TWI276696B - Silicon monoxide sintered product and sputtering target comprising the same - Google Patents

Abstract

A silicon monoxide sintered product prepared through forming a raw material powder which consists of 20 to 80 mass % of a silicon powder doped with boron, phosphorus or antimony and the balanced amount of silicon monoxide or a mixture of silicon monoxide and silicon dioxide, wherein the content of silicon monoxide in the mixture is 20% or more; and a sputtering target using the silicon monoxide sintered product. The sputtering target can be used for securing a satisfactorily high rate of film formation while providing a film reduced in variations of film characteristics, and thus can be widely and advantageously used for forming a silicon oxide thin film as a film for optical use, for example, for use in the prevention of gas permeation in a transparent plastic and the prevention of dissolution of Na from a glass and the protection of the surface of a lens.

Description

1276696 (1) Description of the Invention [Technical Field] The present invention relates to a niobium oxide sintered body and a sputtering target therefor. More specifically, it refers to an optical film for preventing the transparent plastic from being ventilated, and a yttria sintered body which is used for preventing dissolution of sodium in the glass or a protective film on the surface of the lens, and a sputtering target thereof. [Prior Art] A ruthenium oxide film such as a ruthenium dioxide film or a SiOx (1<X<2) film is used as an insulator for various optical parts because of its excellent electrical insulation and high mechanical strength; It is transparent and has good barrier properties to gases. It is also used as a protective film for transparent plastics to prevent gas permeation. When a film is formed by using ruthenium dioxide and SiOx as a base material, ruthenium, ruthenium oxide and ruthenium dioxide are sputtering targets, which are carried out by reactive sputtering. This reactive sputtering method is applied by a two-pole DC reactive sputtering method and a high-frequency reactive sputtering method. First, when a film is formed by a two-pole DC reactive sputtering method, an inert gas such as argon is mixed with nitrogen or oxygen under reduced pressure, and a direct current high voltage is applied between the electrodes to discharge (glow discharge). This discharge causes the inert gas to ionize and rushes toward the cathode at a high speed to fly the substance (target) disposed on the cathode. These flying substances are deposited on the surface of a substrate such as a nitride or an oxide to form a film. The relatively high-frequency reactive sputtering method replaces the DC high-voltage electricity applied by the above-mentioned two-pole DC reactive sputtering method, and applies a high-frequency electric wave of 1276696 (2) above 50 kHz, causing high-cycle glow discharge, which is the same as the above case. A film is formed on the surface. The above two-pole DC reactive sputtering method has the advantages of simple device and easy operation, and rapid film formation. However, when the target is a high-resistance substance or an insulator, it is unlikely to be charged and sputtered by positive ions. On the other hand, since the high-frequency reactive sputtering method utilizes high-frequency discharge, it is possible to maintain a glow discharge even when an insulator or the like is used as a target, and a thin film can be formed. However, the high-period reactive sputtering method is slower than the two-pole DC reactive sputtering method, and even more complicated in its power supply structure, resulting in high equipment manufacturing costs, and the reliability or maintainability of the power supply is also disturbing. Therefore, this method has the problem of achieving stable high-cycle current. In order to cope with such a problem, it has been attempted to form a film by a DC reactive sputtering method using a base material which is formed by a high-frequency reactive sputtering method and which is formed into an insulating film. For example, it is known that a main material (P L Z T, P Z T system) is deficient in a part (oxygen-containing component), and after reducing its electric resistance, it can be processed by DC reactive sputtering. In order to reduce the electric resistance of the sintered body, a conductive material and an insulating material are mixed and sintered to obtain a highly conductive sintered body, which is suitable for DC reactive sputtering (JP-200-256) 7 3 Bulletin No. 1, No. 200 1 - 5 8 7 1 , etc.). However, in the above method, the method of using the defective oxygen to make the sintered body electrically conductive is limited, and the material to be used in the present invention is not applicable to the material of the present invention. In addition, the method of obtaining a highly conductive sintered body by mixing the insulating material with the conductive material is carried out, and the sintered -7 - 1276696 (3) body of different materials is mixed, and the different materials are simultaneously formed at the time of sputtering. The film properties are caused by problems such as unevenness in the resistivity of the mixed sintered body's plated crucible. SUMMARY OF THE INVENTION As described above, an oxidized sand-based film is produced by a reactive sputtering method using a shape of 7, yttrium oxide oxide as a sputtering target. However, the stage of crystal growth, doping with boron, phosphorus or antimony, is likely to cause low electricity. Therefore, the doped powder which is usually doped is used for the DC sputtering apparatus gas, and the film can be formed by DC reactive sputtering. On the other hand, when a sintered body of cerium or cerium oxide is used as a sputtering target, the material is not formed by high-frequency reactive sputtering. The use of doped bismuth powder in a DC reactive sputtering method produces a high film speed, but the reactive sputtering conditions are easily changed, resulting in variations in the characteristics of the ruthenium-based film. Moreover, the high output power is discharged and the problem is easily broken. Further, when SiOx (l < X < 2) film and cerium oxide film are formed, one of cerium oxide and cerium oxide is used as a target, and the oxygenation amount is reduced, and the film characteristics are homogenized. As described above, and ruthenium dioxide have low conductivity and a layer of insulating material, it is required to be used in a reactive sputtering apparatus. Therefore, compared with the DC reactive sputtering method, it is slow, and it is difficult to enlarge the sintered body. The present invention is a versatile change in the production of oxidized stone by reactive sputtering. First, the occurrence of bismuth and bismuth in the mono-resistance can be introduced into the oxygen-oxidized conductivity, the film, which forms the film of oxygen, doping, using the membrane to the atmosphere to conduct oxidation Film speed film, -8- 1276696 (4) Identify the problems that occur during film formation; reduce the resistance of the sintered body, make it suitable for DC reactive sputtering devices, ensure the film formation speed, and also make the film The characteristics are stabilized; more than a different material, a single-component film can be produced to provide a cerium oxide sintered body and a sputtering target thereof. The inventors of the present invention have focused on solving the above-mentioned problems, and have conducted various review results on a film formation method of a ruthenium oxide-based film, and have found that it is applicable to a DC current sputtering apparatus if a sintered body of yttria having conductivity can be produced. Can be made into a ruthenium oxide film. According to this result, it is possible to ensure the film forming property to be stable, and at the same time, the film forming speed can be increased, the productivity is improved, and good film forming efficiency is obtained. In the above review, it was learned that the doped cerium powder and the cerium oxide powder or the mixed powder of cerium oxide and cerium oxide were mixed and sintered, and the inside or the surface of the oxidized sand powder was oxidized. Cut, the heat is broken down into "Shi Xi 12 oxidized sand." In other words, the cerium oxide of the insulator is mixed with the conductor which becomes strongly doped, and the thermal decomposition sand interacts with the mixed sand through sintering to obtain good conductivity. Moreover, even if they are mixed and sintered, or yttrium, lanthanum oxide and cerium oxide are all used for reactive sputtering, since the films of the same composition are formed by the ruthenium oxide film, the occurrence of the conventional mixed sintering, such as film properties, is solved. Change, sputtering target resistance is not uniform. The present invention is based on the above findings, and mainly completes a sputtering target of a cerium oxide sintered body of (1) to (4) and a sintered body of cerium oxide (5). -9- 1276696 (5) (1) A powder of boron, phosphorus or cerium doped with cerium, and a mixture of oxidizing and oxidizing is used as a raw material powder to form an oxide. (2) A cerium oxide sintered body characterized by being doped with boron, phosphorus cerium powder and containing the remaining cerium oxide in a mass percentage of 20 to 80% as a raw material powder. (3) It is characterized in that boron, phosphonium powder is doped with 20% to 80% by mass, and the other cerium oxide and cerium oxide mixture (in which the cerium content is 20% or more) is sufficiently mixed and used as a raw material powder. One of the yttria sintered bodies. The cerium oxide sintered body as recited in the above items (1) to (3) has a bulk density of at least 95% after the knot. (4) A sintered body of yttrium oxide having a specific resistance ratio of 8 Ω · cm to 4 X 1 Ο·3 Ω · cm. (5) A sputtering target having one of the characteristics described in the above items (1) to (4). [Embodiment] The present invention is a sintered body of cerium oxide characterized by being doped with boron in an amount of 20 to 80% by mass. Further, it is desirable that the sintered body of the content 3 which is made of the doped strontium powder can be used as a target of a direct current power source sputtering apparatus because of its conductivity. At the time of reactive sputtering, a film made of a cathode (target) as a sputtering device has a characteristic of reducing variation, and good sputtering can be obtained!矽 Powder 矽 Sintered or 锑 成 成 锑 锑 锑 希望 希望 希望 希望 希望 希望 希望 希望 希望 希望 希望 希望 希望 希望 希望 希望 希望 希望 希望 希望 希望 希望 6 6 6 6 6 6 6 6 6 6 6 6 6 6 -10- 1276696 (6) A part containing doped yttrium powder and some of the Si powders are in contact with each other to exhibit conductivity, but in the case of mixed sintering, one part of the oxidized portion or the surface SiO is thermally decomposed. At this time, in the crucible where the thermal decomposition is completed, the elements in the conductive niobium powder such as boron, phosphorus or antimony are increased in electrical conductivity due to thermal diffusion. According to the experimental results of the inventors, the sintering temperature of the sintered body is confirmed. The resistivity can drop rapidly. In the sintered body of the present invention, if the amount of doping contained is less than 20%, the electrical resistivity cannot be sufficiently lowered. This is because the doped particles are too coarsely distributed. Therefore, the minimum content of doping at the end of the doping: is expected to be 30%. On the one hand, when the content of the tantalum powder is more than 80%, the ruthenium oxide disappears, and like the target of the ruthenium, the film produced has a defect in film characteristics, which is easy to be cut when the power is input. Therefore, the amount of doping is up to 80%, and the desired enthalpy is 60%. At the time of the mixed sintering, the cerium oxide was not mixed, and even if the doping was mixed with the cerium oxide powder and sintered, 95% of the bulk density as a target could not be achieved. However, if there is a cerium oxide powder during hot pressing, the bulk density can be charged above 95%. It is presumed that the reason is that the temperature of sublimation of nitric oxide is low, and the hot pressing becomes glassy at the same time, and the mixed cerium in the raw material powder is soaked in the gap between the powder and the cerium oxide powder to form a glass body. From the above, it is understood that the raw material powder of the sintered body of the present invention is doped in the tantalum powder. When the pick-up is made, the sorghum powder has a characteristic of 20%, and the high-transmission and high-content Shishi end requirement reaches 1 200 °C. The oxygen-like sintering needs to be mixed with -11 - 1276696 (7) The sputum is mixed with the cerium oxide powder. However, in order to adjust the oxygen concentration of the target, the mixed raw material of the doped cerium oxide and the cerium oxide powder is mixed with the dioxide: 5 powder, which is also effective. In this case, the characteristics of cerium oxide are not lost, and in order to uniformize the film properties of leather E, the content of cerium oxide powder needs to be more than 20%. The expectation is 30% or more. Further, in the sintered body of the oxidized sand, the average particle diameter of the raw material powder is desirably small from the viewpoints of improvement in sinterability, uniformization of electric conductivity, and uniformity of film composition. On the one hand, the raw material powder is too fine, and the problem of poor mixing may occur. Therefore, it is desirable that the average particle diameter of the raw material powder is in the range of 1 to 2 〇μm. At the end of the doping of the oxidized sand sintered body of the present invention, it is desirable that the specific resistance is 0.01 Ω · cm (local resistivity). The target is 0.0001 Ω · cm (low resistivity). When the high resistance is exceeded, sufficient conductivity cannot be ensured, and when the resistance is lower than the low resistance, the material cost is increased. The method of doping boron, phosphorus or antimony is not particularly limited, and it is usually a method employed in the breeding stage of monoclinic crystals. The doping amount of boron, phosphorus or antimony is added by the specific resistance as noted above for the singly grown single crystal. In the cerium oxide sintered body of the present invention, the powder containing cerium oxide as a main component, that is, the powder of cerium oxide and the mixed powder of cerium oxide and cerium oxide, contains 20 - 80% doped cerium powder, and is thoroughly mixed. The obtained powder is applied at a pressure of 1000 kg/cm 2 or more, and it is desired to be pressure-fired at a temperature of 1,250 to 1,400 ° C. When the sintering temperature is too high, the bismuth powder is dissolved, and a good burned body cannot be obtained; on the contrary, the sintering temperature is too low, the sintering is insufficient, and the thermal diffusion of the doped borophosphide-12-12276696 (8) is insufficient. Therefore, it is preferred to produce a cerium oxide of the present invention having a sintering temperature of from 1,250 to 140 (TC, but preferably from 1 300 to 1400 ° C. Examples of the present invention are obtained by using the present invention as a cerium oxide sintered body. The effect is illustrated as an example.

In the example, boron is doped and the specific resistance is adjusted to 0.0004 Ω · cm. The average particle size of the finely pulverized powder at the end of the sputum and the end of the cerium oxide is less than 10 μm. The content of cerium in the end of cerium oxide is in the range of 10 to 90%, and the powder is applied with a pressure of 9.8 MPa (10 〇〇 kgf/cm 2 ), and after being pressed and sintered at 1 400 ° C for 2 hours, it is 0 6 in x t 5 mm. Machining, making a sputtering target. The surface resistivity and the percentage of density of various sintered bodies prepared under the above conditions were measured, and further, these sintered bodies were used as targets, and a tantalum oxide film was produced by DC power source reactive sputtering, and sputtering of a film thickness per unit time was measured. Rate while observing membrane property deviations.

The surface resistivity is measured by the four-terminal method, and the density ratio (body density/ideal density) is represented by X 1 0 0 %. The variation in film properties was observed based on the measurement results of the transmittance and the yield. The above measurement results and observation results are shown in Table 1. -13- 1276696 (9) Table 1 Number of trials 1st 2nd 3rd 4th 5th 6th 7th 矽 content (%) 10 20 30 50 80 90 30 cerium oxide content (%) 0 0 0 0 0 0 10 specific resistance (Ω · cm) 70 8 8 xlO·2 6 xlO·2 4 χΚΤ3 4 xlO'4 1 xlO'1 Density ratio (%) 100 100 100 99 99 100 100 Sputtering rate Δ 〇 ◎ ◎ ◎ 〇 ◎ Membrane characteristic deviation 〇〇〇〇〇Δ 〇 According to the results of Table 1, according to the provisions of the present invention, it is known that the content of doping in the oxidized powder is in the range of 20 - 80%, the sputtering rate And the deviation of the film characteristics is good. Further, as a reference test, a sintered body was produced by using cerium oxide powder under the same conditions as described above, and the obtained sintered body was machined to form a sputtering target to form a ruthenium dioxide film. At this time, the same measurement and observation were carried out, and the surface resistivity of the sintered body was confirmed to be 1 Ο 7 Ω · cm or more, and the sputtering rate was poor, which was the same as in the first test of Table 1. As described above, the yttria sintered body of the present invention has a reduced electrical resistivity and is suitable for use in a DC reactive sputtering apparatus, in addition to ensuring the film forming speed, and at the same time ensuring the film properties of -14-1276696 (10). Industrial use possibility

When the yttria sintered body of the present invention is applied, the resistivity of the sintered body is lowered, and it can be applied to a DC reactive sputtering apparatus. In addition to ensuring the film formation rate, the film properties of the film formation can be promoted, and the heterogeneous species are not used. The material can be made into a single component film. Therefore, such a niobium oxide sintered body and a sputtering target thereof are used to ensure a plating reaction such as a good sputtering rate and a small variation in film characteristics. According to the present invention, it can be widely applied to film formation for preventing the optical film of the transparent plastic stomach m, preventing the dissolution of the glass sodium and the yttrium oxide film for the surface protective film of the lens.

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Claims (1)

J276696\ χ. Patent scope No. 92 1 06660 Patent application Chinese patent scope selection - car 圏兮曰1 · A niobium monoxide sintered body characterized in that it contains 20 to 80% of cerium powder doped with boron, phosphorus or cerium in the mass%, and the balance is cerium oxide or cerium oxide a mixture of cerium oxide having a cerium oxide content of 20% or more. In the case of mixing cerium oxide, a raw material powder having a cerium oxide content of 10% or less is formed, and an average particle diameter of the raw material powder is formed. It is 1 to 20 μm, the bulk density after sintering is 95% or more, and the specific resistance is 8 Ω · cm 〜 4 X 1 (Γ3 Ω · cm. 2 · a cerium oxide sintered body characterized by mass % The raw material powder containing 20 to 80% of boron, phosphorus or strontium doped with cerium oxide is thoroughly mixed and formed, and the obtained powder is pressurized at a pressure of 1 000 kg/cm 2 or more. At the same time, it is pressed and fired at a temperature of 1,500 to 1400 ° C, and the bulk density after sintering is 95% or more, and the average particle diameter of the raw material powder is 1 to 20 μm. 3·-one cerium oxide sintered body, characteristics thereof In order to obtain, by mass%, 20 to 80% of cerium powder doped with boron, phosphorus or cerium, The remainder is formed by a mixture of cerium oxide or cerium oxide and cerium oxide, and the raw material powder having a cerium oxide content of 20% or more in the mixture is sufficiently mixed and formed, and the obtained powder is above l〇〇kg/cm2. The pressure is pressurized and simultaneously pressed at a temperature of 1,500 to 1 400. (:: the body density after sintering is 95% or more, and the average particle diameter of the raw material powder 1276696 (2) is 1 to 20 μm. The yttria sintered body according to claim 2 or 3, wherein the specific resistance is 8 Ω · cm 〜 4 χ 10' 3 Ω · cm. 5 - a sputtering target, which is characterized by the first scope of the patent application. A sintered body of cerium oxide according to any one of the three items. 6. A sputtering target according to claim 5 of the patent application, which is used for reactive sputtering using a DC power source. -2-