller than the oxygen and '' force, and it is presumed to show the effect of becoming an amorphous film. In the oxygen bond month, 84 ^/&quot;^ or K ( Oxygen bond energy: 54 kJ/mol) Although:: bond: 2: When added to an indium oxide-based transparent conductive film, it is not suitable due to adverse effects or damage to environmental resistance. Refer to the temptation of the 'Southerners' broken glass ~ the scientific introduction of amorphous body - 聿 聿 Books (shares), pp. 34-36). The content of the added elements of the 千 Μ Μ , , , , The effect of copper addition is not significant. If the amount is less than this, the resistance of the conductive film will increase. The formation of a halogen in the transparent conductive film formed by the upper two Q and the yellowish degree of the veins. The content of the emulsified indium-based target used in the π-sec (4) is the same as the content of 320650 9 200927657 。. Further, the content of tin is in the range of 莫. 3 moles with respect to the indium bismuth. In the case, it is preferable to contain a range of Q.001 to 0.3 mol with respect to the indium lanthanum. If it is within this range, the density of the electron carrier (carrier electr) of the indium oxide sputtering target can be appropriately controlled. The mobility is maintained in a good range. 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 is 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. Sputter target with DC magnetron sputtering (DC magn Etron sputtering) can be sputtered at a lower cost DC magnetron sputtering. Of course, a high frequency magnetron sputtering device can also be used. By using such an indium oxide target, An oxidized iridium-based transparent conductive film having the same composition can be formed. The composition analysis of the indium oxide-based transparent conductive film can also be performed by ICP (inductively coupled plasma) after the single film is completely dissolved. When the film itself is formed into an element structure, the section of the 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). A 70-cell analysis device (EDS (Energy Dispersion Spectrometer) or wds (Wavelength Dispersive Spectrometer), Auger electr〇n spectr〇sc〇py, etc.) can also be specified. Since the cerium oxide film formed by the indium oxide-based target of the present invention has a predetermined amount of added elements, it is considered to contain yttrium, and it is more than room temperature and the crystallization temperature is The film is formed into a film in a state of being amorphous, for example, a temperature lower than the temperature condition, preferably less than 15 generations, and more preferably a temperature lower than _c:. Further, such a non-S-shaped release, u, and such a non-day-shaped film have the advantage of being able to perform (4) with a weakly acidic etchant. Here, in the present specification, the Ο is included in the ® (4) towel, and the (4) system _ fixed image _. Further, the specific resistance of the obtained transparent conductive film varies depending on the type and content of the added elements, but the specific resistance is usually 1 〇 > <1 〇 _ 4 to i serv % · Further 'uses indium oxide The crystallization temperature of the film formed by the target varies depending on the type and content of the added element, and increases as the content increases. For example, the temperature is 10 (TC to 3 〇C). Annealing treatment can be crystallized. Since this temperature region is used in the usual semiconductor edge-making process, it can also be crystallized in such a process. Preferably, it is crystallized at 1 〇 m 3 〇〇 &lt; t, more preferably crystallization at 15 ° C to 25 ° C, preferably at 200 ° C to 250 ° C Here, the annealing treatment refers to the heating in the atmosphere, in the ambient gas, in the vacuum, at a desired temperature for a certain period of time. The certain time 'generally means from minutes to numbers. The degree of hour, but industrially, if the effect is the same, then it is shorter than the shorter one. The transparent conductive film crystallized by the annealing treatment has an improved transmittance on the short-wavelength side. For example, the average wavelength of 4,650 to 5 nm at a wavelength of 4 〇〇 to 5 〇〇 nm will be 85% or more. In the case where IZ〇 (indium zinc oxide) is a problem, the film will not have a yellow color. Here, in general, the higher the transmittance on the short-wavelength side, the better. On the other hand, the crystallization is transparent. The etching resistance of the conductive film will be improved, so that the amorphous film can be etched by the weakly acidic ink engraving agent, thereby improving the corrosion resistance in the subsequent process or the environment resistance of the component itself. 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, and thus the film is formed. After that, it can be formed into a heat-resistant manner at a temperature higher than the crystallization temperature, and the amorphous state can be maintained. After the film is formed and patterned, the heat treatment is performed at a temperature higher than the temperature at which the crystallization is performed. In order to change the etching resistance. Here, if the additive element is Sr, it will become an amorphous film when it is not 〇〇c, and then at 100X; to 3〇〇°c. When the annealing treatment is performed, the composition range of the crystallized film can be formed, which is the molar ratio y (mole) of the tin of the indium 1 molar, and is the molar ratio of the sr relative to the indium 1 molar. In the case of X, the value of (-4· ΙχΙΟΛηΟΟ-9. 2χ1 (Γ2) is equal to or greater than (_2. 9 ΧίΟΊι^χ^δ^χΙΟ-1). Further, in this range, Yes, if the molar ratio y (mole) relative to the tin of indium bismuth is above (1). 2x1Q-WxH.wr) when the molar ratio of Sr relative to the indium bismuth is represented by X In the range, the annealing treatment temperature is less than 20 (TC does not crystallize, but passes through 2 〇〇. When the above annealing treatment can form a range of crystallized film, it is more appropriate to consider the film forming procedure 320650 12 200927657 « (process). Further, in the above range, as in the range of 0.15 m or more and 〇28 mol γ mol of tin relative to the molar ratio y, the film formation is 25 (the resistivity after TC annealing treatment) From the next case, the following film, and more suitable. ' 〇xlO 4Q . cn] ❹ If the additive element is Li, at 1 〇 (rc is a crystalline film, then, at 10 CTC to 3 〇〇. When the film is formed under the armpit and the film is formed into a film, the composition range of the film is not the film, and it is a ratio of y (mole) to the steel, and is the tin of the ear and the tin of the ear. In the range of Mohr's time (-1.6.10χ10'η〇〇-5. 9X10-1), the ratio of the ear to x is equal to or less than the value of -5·7x10'. ο Also, in this range, In particular, such as Moerby y (mole), in the case of the tin X relative to the 锢丨moer, steel 1 Mo (-7. Curry) - 1.6 χ 1 (), on the Mo When the annealing treatment temperature is less than 2 〇 (the rc is not in the rc, the target is formed, the annealing treatment is formed into a film W shape; the above is more suitable. In the system, as in the relative to the indium U' ear 0.28 Moules and below (4) with respect to the Mo of the indium J Moer's Mo == is a film which can be a resistivity of 3. 〇χ1〇-4 Ω · (10) or less after annealing by 25Qt, and更/ If the additive element is La, it becomes an amorphous film when it is formed under 1〇〇t, and then it can be 13 320650 200927657 when it is annealed under (10) 匚 to 3〇{rc.

• V film is the composition range of the crystallized film, relative to the indium 丨moby y, is the molar of the molar relative to the indium i Mo, the tin of the tin (-6. 7XHTLOO-2. 2χΐη The value above X represents the range below the value of -7. 7xl0_1). '3x10 Ln(x) ο Again, in this range, in particular, as opposed to the molar ratio y (mole), when expressed in relation to the tin X of the horn of the surface 1 -8.7xl〇.2Ln(x)-2.()Xir) or more. The molar ratio of the annealing treatment is less than 2Q (the crystal will not crystallize when rc), and the film can be crystallized during the annealing treatment. It is more suitable when the film is in the range of 2QG C or more. In the above range, if it is 0.23 moles or less relative to the molar ratio, it is annealed. The post-forming film resistivity is 3·0χ1 (Γ4Ω·, which is more suitable for the group 25〇C. The film below cm is ,, for example, when the additive element is Ca, in the case of 1〇〇. Then, when the boot is in the battle, the film is formed into a crystallized film, which is in the range of the indium 2; the ear ratio y is in the c, the ear relative to the indium 2 The value of _ 5· 7x10 ) is below the range. Χ1ϋ Also, in this range 'especially, such as the recognized Moerby y (mole), in relation to the indium id: tin, when the annealing temperature is not full, ::: Two 320650 14 200927657 ·» The annealing process can form a film into the range of the crystallized film, so it will be more suitable when testing. 'The film-forming procedure, in the above-mentioned garden, if it is 0.28 mol or less with respect to indium 丨 molar ratio y (mole), it becomes 25 〇χ: film formation after annealing treatment It is more suitable for a film having a resistivity of 3·0χ1 (Γ4Ω·cm or less), and thus, a predetermined effect can be obtained as a result of adding an additive element, but if the added elements are not the same, the reservation can be obtained. The range of effects will vary somewhat, but in the range common to the above-mentioned Sr, Li, La, and Ca elements, it is less than 1 (. (: It becomes an amorphous film at the time of film formation, and then, at 100 ° C When the annealing treatment is carried out at 300 ° C, the composition of the film can be formed into a crystallized film. The 'range' is a molar ratio y with respect to the tin of indium 1 mole, and is a molar element added with respect to the indium 1 molar. The value is equal to or greater than the value of -9. 3xl (T2Ln(x) -2. ΙχΗΓ1) and the value of (-2. 5xlO-1Ln(x)-5·7xl0_1) is less than or equal to the value of X. The method for producing the indium oxide-based dry material of the present invention will be described, but is 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. In the case of a compound, a procedure which can be used as an oxide is carried out in advance. The method of mixing and blending the raw materials into the desired blending ratio is not particularly limited, and various wet types known from the prior art can be used. Law or dry method. 15 320650 200927657

The V dry method is exemplified by the 'cold house (five) dpi_ess method or the hot press method. In the cold 黯, the mixed powder is filled in a molding die to prepare a molded body and calcined. In the hot dust method, the mixed powder is calcined and sintered in a molding die. For the wet method, it is preferable to use, for example, a filter molding method (Japanese Patent Application Laid-Open No. Hei 11-286002). The filtration molding method is a filtration molding die obtained by dewatering and dewatering water from a ceramic raw material slurry to obtain a water-insoluble cerium material for a molded body, and the molding film is made of a material. The molding die for forming the above-mentioned drainage hole, the water-passing filter placed on the lower mold for molding, and the molding frame which is sandwiched from the upper surface by sealing the sealing material for the filter And the assembly, the mold for molding, the molding die, the sealing material, and the filter, and the filtration of the moisture in the slurry only from the side of the filter Forming a mold to prepare a slurry of mixed powder, ion-exchanged water, and an organic additive, and injecting the aggregate into the over-molding mold, and only performing moisture in the aggregate from the side of the filter The reduced pressure is removed to prepare a molded body, and the obtained ceramic formed body is dried and degreased, and then calcined. The calcination temperature of the person formed by cold pressing or hot pressing is preferably 13 to 2, and more preferably 1500 to 'the environment is atmospheric environment, oxygen environment, non-oxidizing environment, or vacuum environment, etc. . On the other hand, in the case of the hot pressing f, it is preferable to make H in the vicinity of l_t: and the environment is a non-oxidizing environment or a vacuum environment. In addition, in each method, simmering, 'is applied to a predetermined size, mechanical processing for processing;:, to make palladium ο 320650 16 200927657 Λ, [Embodiment] [Examples] The present invention is described by way of example of the invention, but the invention is not limited by the examples. (sputter target production example 1) (Sr-IT0) (addition of Sr ΙΤ0, Sr=0. 02-Sn=〇. 1) Preparation purity &gt;99. 99% of In2〇3 powder, and purity&gt; 99. 9% bismuth SrC〇3 powder. First, according to the In2〇3 powder 65. 3 wt% and the ratio of (: 〇 3 powder 34.7 畺 畺 %), prepare a full amount of 200 g, and perform ball milling in a dry state (ball mi 11 mixing) in the atmosphere 120 (rc The pre-calcination was carried out for 3 hours to obtain a 丨n2〇4 powder. Next, the total amount of the SrIn2〇4 powder was 2.2% by weight, “.86.6% by weight of the powder, and 11.2% by weight of the Sn〇2 powder. 1〇kg (kg) (The composition of each metal atom is In=88. 〇at %, STi=1〇〇at %, Sr=2 〇at.%), and this is mixed by ball milling. Then, pVA ( Polyvinyl alcohol) An aqueous solution of hydrazine is used as a binder, mixed, dried, and cold pressed to obtain a molded body. The molded body is heated at a rate of 10 hours in the air for 10 hours to degrease. Next, calcination was carried out at 1550 C for 8 hours in an oxygen atmosphere to obtain a sintered body. Regarding the calcination conditions, specifically, from room temperature to 80 (rc was 2 〇 (rc/hour, temperature was raised, k 800 c to 1550 ° C, then press 400 ° C / hour to increase the temperature, after 8 hours, from 155 (TC to room temperature stop 10 (rC / M, the speed of the cooling is lacking) Member then processing the obtained sintered body dry. At this time, a density of 7 billion $ cm3. § / 320650 17 200927657 same manner as a sputtering target made Sr = G.〇_

Sr: 0.01, Sr = 〇. 〇5 Further [Table 1] A sputtering target having the composition shown in Table 1 was produced in the same manner.

(Adding Li no, Li=0. 02-Sn=0. 1) Preparing purity &gt;99. 99% of In2〇3 powder, Sn〇2 powder 'and purity>99·9% 18 320650 200927657 χ. Li2C〇3 powder. First, a total amount of 200 g of In2〇3 powder of 79.0% by weight and Li2C〇3 powder of 21. 0% by weight is prepared, and the mixture is ball-milled in a dry state, and pre-calcined at 1000 ° C for 3 hours in the atmosphere. LiIn〇2 powder. Next, a total amount of about 1.0 kg is prepared in addition to the above-mentioned Li In〇2 powder 2.2% by weight, In2〇3 powder 86.8 wt%, and Sn〇2 powder 11.0 wt% (the composition of each metal atom is In=88). 0 at. %, Sn=10. 0 at. %, Li=2. 0 at. %) The target was produced in the same manner as Sr-ITO (Sr=0. 02). However, the calcination temperature was 1450 °C. The density at this time was 6.85 g/cm3. In the same manner, a sputtering target having a composition as shown in Table 2 below was fabricated. ❿ 19 320650 200927657 [Table 2] Sample composition Cat%) Relative to In (indium [mole) 1 molar ratio ear] No. — in S n L i Li s η b 1 9 4. 5 5. 〇0. 5 0 . 0 0 5 ο. 0 5 3^ b 2 8 9. 5 10, 0 0. 5 - 0. 0 0 6 0 1 12 b 3 8 4. 5 1 5. 0 0. 5 0. 0 0 6 0 1 7 8 b 4 - . -7 9. 5 2 0.0 0. 5 0 . 0 0 6 0 2 5 2 b 5 9 4. 0 5. 0 1. 0 0. Oil 0 0 5 3 b 6 8 9. 0 10.0 1. 0 0 . Oil 0 1 12 b 7 8 4. 0 15.0 1 . 0 0 . 0 12 0 1 7 9 b 8 7 9. 0 2 0.0 1. 0 0 . 0 13 0 2 5 3 b 9 _______ 9 3. 0 5. 0 2. 0 0. 0 2 2 0 0 5 4 b 1 0 8 8· 0 10. 0 2. 0 0. 0 2 3 0 1 1 4 b 1 1 8 3. 0 15.0 2. 0 0. 0 2 4 0 1 8 1 b 1 2 7 8. 0 2 0.0 2 . 0 0. 0 2 6 0 2 5 6 b 1 3 9 2. 0 5. 0 3. 0 0 · 0 3 3 0 0 5 4 b 1 4 .——~ 8 7. 0 10.0 3.0 0. 0 3 4 0 1 15 b 1 5 8 2. 0 15.0 3. 〇0. 0 3 7 0 1 8 3 b 1 6 ------ 7 7. 0 2 0. 0 3. 0 0 . 0 3 9 0 2 6 0 b 1 7 9 〇. 0 5. 0 5. 0 0 . 0 5 6 0 0 5 6 b 1 8 8 5· 0 10.0 5. 0 0. 0 5 9 0 1 18 b 1 9 8 0. 0 15.0 5. 0 0. 0 6 3 0 1 8 8 b 2 0 7 5. 0 2 0.0 5 . 0 0. 0 6 7 0 2 6 7 b 2 1 8 5. 0 5. 0 10· 0 0 . 118 0 0 5 9 b 2 2 so. 0 10.0 10 · 0 0 . 12 5 0 1 2 5 b 2 3 _^--- 7 5. 0 Γ5. 0 10 · 0 0. 13 3 0 2 0 0 b 2 4 7 〇. 0 2 0.0 1 0 _ 0 0 . 14 3 0 2 8 6 b 2 5 89. 995 10. 000 0· 005 0. 000056 0. 111117 b 2 6 82. 800 17. 000 〇. 200 0. 002415 0. 205314 b 2 7 89. 900 10.000 0, 100 0. 001112 0. 111235 b 2 8 84. 900 15.000 0. 100 0.001178 0. 176678 b 2 9 82.000 17. 000 L000 0.012195 0.207317 b 3 0 80. 000 __.-- 18.000 2.000 0. 025000 0. 225000

(sputter target production example 3) (La_IT0) (addition of La ΙΤ0, La=0. 02_Sn=0. 1) Preparation purity &gt;99. 99% of In2〇3 powder, Sn〇2 powder, and purity&gt; 99. 99% of .La2(C〇3)3 · 8H2O powder. First, according to the ratio of ImCh powder 31.6 weight La2 (c〇3) 3 · just powder 68 4% by weight, the whole quantity is purchased, in the Lang «lower domain ball mill mixing, 320650 20 200927657, in the atmosphere at 1200 ° C Pre-calcined for 3 hours to prepare LaIn〇3 powder. Then, in addition to the above-mentioned 1»&amp;111〇3 powder 4.3% by weight, 1112〇3 powder 85.0.% by weight, and Sn〇2 powder 10.7% by weight, the total amount is about 1.0 kg (the composition of each metal atom is In=88). 0 at. %, Sn = 10. 0 at. %, La = 2. 0 at. %) The target was prepared in the same manner as Sr-ITO (Sr = 0.02). The density at this time is 7. 04g/cm3. In the same manner, a sputtering target having a composition as shown in Table 3 below was fabricated. 〇❹ 21 320650 200927657 [Table 3] Sample composition (at%) relative to In丨^ I nsn L a La sn C 1 9 4 .5 5 . 0 0 . 5 0 . 0 0 5 0 • Π 5 C 2 8 9 • 5 10 .0 0 . 5 0. 0 0 6 0 11 9 C 3 8 4 .5 15 .0 0 . 5 0 . 0 0 6 0 1 7 DC 4 7 9 • 5 2 0 • 0 0. 5 0 . 0 0 6 0 9. tz C 5 9 4 0 5. 0 1. 0 0· Oil 0 0 5 ~ C 6 8 9 • 0 10 .0 1. 0 0. Oil 0 1 1 — I. oc 7 8 4 0 15 0 1 . 0 0. 0 12 0 1 7 Ci 9 *— 3 C 8 7 9 0 2 0 0 1. 0 0. 0 13 0 2 5 C 9 9 3 0 5 . 0 2. 0 0. 0 2 2 0 〇5 4 cl 0 8 8 0 10.0 2. 0 0 . 0 2 3 0 11 A cl 1 8 3 0 15 0 2. 0 0. 0 2 4 0 — _ 18 -2- 1 cl 2 7 8 0 2 0 0 2. 0 0. 0 2 6 0 2 5 6 cl 3 9 2 0 5 . 0 3. 0 0 . 0 3 3 0 0 5 4 Cl 4 8 7 0 10 0 3. 0 0 0 3 4 0 11 5 cl 5 8 2. 0 15, 0 3. 0 0. 0 3 7 0 18 3 cl 6 7 7· 0 2 0 · 0 3. 0 0. 0 3 9 0 2 6 〇cl 7 9 0· 0 5. 0 5. 0 0. 0 5 6 0 0 5 6 , Cl 8 8 5. 0 10 . 0 5. 0 0. 0 5 9 0 11 s cl 9 8 0. 0 15· 0 5, 0 0. 0 6 3 0 18 8 c 2 0 7 5, 0 2 0. 0 5, 0 0. 0 6 7 0 2 6 7 c 2 1 8 5, 0 5 . 0 10. 0 0 . 0 0 5 9 c 2 2 8 0. 0 10. 0 10. 0 0 . 12 5 0 12 B c 2 3 7'5. 0 15· 0 1 0 . 0 0. 13 3 0 2 0 0 c 2 4 7 0. 0 2 0 . 0 10.0 0 . 14 3 0 2 8 6 —c 2_ 5 89. 992 10. 000 0.008 0.00009 0. Ill c 2 6 86. 900 13. 00.0 0. 100 0. 00115 0. 150 c 2 7 79. 900 20 . 000 0. 100 0.00125 0. 250 c 2 8 81.000 18. 000 1.000 0.01235 0. 222 c 2 9 81.800 18. 000 0.200 0. 00244 0. 220 -C 3 0 84. 960 15.000 0. 040 0. 00047 〇 177 (sputter target production example 4) (Ca-IT0) (addition of Ca to ΙΤ0, Ca=0. 02-Sn=0. 1) Preparation of purity &gt;99·99% of In2〇3 powder, Sn〇2 Powder, and purity &gt; 99. 5% CaC〇3 powder. First, according to the ratio of In2〇3 powder 73.5 wt% and CaC〇3 powder 26.5 wt%, the total amount of 200 g 'ball milled in the dry state is off' in the atmosphere 320650 22 200927657

Pre-calcined at 1200 ° C for 3 hours in V to prepare CaIn 2 〇 4 powder. Okg( Each metal atom has a composition of In, in addition to the above-mentioned CaIm〇4 powder 4.8 wt%, In2〇3 powder 84.3 wt%, and Sn〇2 powder 10.9 wt% ratio. 0: 0 at. %, Sn = 10. 0 at. %, Ca = 2. 0 at. %), and the rest was made in the same manner as Sr-ITO (Sr=0. 02). The density at this time was 6.73 g/cm3. In the same manner, a sputtering target having the composition shown in Table 4 below was fabricated. 〇❹ 23 320650 200927657 [Table 4] The composition of the sample relative to the ratio of n (indium) 1 moles----_ (at%) [mole] In S nca C a S nd 1 9 4. 5 5· 0 0 . 5 0 . 0 0 5 0. 0 5 3 d 2 8 9. 5 10.0 0 . 5 0 . 0 0 6 0. 112 d 3 8 4 5 15.0 0 . 5 0 . 0 0 6 0. 17 8 d 4 7 9 5 2 0.0 0 . 5 0 . 0 0 6 0. 2 5 2 d 5 9 4. 0 5.0 1. 0 0 . Oil 0. 0 5 3 d 6 8 9 0 10.0 1.0 0 . 0. 112 d 7 8 4. 0 15.0 1. o 0 . 0 12 0. 17 9 d 8 7 9. 0 2 0.0 1. 0 0 . 0 13 0. 2 5 3 d 9 9 3. 0 5.0 2. 0 0. 0 2 2 0. 0 5 4 d 1 0 8 8 0 10.0 2. 0 0. 0 2 3 0 . 114 dll 8 3 0 15.0 2. 0 0. 0 2 4 0. 18 1 d 1 2 7 8. 0 2 0.0 2. 0 0. 0 2 6 0. 2 5 6 d 1 3 9 2 0 5. 0 3. 〇0. 0 3 3 0. 0 5 4 d 1 4 8 7. 0 10.0 3 . 0 0 . 0 3 4 0 · 115 d 1 5 8 2. 0 15.0 3. 〇0 . 0 3 7 0. 18 3 d 1 6 7 7. 0 2 0 . 0 3. 0 0 . 0 3 9 0 . 2 6 0 d 1 7 9〇. 0 5.0 5. 0 0 . 0 5 6 0. 0 5 6 d 1 8 8 5 0 10.0 5. 0 0 . 0 5 9 0. .118 d 1 9 8 〇. 0 15.0 5. 0 0 . 0 6 3 0 . 18 8 d 2 0 7 5· — 0 2 0.0 5. 0 0 . 0 6 7 0. 2 6 7 d 2 1 8 5. 0 5. 0 10 · 0 0 . 118 0 . 0 5 9 d 2 2 8 0 0 10. 0 10. 0 0 . 12 5 0 12 5 d 2 3 7 5. 0 15.0 10. 0 0 . 13 3 0 . 2 0 0 d 2 4 ... L〇^〇2 0 . 0 10· 0 0. 14 3 0 . 2 8 6 d 2 5 — 94.800 5.000 0. 200 0.002110 0.052743 d 2 6 -86. 950 13. 000 0.050 0. 000575 0- 149511 d 2 7 82. 900 17. 000 0. 100 0.001206 0. 205066 d 2 8 79. 9〇n 20. 000 0. 100 0. 001252 D. 250313 d 2 9 -.90- 900 9. 000 0. 100 0. 001100 0. 099010 d 3 0 76. onn n. ooo 2. 000 0. 026316 0. 289474 (sputter target reference manufacturing example l) (Mg-IT0) (add Mg to ΙΤ0, Mg= 0。 02-Sn = 0. 1) Preparation of purity &gt; 99. 99% of I112O3 powder, Sn 〇 2 powder, and cesium carbonate oxidized powder (MgO content 41.5 wt%). First, according to the ratio of In2〇3 powder 87.3% by weight and magnesium hydroxide powder 12.7% by weight, prepare a total amount of 200g, and perform ball milling in a dry state, 320650 24 200927657, in the atmosphere at 1400 ° C After calcination for 3 hours, MgIn2〇4 powder was obtained. Okg( The composition of each metal atom is In=88, the total amount of the metal atoms is about 1. 0% by weight. 0 at. %,Sn=l0. 0 at. %, Mg=2. 0 at. %), the rest was made in the same manner as Sr-ITO (Sr=0. 02). The density at this time is 7. 02g/cm3 . In the same manner, a sputtering target of Mg = 0.05 and Mg = 0.12 was produced. (Sputter target reference production example 2) (Y-ITO) w (ITO added with Y, Υ=0·02-Sn=0. 1) Preparation purity> 99. 99% of In2〇3 powder, Sn〇2 Powder, and purity &gt; 99. 99% of Y2(C〇3)3 · 3H2 〇 powder. First, prepare the whole amount of 200g according to the ratio of In2〇3 powder 40. 2% by weight and Y2(C〇3)3 · 3H2〇 powder 59.8-% by weight, and perform ball milling mixing in the dry state, 1200° in the atmosphere. Pre-calcined at C for 3 hours to prepare YIn〇3 powder. 0公斤( The composition of each metal atom is In, in addition to the above ΥΙ 〇 〇 3 powder 3.6 wt%, Im 〇 3 powder 85. 6 重量©% and Sn 〇 2 powder HK 8% by weight ratio of the total amount of about 1. 0kg (each metal atom composition is In The target was produced in the same manner as in the case of Sr-ITO (Sr = 0.02) except for the case of Sr-ITO (Sr = 0.02). The density at this time is 7. 02g/cm3. In the same manner, a sputtering target of Y = 0.05 was produced. (Sputter target reference production example 3) (Β-ΙΤ0) (ITO with Β added, Β=0· 05, Sn=0. 1) Preparation purity &gt;99. 99% of In2〇3 powder, Sn〇2 powder , and purity &gt; 99. 99% of B2O3 powder. 25 320650 200927657 In addition to these powders in accordance with Im (h powder 87.5% by weight and Sn 〇 2 powder 11. 2% by weight, β2 〇 3 powder 1.3% by weight ratio to prepare the full amount 〇 kg (each metal shoulder The composition is ίη=85. 0 at. %,Sn=l〇.〇at. %, β=5. 〇at. %), and the rest is in the same way as Sr-ITO (Sr=〇.〇2) The target was produced. However, the calcination temperature was 140 (TC. The density at this time was 5 〇 lg/cm 3 . ο (Guan Guan 1 to 13, Reference Examples 1 to 5, and Comparative Example 二 Example 2 = manufactured as described above) This method was carried out. As shown below, Comparative Example L, which is a composition of film formation m to 13, and Table 5, was separately mounted (4) ^Example m and the temperature was set to room temperature (about 20. Diameter sputtering device) , the substrate L &gt;&gt;, the partial pressure of oxygen is changed between 〇$q Λ standard cubic centimeter) (equivalent 〇_(card per minute)): a film forming example U13, a reference example is obtained. Transparent conductive film. 3 from 及 320650 26 200927657 [Table 5] Ο

Oat%) Film Formation Example 2 (Sr=〇. 02) Film Formation Example 10 ί^ΐ^οοοοί) Film Formation Example 11 00005) Formation Example 12 Ιίί^ΟΟΟΟβ) Film Formation Example 1 (Sr=0. 01) Film Example 6 (La=0. 01) Film Formation Example 4 (Li=〇. 02) Film Formation Example 7 (La=0. 02) Film Formation Example 8 (Ca=〇. 02) Reference Example I (Mg=0) 02) Reference Example 3 (Y=0. 02) Film Formation Example 3 (Sr=0. 05) Film Formation Example 5 (Li=0. 05) Film Formation Example 9 (Ca=0.05) Reference Example 2 ( Mg = 0.05. Reference Example 4 (Y = 0.05) Comparative Example 1 (Β = 0.05) Film Formation Example 13 (Ca = 0.10) Reference Example 5 (Mg = 0.12) The conditions were as follows, and a film having a thickness of 1200 A was obtained. Dry size · φ=4ίη. t=6mm Sputtering method: DC magnetron sputtering Exhaust device: Rotary pump (rotary pumpH cryopump) Vacuum degree: 5.3xl0-6[Pa] ο

Ar (argon) bad force: 4. 〇xl〇1 [Pa] Oxygen pressure: 〇 to 1. lxl〇-2 [Pa] Water pressure: 5. Oxl 〇 _6 [pa] Substrate temperature: room temperature 贱 plating power : 130 W (watt) (power density 1. 6 W/cm 2 ) Substrate: Corning #1737 (glass for liquid crystal display) t (thickness) = 〇. 8 mm Measure the resistance of the film under the partial pressure of oxygen The rate and the resistivity of each film after annealing at 250 c. The results are shown in Figures 1 through a, 320650 27 200927657. 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 partial pressure of oxygen at room temperature and the oxygen partial pressure at the time of film formation with the lowest resistivity after annealing at 250 °C. From this, it was found that in Film Formation Examples 1 to 9 and Reference Examples 1 to 5, the partial pressure of oxygen at the time of film formation having the lowest resistivity after annealing at 250 ° C was carried out, and then, at 250 ° C. When the annealing treatment is performed, the film with the lowest electrical resistance can be obtained. 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-gas 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 〇, and the optimum oxygen partial pressure change is indicated by X. (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 13 mm squares, respectively. The size was measured and the samples were annealed at 250 ° C for 1 hour in the atmosphere. The film XRD pattern table 28 320650 200927657 before and after the annealing treatment is shown in Figs. 13 to 19. Also, regarding the film formation example! 4, Reference Examples 1 to 4, and Comparative Example 1 1 At room temperature film formation and 25 (the crystal state after annealing treatment), the amorphous form is a, the crystal is c, and these are shown in 2. As a result, it was confirmed that the film formation examples 1 to 9 and the reference examples 1 to 4 which were formed at room temperature were amorphous films at the time of film formation, but were crystallized by 25 (rci annealing treatment). On the other hand, in the comparative example of B in which the oxygen bond can be added, or in the film-forming example 13 and the reference example 5 in which the amount of addition is large, although it is amorphous at the time of film formation, it is still not crystallized after 25 (rc annealing treatment). In addition, it has been confirmed that the film formation is not crystallized even at 3 〇 (the annealing treatment at rc. Moreover, in the film formation examples 1 () to 12 in which the amount of addition is small, the film formation is confirmed. It also crystallizes and does not form an amorphous film. (Test Example 2) Measure the optimum oxygen partial pressure film formed by film formation at room temperature. The resistivity at time ρ (Ω · cm). Further, the resistivity of the sample after annealing in 〇 test 1 was also measured. These results are shown in Table 6. In the case of Film Formation Examples 1 to 12, Reference Examples 1 to 4, and Comparative Example 1, the specific resistance was about 1 〇-force·cm. However, it was found that in Film Formation Examples 13 to 14, the specific resistance became 1 (High resistance of about 1 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 material produced by the optimum oxygen partial pressure at room temperature film formation was used. The film was cut to a size of 13 Å square to measure the transmission spectrum, and the transmission spectrum was also measured for the film after the annealing treatment of Test Example 1. The results are shown in the same section. 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. The transmission spectrum before the post-annealing treatment is a fact that the absorption end migrates to the low-wavelength side by the annealing treatment at 250 ° C for 1 hour, and the tint is improved. _ (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 separation at room temperature was cut into a size of 10×50 mm, and ΙΤ〇- 〇5Ν (oxalic acid system, Japan Kanto-Chemical Co., Ltd.) (oxalic acid concentration: 50 g/L) was used as an etching solution, and it was confirmed whether or not etching was possible at a temperature of 30 °C. Further, 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 φ as "〇" 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. 30 320650 200927657 ^ [Table 6]

Can I etch 1 .... [〇 or X] 1 0 0 o 0 0 o 〇oo XXX oo 0 0 ooo fn.tw Both wear E 96.9 93.5 91.1 E7.8 92.1 | 98.3 I 98.8 96.2 95.1 u&gt;〇&gt; 95.6 98.2 89.9 95.5 94.1 79.9 | 93.2 93.7 93.4 1 Annealing 1 Crystallinity (2503⁄4) 3 ο ο ooo O ooo O oo &lt;0 o 0 a υ o (0 Crystallinity at film formation [a or d | η a (Q (0 CD (D (D &lt;0 φ ooo «0 CO &lt;D « 0 after annealing treatment resistivity f ά 1 χ •-1 5 CO CO &lt;0 CO eo οά s 〇〇j S 〇&gt ; ai 00 〇&gt;〇&gt; 17.8 eo CO 〇} Bu· U.6 I CO esi es CD Resistivity when filming [xi〇-4Q-cm] u&gt; IA CD 5 CO IO o lO to ui 5 in 〇&gt; CM· ΟΪ CM m 14.3 a&gt; iq 10.5 in (O 〇&gt; £ 1111 i[〇 or X]l ο ooooo 〇oo XXX 〇ooooo X 5 毋Indium)1 molar ratio h [mole] 1 0.011 1 0.023 | 0.059 0.023 0.059 0.011 0.023 0.023 0.063 0.000011 0.000056 0.000089 0.125 0.023 0.063 0.154 0.023 0.059 0.059 S? Adding dollars to ο 5 5 o C4 so 5 s 5 0.001 0.005 0.008 1Q.0 o 04 o in 12.0 o eg 5 s 10.0 10.0 10.0 100 10.0 1 0.0 10.0 10.0 10.0 10.000 | 10.000 | 10-000 10.0 10.0 10.0 10.0 10.0 10.0 i 10.0 of .0 88.0 85.0 88.0 85.0 I 89.0 I 88.0 88.0 80.0 89.999 89.995 89.998 80.0 88.0 80.0 78.0 1 88.0 85.0 85.0 Adding element ά) CO □ Ώ 3 3 ¢5 &lt;3 ¢0 3 δ &gt;- &gt;- SD Sample name Sr=0.01 Sr=0.02 I Sr=0.05 U=0.02 U=0.05 La-0.01 | La=0.02 Ca=0.02 Ca=0.05 Sr =0.00001 U=0.00005 La=0.00008 Ca=0.10 | Mg=0.02 | Mg=0.05 | Mg=0.12 1 Y=0.02 Y=0.05 | B=0.05 Film Formation Example / Comparative Example 1 Film Formation Example 1 CSJ eo in CD r ** 00 O) o 2 CO 1 Reference Example i | &lt;^j to to 1 Comparative Example i 31 320650 200927657 » (Transparent Conductive Film Containing Sr Composition) Using the composition shown in Table 1 manufactured as described above The target is mounted on a 4 DC DC magnetron sputtering device, and the substrate temperature is set to room temperature (about 20 ° C), and the oxygen partial pressure is changed between 0 and 3.0 sccm (equivalent to 0 to 1). . lxlO_2Pa), a transparent conductive film of each composition was obtained. The conditions of the sputtering were as follows, and a film having a thickness of 1200 A was obtained. Geb size: &lt;M4in. t=6mm Sputtering method: DC magnetron sputtering Exhaust device: rotary pump + cryogenic pump Reach vacuum: 5. 3xlO_5[Pa]

Ar pressure: 4. 0x10-iPa] Oxygen pressure: 0 to 1. lxl (T2 [Pa] water pressure: 5. 0x10 - 5 [Pa] substrate temperature: room temperature sputtering power: 130W (power density 1. 6W / Cm2) Q Substrate: Corning #1737 (glass for liquid crystal display) t=0.8mm Here, the optimum oxygen partial pressure of film formation at room temperature, and the oxygen content at the time of film formation with the lowest resistivity after annealing at 250 °C There are many samples with different pressures, but some compositions have no change in the optimum oxygen partial pressure. In Table 7 below, there will be the optimum oxygen partial pressure change, indicated by ,, there will be no optimum oxygen partial pressure change. Further, the transparent conductive film produced by the optimum oxygen partial pressure at the room temperature film formation of each composition is cut into a size of 13 mm square, and the samples are 250° in the atmosphere. Annealing treatment was carried out for 1 hour at C, and film formation was carried out at room temperature for 32 320 650 200927657 嫕 and 25 (the crystallization state after TC annealing treatment, with amorphous as a and crystallization 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 was formed at 100 Å after film formation. When the temperature of crystallization is increased, and it is not amorphous when it is formed into a film, it is considered to be less than 1. Further, each of the transparent conductive films formed into a film is formed into a film at an optimum oxygen partial pressure at room temperature. Then, the electric enthalpy resistivity Ω (Ω · cm) of the sample which was annealed and crystallized was shown in Table 7. Further, the optimum oxygen partial pressure at the time of film formation at room temperature was used. The manufactured transparent conductive film was cut to a size of 13 caffe squares, and the transmission spectrum was measured on the annealed film. The average transmittance after annealing treatment is shown in Table 7. X, will be room temperature At the time of film formation, the optimum oxygen is statically formed and annealed to make the transparent conductive film after U匕 cut into 2 〇湖mm 2, and IT(H)5N (oxalic acid system, Guan Guo Chemical) ))) (( 草 ❹; X 50g / L) as a liquid smoke, at a temperature of 3 〇. Under the ,, can you carry out the rhyme engraving confirmation. It can be (4) as "〇", not marriage as "X", indicating The result is shown in Fig. 28. In the figure, it will be less than 100 〇 (the film can be formed into an amorphous film at a degree of 曰 、, and at 100 ° C to 300 ° In the month of C1, the test H filament and the other phase ▲ are indicated. From this result, it is known that if the film is formed at a temperature of - ° C, it will become a non-Japanese 70-state Sr. When the annealing treatment is less than 10, Chitosan 'then' is at 10 (rc to 30°.. The composition range of the next 1 m day is relative to indium 1) 320650 33 200927657 » The molar ratio of tin to y (mole), in The molar ratio of Sr to Inr 1 molar is greater than the value of (-4. 1χ10_21η(χ)-9. 2xl0_2) and (-2. 9χ10_11η(χ)-6. 7x10—. The value below the range. It is also known that, in this range, in particular, such as Mohr ratio y (mole) with respect to tin of indium 1 mole, when the molar ratio of Sr with respect to indium 1 mol is represented by X (-8. 2χ10_21η(χ)-1. 9 parent 10-1) The above range does not crystallize when the annealing temperature is less than 200 °C, but crystallizes when it is annealed at 200 °C or higher. The range is considered to be more suitable for the film formation procedure. Further, it is known that, in the above range, if the molar ratio y of the tin relative to the indium 1 molar is 0.15 m or more and 0.28 m or less, the annealing is performed at 250 ° C. After the resistivity is 3.0 χ 10_4 Ω · cm to - down, and more suitable. 34 320650 200927657 ' [Table 7]

320650 35 200927657 Splashing method: DC magnetron sputtering venting device: Rotary pump + cryogenic pump reaching vacuum: 5. 3xl (T5[Pa] Ar Pressure: 4. OxlO_1[Pa] Oxygen pressure: 0 to 1. lxl 〇_2[Pa] Water pressure: 5·0xl (T5[Pa] Substrate temperature: room temperature 〇 Sputtering power: 130W (power density Uw/aq t=〇8mm / here, the optimum oxygen content to the temperature film) After the 25th generation of retreat, the oxygen with the lowest resistivity after the retreat of the film is divided into the same day. The samples with different knives are different, but some compositions have no change in the optimum oxygen partial pressure. In the 8th, there will be an optimum oxygen partial pressure change. The optimum oxygen partial pressure change is indicated by X. No, it will be transparently conductive under the optimum oxygen partial pressure at the room temperature of each composition. The film was cut to a size of 13 caffe squares, and the samples were annealed in the atmosphere at 25 °C (hours, at room temperature, and after annealing at 25 〇t). The crystal form is represented by a, 、, ', and the day of the mouth as c ' and is shown in Table 8. The crystallization temperature of each composition is also measured and shown in Table 8. The crystallization temperature is 1 〇〇. The temperature at which crystallization is carried out after film formation under the enamel, and if it is not amorphous at 100 ° 〇 film formation, it is considered to be less than 1 〇〇χ: After measuring the optimum oxygen partial pressure of each transparent conductive film formed at room temperature, the sample was annealed to crystallize the sample 36' 320650 200927657, and the resistance was p(1)·cm). The results are shown in Table 8. Further, the size of the transparent guide layer produced by the optimum oxygen partial pressure at room temperature film formation was measured, and the scale was transmitted through the annealed 8 film. The average dressing is expressed by the optimum oxygen partial pressure at the time of film formation at room temperature, and the transparent conductive film after annealing is cut into ι〇χ_ ❹ ❹ and /) respectively as a residual liquid. Temperature 3 (at TC, the rate of money was measured (A / sec). The results are shown in Table 8. 1 =: fruit: t is shown in Figure 28. In the figure, will be crystallized in the _ The sample is indicated by •, and the others are known from H1000 to 300 c, such as adding element:: when forming a film, it becomes an amorphous film' then In the range of the composition of the film which is crystallized, the molar ratio of tin to y (mole) is less than the value of the relative i.7xlr). In such a range of 'in particular, if it is relative to the indium 1 molar ratio, it is not the case (_7 〇1fK2 becomes the film forming annealing temperature is not; the C or more annealing treatment day will crystallize, and The scope of the film of the military mouth is becoming more and more suitable, so it is more appropriate to consider the film formation 320650 37 200927657. In the above range, as in the case of Moerby y relative to the marriage tin, it is 〇.28 Above Moule, and relative to indium 1 Moth ^ below 0. °15, the film can be formed into a film having a resistivity of 3 1 π - 4 π dry υχ ο ο ο ο ο ο ο ο ο And more suitable. [Table 8] ❹ ❹

Proportion, [Mo 1

(Transparent Conductive Film Containing La Composition) Using the target of the composition shown in Table 3 manufactured as described above, the 38 320650 200927657 was attached to a 4 DC DC magnetron sputtering apparatus, and the substrate temperature was set to room temperature ( About 20 ° C), the partial pressure of oxygen is changed between 0 and 3. Osccm (corresponding to 〇 to 1. lxl (T2Pa), a transparent conductive film of each composition is obtained. The conditions of sputtering are as follows A film with a thickness of 1200 A is produced. The size of the child is Φ=4ίη. t=6ram Sputtering method: DC magnetron sputtering. Exhaust device. Rotating system · + low temperature fruit ❹ Reaching degree of vacuum: 5. 3xl (T5 [Pa]

Ar, ": 4.0xl01 [Pa] Oxygen pressure: 0 to 1. lxl 〇 - 2 [Pa] Water pressure: 5. 0xl (T5 [pa]. Substrate temperature: room temperature ' Sputtering power: 130W (power density 1 6W/cm2) Substrate: Corning #1737 (glass for liquid crystal display) t=〇8mm Here, the optimum oxygen partial pressure of film formation at room temperature is the lowest resistivity after annealing with 25〇&gt;c. The sample with different oxygen partial pressure at the time of film formation has a good date, but there is some composition, and the optimum oxygen partial pressure does not change. In Table 9 below, the optimum oxygen partial pressure change is indicated by ,, The change of the optimum oxygen partial pressure is expressed by x. 'X' will be cut into the size of 丨3mm square, which is the optimum oxygen labeling film at the room temperature of each composition. 250 in the atmosphere ((: the next annealing treatment i hours, the film formation at room temperature = and 25 (the crystal state after TC annealing treatment, the amorphous form as a, the,,, ° crystal as c ' and these The results are shown in Table 9. 320650 39 200927657 Further, the crystallization temperature of each composition was measured and shown in Table 9. After the film formation temperature was 100 ° C, the film was formed. When the temperature at which the crystallization is carried out is not amorphous when it is formed into a film, it is considered to be less than 〇〇c. Further, when each of the transparent conductive films to be formed is formed at room temperature, the film is formed. The optimum resistivity ρ (Ω · cm) of the sample which was annealed and crystallized after the partial pressure of oxygen was formed into a film, and the results are shown in Table 9. Further, when the film was formed at room temperature The transparent conductive film produced by the optimum oxygen partial pressure was cut into a size of 13 nm square, and the transmission spectrum was measured for the annealed film. The average transmittance after annealing treatment is shown in Table 9. The transparent conductive film which is formed by the optimum partial pressure of oxygen at room temperature and is annealed by annealing is cut into a size of 1 G x 5 〇 inm ' using ITO-0.5N (oxalic acid system 'Kanto Chemical ( (manufactured by the system) (oxalic acid + 50 g / L) as (four) liquid 'under temperature ,, the measurement of the rate (A / sec). The results are shown in Table 9. In Figure 29, in the figure, It will be an amorphous film at a filming temperature of less than 1 C, and it can be crystallized in 1 to 3 times. The surface is represented by other phases ▲. If it is known that the additive element is La, it will become an amorphous film when it is less than 1 纟 film, and then, when it is under lore to 。, the film is a crystallized film. The Mohrby y of the composition of Zeng Moer's tin is the value of La and A Urrh η / (Χ)_2·2Χ1 (Γ1) of (1) 7χ10-2ΐηη9〇 when expressed in 相对 with respect to the molar ratio. And (3.3xlG 1η(χ)-7.7χ1(Γ1) has the value 320650 40 200927657 r. It is also known that in this range, in particular, such as the molar ratio y (mole) of the relatively scratched tin, Compared with indium bismuth; the fine 1 molar ratio is represented by X (_8. 7χ1〇-2ΐη(χ)_2 〇χ1(Γΐ) above La Moer becomes capable of film formation for annealing temperature below 200 When the temperature is not higher than °C, the range of the film which will crystallize during the annealing treatment of TC or higher is more suitable. Considering that the composition is known to be in the above range, such as when 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 after annealing at 250 C. The resistivity of the film is 3. 0x10 4 Ω .cm or less, and is more suitable. 〇 320650 41 200927657 [Table 9]

ο ο (Transparent Conductive Film Containing Ca Composition) Using the composition (4) of Table 4 manufactured as described above, this was separately mounted on a 4-pair DC magnetron hybrid device, and the substrate temperature was set to room temperature (20 ° C). A transparent conductive film of each composition was prepared by dividing the oxygen pressure into a dish varying from 3 〇sccm ^ to 0 to L bdO-(iv). The conditions for the destruction of the ore were prepared as follows, and a film having a thickness of 12 〇〇 A was obtained. Dry size: 0=4in. t=6mm 320650 42 200927657 Sputtering method: DC magnetron sputtering Exhaust device: rotary pump + cryogenic pump Reach vacuum: 5.3xl (T5[pa]

Ar pressure: 4. OxlOjPa] Oxygen pressure: 〇 to 1. lxl〇-2 [Pa] Water pressure: 5. 0xl (T5[pa] Substrate temperature: room temperature 溅 Sputtering power: 130W (power density uw/cv) Substrate used: Corning #1737 (glass for liquid crystal display) t=〇8mm Here, the optimum partial pressure of oxygen at room temperature is different from the partial pressure of oxygen at the lowest resistivity after annealing at 25 〇ΐ. There are many wolves in the sample, but some compositions have no change in the optimum oxygen partial pressure. In Table 10 below, the optimum oxygen partial pressure change is indicated by 〇, and the optimum oxygen partial pressure change is indicated by χ. Moreover, the transparent conductive film produced by the optimum oxygen partial pressure at the time of film formation of each composition is cut into a size of 13 mm square, and these samples are placed in the atmosphere at 25 (TC). When the annealing treatment was performed for a few hours, the film was formed at room temperature and in the crystal state after 25 (TC annealing treatment, the amorphous form was taken as a, and the crystal was used as C, and these were shown in the table. The crystallization temperature is shown in Table 1. The crystallization temperature is crystallization after lamination at TC. When the temperature is not formed into a film at the time of C film formation, it is considered to be unsatisfactory. Further, each of the transparent conductive films formed into the film is formed into a film at room temperature, and then annealed to form a film. Crystallized sample (4) 320650 43 200927657 Resistivity ρ (Ω · cm). These results are shown in Table 1〇. Also, the transparent conductive film produced by the optimum oxygen partial pressure at room temperature film formation. , cut to a size of 13 mm square, and measure the transmission spectrum of the annealed film. The average penetration after annealing is expressed in Table 1 0 0, and the optimum of 〇 仫 级 级 胰 胰The transparent conductive film which is produced by oxygen partial pressure and crystallized by annealing is cut into a size of 10×50 mm, and is made of ΙΤΟ-0·5Ν (oxalic acid system, manufactured by Kanto Chemical Co., Ltd.) (oxalic acid concentration: 50 g/L) As an etching solution, the etching rate (Α/sec) was measured at a temperature. The results are shown in Table 1. The results are shown in Figure 3. In the figure, it will not be 1 〇〇t: The film formation is made into an amorphous film under filming/melting, and can be knotted at t to 3 (8). The sample is represented by φ, and the other is represented by ▲. From this result, it is known that, if the element A Ca is added, it will become an amorphous film when it is formed under a film of less than 1 〇〇^, and then, in 丨(10). 匚至纲. The composition range of the film which can form a film into crystals, which is based on the tin ratio y of the tin of the indium material, is that the molar ratio is broadly expressed by x. The value of Ca ς 4. lxlG InW-UxHT1) is in the range of (-2:5χ10 1η(χ)_57χ1〇, the value of tin is :ί: μ in this range, especially 'as opposed to indium 1 Mohr = Indium 1 Mohr _ ear becomes capable of film formation annealing temperature is not 20 (TC or more, pp ★ crystallizes at less than 2〇〇C, and crystallizes upon annealing treatment The range of the film, so consider the film formation process 320650 200927657 ▼ The order will become more suitable. Tin 苴 ☆ In the above range, 'is more suitable than indium 1 mole. The hand is in the mold below 3.0x10 Q.cm, and the sample number is [Table 10]

I—Π. 026316 0 289474 __c__&lt;1〇〇__2· 1 乂I a 300 3. 2~~2~~~Tp~ So ♦ By adding the added elements, you can get the pre-fruits such as &quot;j When the elements are not the same, although the expected effect 320650 45 200927657 is different, the range of the common elements of Sr, u, La and the elements mentioned above is less than 1G (rc). When the film is formed, it becomes an amorphous film, and then the annealing process is performed at 1 GGT: to 3 GSt, and the composition range of the film which is formed into a film by crystallization is compared with the molar ratio y (mole) of the tin of indium 1 , which is greater than the value of (-9.3χ1(Γ21η(χ)·_2.1χ1{Γΐ)) when the molar ratio of the additive element relative to indium oxime is expressed by 且 and ({km (1) -5. 7x1 ( The range below the value of Γ1). This result is shown in Fig. 31. In the figure, it will be formed into an amorphous yt at a film formation temperature of TC in all the elements, and at (10) to 3QGtT. Samples that can be crystallized are marked with • and others are marked with ▲. Also, the sample number is indicated by the number with the Roman letter removed. [Simplified illustration] Figure 1 (a) to (C) The film formation example of the present invention is shown in the graph of the relationship between the partial pressure and the specific resistance. ❹ Fig. 2 (a) and (8) show the relationship between the film formation example 4 of the present invention and the partial pressure and the specific resistance. Fig. 3 (a) and (5) are diagrams showing the relationship between the partial pressure of the film formation examples 6 to 7 of the present invention and the specific resistance. Fig. 4 (a) and (8) show the film formation examples 8 to 8 of the present invention. Fig. 9 is a diagram showing the relationship between the partial pressure of gas and the specific resistance. Fig. 5 (a) and (b) show the relationship between the partial pressure and the specific resistance of the reference example of the present invention. The oxygen of the reference material 3 to 4 is 320650 46 200927657 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 view showing the oxygen content of the film forming example 1 of the present invention. Fig. 9 is a graph showing the relationship between the oxygen partial pressure and the specific resistance of the film forming example u of the present invention. Fig. 10 is a view showing the oxygen partial pressure of the film forming example 12 of the present invention. Fig. 11 is a view 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 view showing the relationship of the present invention. Fig. 13 is a graph showing the relationship between the partial pressure of oxygen and the specific resistance. * Fig. 13 (3) to (&lt;&gt; shows the film XRD (X-ray diffraction) before and after the annealing treatment of the examples 1 to 3 of the present invention. Fig. 14 (a) and (b) are diagrams showing the XRD pattern of the film before and after the annealing treatment of Examples 4 to 5 of the present invention. Fig. 15 (a) and (b) The figure shows the XRD pattern of the film before and after the annealing process of the film formation examples 6 to 7 of this 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 diagrams showing the XRD pattern of the film before and after the annealing treatment of Reference Examples 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. 320650 200927657 Fig. 19 is a view showing a film XRD pattern before and after the annealing treatment of Comparative Example 1 of the present invention. Fig. 20 (a) to (c) are diagrams showing the 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 the 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 transmitted light 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. 48 320650 200927657 * Fig. 31 is a view showing the results of the transparent conductive film containing Sr, Li, La, and Ca of the present invention. [Main component symbol description] No 0 ❹ ❹ 49 320650

Claims (1)

200927657 « VII, Shen § 青 patent scope: = indium oxide H features: with indium oxide and as needed &amp; and relative to indium i molar containing oxygen bond energy in the range of 1 〇〇 to 1 production of added alizarin (However, Ba, such as, except for the laborer of Y) 咖. Coffee 1 mole above the 〇. 10 mole oxide sintered body. 2. = Please invent the patent (4) indium oxide green, the towel, the additive element, which is selected from the group consisting of Sr, Li, La, and Ca. ❹·, apply for the indium oxide green of the third paragraph of the patent, which contains tin bismuth to 〇. 3 moles relative to the marriage. 4摩尔。 It is difficult to (4) 2 items of indium oxide green, the towel, relative to the indium 1 molar containing tin 0 to 0.3 m. _ 5. ^Applicable to the copper oxide system of any of items 2 to 4 of the patent range, the molar ratio y of t ' relative to the tin of indium 1 molar is relative to the indium 1 molar The molar ratio of the added element is above the value of (U, xlOlnOOilxliT1) and below the value of (_2.5xlG_lln(1)-57 $ χίο b. 6. Please refer to the second to fourth patent scopes. Any of the oxidized marriage targets/wherein the addition element g Sr, and the ratio y of the tin relative to the indium is in the (iv) indium bismuth d molar ratio, -4. lxl〇-2ln(x)-9. 2xi〇-2) The value is greater than or equal to ("2.9" WUnCx^iUxHr1). 7. If the scope of application is 2nd to 4th In any one of the singularity, it is added to the heart of the element, and relative to the pin! Moer = Moerby y, which is in the molar ratio relative to the indium} Moer to X 320650 50 200927657 « Indicates the range below the value of the value r mOO-UxHTi) of (-l.exio^noouwp). And (“2.5X 8. The copper oxide target of any of items 2 to 4 of the range], in which the added element is La, and the kick relative to the indium i moir = Mo^7' It is equal to or greater than the value of K7Xl (nn(x) - 2.2χί(Γ1)) and the value of (_33χ 1η(χ)-7·7χ10_1) when the molar ratio of La with respect to indium 1 molar is expressed by x. Scope. The oxy-oil system of any of items 2 to 4 of the range of interest is Ca' and relative to _1 mole of tin 々 Mo = ratio y, is relative to the money! Mo Ca The range of the molar ratio is not more than the value of (1·1·10 2 ιη(1)_9. 3χ1()-2) and is less than the value of (1 2×X 〇ln(x)-5. 7χ10_1). = f• is a dry, which is a sintered body of a telluride containing at least one of a group of indium oxide and tin, and containing at least one of a group of octyl groups and a group of C &amp; ·· = When the additive element is Sr, it is relative to the tin of indium i mole: Mo: ratio y, compared with the molar ratio of indium 1 to Mo, :,, (-4. 1χ10 ηηω_9 · 2χ1〇, a value equal to or greater than the value of (2. nCx^UxlO1); When u, then the phase (1) poses two Mo: ratio, 'system, in the relative to the indium 1 Mo Ll's MoΙο'πγΤΪ1* 1]nCX)~5* 9XlrI)^^^^-C-2. 5&gt; The range below the value of η(Χ)-5·7χ1〇); if the addition of TL is La, the molar ratio y of indium bismuth 320650 51 200927657 is relative to indium 1 The molar ratio of La of the molar is expressed by X (-6. 7xl〇-2ln〇〇-2. 2χ〗 〇-]) and the value of (_3 j 10 UnU)-?. 7XUT1) is below The range, if the above-mentioned additive element is Ca, then the molar ratio y ' of the tin of the indium] is in the 锢 锢 锢 莫 莫 莫 Ca Ca Ca Ca Ca Ca Ca Ca -4 -4 -4 -4 -4 -4 -4 -4 (nn (x> 9.3xin value or more and (_25χ ίο ln(x)-5. 7χ10_1) value below the range. For example, the indium oxide wire of claim 1G, wherein the molar ratio y relative to the =1 mole of tin is expressed by X before the molar ratio relative to the 锢 Moth is expressed by (1). (χ)_2 ΐχ , above and 2 · SxlOlnCx) · ^. 7χ1〇-ι) The range under the value. /JmM under Φ 320650 52