TW570909B - Sputtering target for forming transparent conductive film of high electric resistance and method for producing transparent conductive film of high electric resistance - Google Patents

Abstract

To provide a sputtering target for forming a transparent conductive film of high electric resistance which target is applicable to a DC magnetron sputtering apparatus and can form a transparent film of high electric resistance, and a method for producing a transparent conductive film of high electric resistance. The indium-oxide-based sputtering target for forming a high-electric-resistance, transparent conductive film having a resistivity of approximately (0.8-10)x10<-3> Omegacm contains indium oxide, an insulating oxide, and, in accordance with needs, an optional tin oxide.

Description

570909 V. Description of the invention (1) ----- JL He belongs to the technical field of the invention The present invention relates to the high resistance used in the production of high-resistance conductive films with a resistivity of about 0. Sputtering target for resistive transparent conductive film 0 "(Sputtering tar got) and method for manufacturing high-resistance transparent conductive film using electric film *. A $ Electric film manufacturing method of resistive transparent conductive film. Previous technology, due to indium oxide-tin oxide (I rig 〇3-S η 〇2 composite oxide, hereinafter referred to as 'I T0') The film has high visible light transmittance and high conductivity, so it is widely used as a conductive film for liquid crystal display devices and glass. For the prevention, villagers use heating film and infrared reflective film, etc. ° s For example, choose a low electricity and high electricity invention. However, you must also make the device basically transparent in view of the transparency.

The transparent conductive film used in the flat panel display (FPD) is a transparent conductive film with a resistance (resistance of about 2 X 1 0-4 Ω cm). In terms of principle, a transparent conductive film for a resistive keypad is mounted on such an FPD or the like. As a required characteristic, the thin film resistance of the g-resistor is approximately 700 to 100 Q. r J owe a question to Hao Bei;? The problem is as follows:

This way: the strength of the keypad can be ensured. On the right, the resistance of the sputtering target itself becomes high resistance. The second problem is that the high-frequency magnetron is cheaper and the magnetron sputtering device is more expensive. : The same situation; brother ’The object of the present invention is to provide a method for manufacturing high-electricity = leather materials and high-resistance transparent conductive films-sufficient to use DC magnetron sputtering equipment, which can be made transparent and

C: \ 2D-CODE \ 91-O9 \ 91113997.ptd

570909 V. Description of the invention (2) Resistive film.

Means for solving the problem 硖 ^ I ί 2 solution / 夬 The above question, the first aspect of the present invention is high resistance 丄. Residual plating target Ke 'is a high-resistance transparent conductive film with a resistivity of about 0.8 to 10 UL. It is an indium oxide rhenium-plated leather material. Its characteristics are 4 ^ _, 疋' S is oxidized. Indium and tin oxide, as required, contain insulating oxides. In the sample, by adding insulation to the indium oxide-based sputtering target, the chemical resistance of the transparent conductive film formed by the two plates south is not changed so that the resistivity of the material itself is not greatly changed. . The second tragedy of this month is the sputtering target for a high-resistance transparent conductive film. In the i-th aspect, the super-insulating oxide is selected from the group consisting of silicon oxide, aluminum oxide, oxide button, hafnium oxide, At least one of niobium oxide, yttrium oxide, hafnium oxide, tungsten oxide, beryllium oxide, barium oxide, sharp oxide, titanium oxide, gallium oxide, zinc oxide, chromium oxide, bell oxide, and elements of the oxide group. In this second aspect, people can increase the formation rate by adding stone oxide, oxide oxide, niobium oxide, emulsified yttrium, emulsified ytterbium, osmium oxide, etc .; the resistivity changes greatly, and the formation is improved The second resistivity of the transparent conductive film. J

Oxidation # 5 Vanadium oxide Iron oxide Hafnium oxide Boron oxide Molybdenum oxide Oxidize Oxidize

The third aspect of the present invention is high, and in the second aspect, Shi Xi. Sputtering target for resistance transparent conductive film

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570909 V. Description of the invention (4) Indium-based alloy sputtered dry materials can prevent the resistivity of the two magnetrons from forming dry materials. · 8 secondary product = changed transparent conductive film. luxiuucm The eighth complaint of this month is high resistance &amp; It is characterized in that in the seventh energy, μ, +-Γ Jade film manufacturing method 'Shi Xi, oxidized junction Γ and oxidation · ^ insulation oxidation The material is selected from the group consisting of calcium oxide, osmium oxide, iron oxide, hafnium oxide, stone oxide, oxidized phosphorus oxide, hafnium oxide, =, :::, niobium oxide, oxygen, oxide, sharp oxide, titanium oxide, oxide At least one of the following elements: oxide, chromium oxide, manganese oxide, and lanthanum oxide. ^ In the M1 sample, by using the target with oxygen cut, oxide, and sputtering, it is possible to prevent the resistance of the target itself. Rolled indium-rhenium is formed by sputtering a DC magnetron to form a resistivity, = conductive film. 0 10 x io 3 Qcm transparent The ninth aspect of the present invention is a high-resistance transparent conductive switch. In the eighth aspect, the above-mentioned insulating oxide; = In the ninth aspect, by using an indium oxide system to which a silicon oxide has been added = a plating target, the resistivity of the target itself does not change greatly, 'And the resistivity is formed by DC magnetron sputtering to 0.8 ~ 10 The 10th aspect of Qcm's transparent and unmistakable state is a method for fabricating a high-resistance transparent conductive film, which is characterized in that in any of the 7th to 9th aspects, the above-mentioned oxidative oxidation is constituted. C. \ 2D-CODE \ 9l-〇9 \ 9ni3997.ptd Page 8 570909 V. Description of the invention (5) The content of the substance is 1 mol indium relative to 1 mol, which contains 0.0 0 0 0 1 ~ 〇 · 26 mol. In the 10th state of Hai, the transparent conductive film of ㈣cm was produced by the DC resistivity of the magnetron == itself by changing the insulation oxidation of the steel oxide-based degaussing leather material by a certain amount. The resistivity at the end of the ore formation is 0.8 to 的. The first aspect of the present invention lies in the lettuce thirst day, Thai RS, and was characterized in that any of the 7th to 10th electricity translucent: the production of the moon film Method 'Ear indium contains 0 to 0.3 moles of tin.' Sn (Sn) is relative to 1 mole Φ J in the eleventh aspect. 'Sputtering targets containing oxidized tin oxide can be used. The resistivity of the transparent conductive film of 0.8 to 10 x cn] is used to form the resistivity. The ㈣㈣❹f-blocking transparent conductive film of the present invention contains tin oxide as needed, and contains sintered molybdenum as the main component. Each oxide can exist in the original form of the oxide: the form of a dagger or a solid solution, and there is no particular limitation; or the oxidation of oxygen is here, and as an insulating oxide, # magnesium oxide can be listed Rhenium oxide, Mammoth oxide, Rhenium oxide, Zinc titanium oxide, Chromium oxide group elements, etc. As an insulating oxide, oxide group, oxide feed, oxide oxide, oxygen ... = barium oxide, gallium oxide, oxide oxide and Lanthanum oxide, calcium oxide, hafnium oxide, iron oxide, and molybdenum oxide are preferably insulating oxides having a range of 0 to 160 ° C and having lower energy than indium oxide. This is because the standard generation ratio is more chemically stable and difficult to decompose. ·, ', Rhenium indium oxide phase

570909 V. Description of the invention (6) The content of the preferred insulating oxide is 1 mole of indium, which constitutes the range 'of the insulating oxide β: relative to the ear. The reason is that if it is less than this range, the day ',' ,, 0.00 0 0 1 ~ 0.26, and 'if it is more than this range, the formation of 夂: = 果 不 Significant' and the tin (Sn) relative to Ear indium is 0 ~; 7 / and the resistance is too high. In the case of tin, compared to 1 mole of indium, tin. Mole. In the range containing tin, it is preferable. .. BU G.15 Mor's V circumference is. · = 2 moles to ears 0.1 moles range. If it is within this range, the density of the carrier electrons and the moving sound / ° of the plated target material are appropriately controlled within the range of good sputtering. In addition, if it exceeds this range, the mobility of carrier electrons with good electrical properties in the dry material will be reduced, and σσ = = will make the direction of development, so it is not desirable. The degraded sputtering target for a high-resistance transparent conductive film of the present invention has a resistance value to the extent that it can be sputtered by tube sputtering, and can form a transparent conductive film having a thickness of about 10 × 10-3 Ω cm. … Is 0.8 Of course, a transparent conductive film having a resistivity of 0.8 to 10 × 10-3 Dcm can also be formed using a high-frequency magnetron laser plating device. Next, the manufacturing method of the sputtering target of the present invention will be described. This example is not limited to this. 14 ^ ^ First of all, the initial raw materials constituting the sputtering target of the present invention, ## Iri2〇3, Sn〇2, Si〇2 powder. In addition, these simple substances and admixtures, composite oxides, etc. can also be used as raw materials. Using simple substances, compounds ',' + b through the step of turning into oxide in advance. At the desired blending rate, some raw material powder will be transported into the mold,

C: \ 2D-OODE \ 91-O9 \ 91113997.ptd Page 10 570909 V. Description of the invention (7) The method is not particularly limited ′ Various previously known wet methods and dry methods can be used. , / 〆 As a dry method, a cold press (Co Id Press) method or a hot press (Hot Press) method can be cited. In the cold-casting method ', the mixed powder is filled into a stamper to form a molded body, and the mixture is fired and sintered in an atmospheric atmosphere or an oxygen atmosphere. In the hot pressing method, the mixed powder is directly placed in a stamper and sintered. As for the wet method, for example, a filtration molding method is preferably used (refer to Japanese Patent Laid-Open No. 1-286 0 02). The filter-type molding method is a filter-type mold made of a non-aqueous, capacitive material obtained by depressurizing the water from the slurry of Taurman raw materials in a slurry to obtain a molded body, and is prepared by mixing powder, ion-exchanged water, and organic The slurry consisting of additives is injected into the filter die, and the moisture in the slurry is discharged under reduced pressure only from the side of the screening program to produce a molded body. The obtained ceramic molded body is dried and degreased, and then fired. system. The above-mentioned compression mold is composed of a lower mold for molding having one or more water removal holes, a water permeability screening program arranged on the lower mold for molding, and a method for sealing the mold. The sealing mold of the screening program is formed from a molding template that is held from above. The molding lower mold, the molding template, the poor seal, and the screening program can be detachably assembled separately from the screening program.

. The pressure-reduced slurry is discharged at a pressure of ~ 160 ° C, preferably formed into a given size. In various methods, the firing temperature is preferably 1300 1 3 0 0 ~ 1 4 5 0 ° C. Then, it is used for processing and machining to make it into a bar material. [Embodiment of Invention]

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570909 V. Description of the invention (9) Prepare 1112 03 powder and Sn 02 powder with a purity of> 99-99%. The powder was prepared in accordance with the ratio of SnO2 to 0wt% and InA to 90wt%, and the total amount was 15] ^, and a molded body was obtained by a method of sintering. In an oxygen atmosphere, 155 Gt: conditions, the fired body was fired and sintered for 8 hours. The sintered body was processed to obtain the bulk resistivity of the material as compared with the theoretical one. Under the same conditions as in Example 1, the dc magnetron: = fi Λ 'was used to obtain the oxygen resistance for oxygen as shown in Figure 2. Relationship between resistivity at partial pressure and transmittance at a wavelength of 55 nm. Noon (Example 2) Prepare SiO with a purity of &gt; 99.99% I n 〇 pine 松 ^ Λ. Prepare this powder 2 at a ratio of _2 to 10% ^, Si0 = 99% and 99.9%, and the total amount of 匐 .5Kg: Cao grass 1 is 80% by weight (Si is equivalent to about 0.26 mole), A molded body was obtained by using a molding method under conditions of 1 mol and 1 mol of In in an oxygen atmosphere. Then firing and sintering. After processing the sintered material, the fired body was subjected to 8 small targets with a relative density of 100%. : Target ::: phase :: cm of theoretical density. The volume resistivity was 4.0 χ 1 ()-4 Ω. Using this leather material, a film was formed by s-tube sputtering under the same strain as in Example 1 to obtain a thickness of 1200. 『Under the horror piece, it is obtained by DC magnetron resistivity and transmittance; 3 films such as 8: Second, analyze the relationship between the film and the transmittance at a wavelength of 5 50 nm. Rate (performed in Example 3) ''

570909 V. Description of the invention (ίο) Prepare 1112 03 powder and Sn 02 powder with purity> 99.9 9%, and purity> 99 9% = S10 02 powder. The powder was prepared according to Sn () 2 yQwt%, called 5 "%, ㈣ is a spoon ratio and the total weight was 1.5Kg (relative to 丨 0 Moor), and the molded body was obtained by filtration molding method: Under the conditions of ί η ”and 1 450 c, the calcined body was subjected to 8 hours :: 粍 m. The force sintered body 'obtained a target material having a relative thrust of 100% relative to the theoretical close production. The volume resistivity of this target is U: cm 〇 ^

j: 1 ′ Under the same conditions τ as those in the embodiment, a film having a thickness of 1 200 Å was obtained. The analysis of the "rate and transmittance" of the film showed almost the same oxygen partial pressure characteristics as the picture. = Above, the results can be seen through the examples! The volume resistivity of ~ 3 is in the order of cm. The value is almost the same as that of the previous Iτ〇 target shown in Comparative Example 丨 DC magnetron sputtering; money is okay. Second: Knowing the oxygen partial pressure dependence of the previous 1το film shown in Comparative Example 1 Compared with those shown in Examples 1 to 3, they also have almost the same characteristics, and a film forming method of Syntec's I TO film can be used.

Compared with the resistance in the preferred partial pressure of oxygen of the previous IT0 film shown in Comparative Example 1, the resistivity of Example 1 becomes a magnitude of IO times, and, for Example 2, it becomes 〇 × times. the size of. "In fact," if the film thickness applied to a product is set to about 50 A, the sheet resistance is about 700 Ω. $ On the one hand, in the embodiment 丨. ,: The resistance is about 700 0 Ω. In addition, if the film thickness is set to 15,000 A, the sheet resistance is about 70 Ω in Example 1. On the other hand,

570909 V. Description of the invention (11) In Example 2, the sheet resistance is about 700 Ω. In addition, it can be seen that by increasing the amount of Sn02 added, carriers can be generated 'which tends to reduce the resistance. This shows that not only s i &amp; but also the resistivity can be controlled by adjusting the amount of Sn02 added. From the above, it can be known that by controlling the amount of Sn02, s02, resistivity. [Effect of the Invention] As explained above, the present invention can provide a transparent conductive film of about 0.8 ~ 10xl0 ~ and increase the resistivity.

Indium oxide-based bell-extinguishing dry materials, that is, oxide materials containing indium oxide and root thallium; bright conductive Hong Kong tin and containing high-resistance transparent insulating oxides; therefore, basic materials such as magnetron sputtering can be used. t Use a high-resistance transparent conductive film with a plated target to form a transparent ^ resistive film

C: \ 2D-CODE \ 9】 -09 \ 91】 13997.ptd Page 15 570909 Brief Description of Drawings Figure 1 shows the resistivity against the partial pressure of oxygen and the transmittance at a wavelength of 5 50 0 nm in Example 1. Relationship diagram. FIG. 2 is a graph showing the relationship between the resistivity with respect to the partial pressure of oxygen and the transmittance at a wavelength of 5 50 nm in Comparative Example 1. FIG. Fig. 3 is a graph showing the relationship between the resistivity against the oxygen partial pressure and the transmittance at a wavelength of 5 50 nm in Example 2.

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Claims (1)

1. A high-resistance transparent conductive film with a sputter resistance of about 0.8 to 1 ο X 1 Ο-3 Q cm Gure '"" is used to form an indium oxide-based demineralized leather for electrical conductive films, Γ The high-resistance transparent film of the special electrical film contains indium oxide and oxygen as required. Tin. It also contains insulating oxides. 2. As a high-grade material in the scope of patent application No. 1, among which, the transparent 'electric film's spattered leather The above-mentioned insulating oxides are selected from the group consisting of silicon oxide, silicon oxide, oxidized oxide, oxidized period, hafnium oxide, oxidized dream, :: milk dagger group: magnesium oxide, calcium oxide, hafnium oxide, barium oxide, and said: milk Beryllium, oxidized :, oxidized, oxidized, gallium oxide, =: Si iron oxide, her, oxidized scale, and oxidized group 2 = 3. As the high-electric material of the scope of the patent application, the above-mentioned rugged oxidation ^ \ Transparent transparent conductive film ㈣Ge Geba, 丄 本 1 emulsification system is silicon oxide. 4. :: Please apply for the high resistance of the patent scope item! 'J 中' constituting the above-mentioned insulating oxide of indium , Containing 0 · 0 0 0 〇1 ~ 〇 · 2 6 moles.,; ,,, opposite, 1 mole 5 · The material for the second item of the patent application scope, wherein the dry indium that forms the above-mentioned insulating varistors for the translucent conductive film contains splattered dry indium, which contains 0. 0 0 0 0 1 to 0.26 mol. 6 .: The third material in the scope of patent application, in which the indium for the element conductive film constituting the above-mentioned insulating oxide contains 0.00001 to 0.26 mol. Feng relative to 1 mol C: \ 2D-CODE \ 91-09 \ 91113997.ptd Page 17 570909 7. According to claims 1 to 6 of the scope of application for patents, dried dichroic materials for membranes, in which tin (Sn) 0 · 3 moles. The high-resistance transparent conductive of any one is relative to 1 mol of indium, and contains 0 ~ • Shi declared patent Capricorn Sister; [to 6 items of sputtering target for medium film, bean, chanting, # member of the same Resistive transparent conductive 8 ~ 10 X 10-3 Qcm transparent conductive film.乂 The resistance is half of 0.9. · If the lettuce and item 7 in the scope of the patent application are applied to the bean, spread the "target of a transparent conductive film with a sputtering target Ω. χ 10-3 Qcm transparent conductive film. υχιυ 1 0 · — a kind of high-resistance transparent conductive film made of containing indium oxide and oxygen M as required, and containing 1 in the range of 0 · 8 ~ 1 0 X 1 〇 -3 transparent conductive film. The manufacturing method of the high-resistance transparent conductive film according to the tenth item of the patent scope of Patent 1, wherein, the insulating oxide is selected from the group consisting of oxidizing and oxidizing, oxidizing, oxidizing, oxidizing, and oxidizing. ::: Beryllium oxide: Oxidation town, calcium oxide, hafnium oxide, barium oxide, sharp oxide :: titanium, hafnium oxide, vanadium oxide, boron oxide, gallium oxide, zinc oxide, second oxide, two manganese oxide, oxidation •, oxidation Indium, phosphorus oxide and lanthanum oxide C: \ 2D-CODE \ 91-O9 \ 91113997.ptd Page 18 1 2 · For the high-resistance transparent conductive method according to the scope of patent application, the above-mentioned insulating oxide is silicon oxide.乂 仏 1 3. If the high-resistance transparent conductive and skinning method of item 丨 0 of the patent application scope 'wherein' constitutes the above-mentioned insulating oxide is relative to 570909 6. Application patent scope ear indium contains 0.00001 ~ 0.26 moles. 1 4. The method for manufacturing a high-resistance transparent conductive film according to item 11 of the scope of patent application, wherein the element constituting the insulating oxide is 0.001 to 0.26 mol relative to 1 mol of indium. 1 5. The method for manufacturing a high-resistance transparent conductive film according to item 12 of the scope of the patent application, wherein the element constituting the insulating oxide is 0.00001 to 0.26 mol relative to 1 mol of indium. 1 6. The method for manufacturing a high-resistance transparent conductive film according to any one of claims 10 to 15 in the scope of patent application, wherein tin (Sn) is 0 to 0.3 mol relative to 1 mol of indium . C: \ 2D-C0DE \ 91-09 \ 91113997.ptd page 19