JP3651909B2 - Ceramic rotating cathode target and manufacturing method thereof - Google Patents

Description

[0001]
[Industrial application fields]
The present invention relates to a ceramic rotating cathode target used for forming a ceramic film, in particular, a transparent amorphous oxide film having excellent durability by sputtering, and a method for producing the same.
[0002]
[Prior art]
Conventionally, a thin film formed on a transparent substrate such as glass or plastic to add an optical function includes mirrors, heat ray reflective glass, low radiation glass, interference filters, antireflection coatings for camera lenses and eyeglass lenses, and the like.
In a normal mirror, Ag is formed by electroless plating, and Al, Cr, or the like is formed by vacuum deposition or sputtering. Of these, the Cr film is relatively strong and is used as a surface mirror with the coated surface exposed.
[0003]
In heat ray reflective glass, titanium oxide, tin oxide, or the like has been formed by a spray method, a CVD method, an immersion method, or the like. Recently, a metal film, nitride film, tin-doped indium oxide (ITO) film or the like formed on the glass surface by a sputtering method has been used for heat ray reflective glass. The sputtering method is easy to control the film thickness, can form a plurality of films continuously, and can design transmittance, reflectance, color tone and the like in combination with a transparent oxide film. For this reason, demand is growing for buildings that emphasize design.
[0004]
Low emission glass that reflects radiant heat from indoor heaters and walls to the indoor side is a three-layer system of ZnO / Ag / ZnO in which silver is sandwiched between zinc oxides or ZnO / Ag / ZnO / Ag / It has a structure such as a five-layered ZnO system (see Japanese Patent Laid-Open No. 63-239043) and is used in the form of double-layer glass or laminated glass. In recent years, the spread in the cold regions of Europe is remarkable.
An antireflection coating such as a lens is formed by alternately laminating a high refractive index film such as titanium oxide or zirconium oxide and a low refractive index film such as silicon oxide or magnesium fluoride. Usually, a vacuum evaporation method is used. During film formation, the substrate is heated to improve scratch resistance.
[0005]
Antireflection coatings such as surface mirrors, single-plate heat ray reflecting glass and lenses are used in a state where the coated film is exposed to the air. For this reason, it must be excellent in chemical stability and wear resistance. On the other hand, defective products are generated due to scratches during transportation and handling even before low reflection glass becomes multilayer glass or laminated glass. Therefore, a protective film that is stable and excellent in wear resistance or an optical thin film that also serves as a protective film is desired.
[0006]
In order to improve durability, a chemically stable and transparent oxide film is usually provided on the air side. Examples of the oxide film include a titanium oxide film, a tin oxide film, a tantalum oxide film, a zirconium oxide film, and a silicon oxide film, which have been selected and used according to the required performance.
However, titanium oxide films and zirconium oxide films are excellent in chemical stability, but tend to be crystalline films and have a tendency to increase surface irregularities, which increases friction when rubbed and wear resistance. Inferior to On the other hand, the tin oxide film and the silicon oxide film are each weak against acid alkali and cannot withstand long-time immersion. Of these, the tantalum oxide film has both wear resistance and chemical stability, but is not sufficient in terms of wear resistance.
[0007]
Titanium oxide films, tin oxide films, tantalum oxide films, and zirconium oxide films have a relatively high refractive index, while silicon oxide films have a relatively low refractive index, allowing freedom of optical design in order to provide various optical functions. There is a limit on the degree.
[0008]
Thus, there is a demand for a thin film having high durability and having a wide optical design freedom. The present applicant disclosed in Japanese Patent Laid-Open No. 3-187733 as such a highly durable thin film, at least one of Zr, Ti, Hf, Sn, Ta, In, Cr, B (boron), Si (silicon), A target composed mainly of at least one of O (oxygen) and an amorphous oxide film formed by sputtering the target have been proposed.
[0009]
[Problems to be solved by the invention]
On the other hand, a planar target for sputtering is formed through a long process of mixing and forming inorganic compound raw materials and processing and bonding to form a shape suitable for a sputtering apparatus. Of these, the jig, firing, processing, bonding, and other processes do not require a large jig device when the target is small, but the jig device is large for a large production machine target, and ceramics are also used for bonding. When the target is joined to the target holder metal plate, it is manufactured by dividing and joining the target holder. However, labor and cost are required such as using a large-scale apparatus and a large amount of expensive In solder.
[0010]
Furthermore, in sputtering on large-area glass for construction, high sputtering power is applied to increase the productivity to increase productivity. In this case, the film formation rate is limited by cooling the target, Troubles such as cracking and peeling occur.
[0011]
A new type of magnetron type rotary cathode target which improves these points is known (see Japanese Patent Publication No. 58-500194). This is because magnetic field generation means is installed inside the cylindrical target, and sputtering is performed while rotating the target while cooling from the inside of the target, so that a larger power per unit area can be applied than a planar target. Therefore, high-speed film formation is possible. Most magnetron rotary cathode targets are targets composed of a cylindrical rotary cathode made of a metal or alloy to be sputtered, but if the material to be sputtered is soft or brittle, a metal or alloy is cylindrical. A target manufactured on a target holder.
[0012]
However, in the case of a metal target, oxide films, nitride films, carbide films, etc. can be formed in various sputter atmospheres, and coating of multilayer films is possible. In addition, the low melting point metal target has the disadvantage that it melts when power is applied too much, and a ceramic target is desired.
[0013]
In JP-A-60-181270, a method for producing a sputter target by thermal spraying has been proposed. However, the difference in thermal expansion between ceramics and metal is so large that the thermal sprayed film cannot be made thick, and adhesion due to thermal shock during use is also low. There are problems such as lowering and peeling. There is also a method of manufacturing a ceramic sintered body in a cylindrical shape and joining it to the target holder metal with In metal, but it is difficult to make and costs high.
[0014]
[Means for Solving the Problems]
  The present invention has been made to solve the above-mentioned problems, and in a method for manufacturing a ceramic rotating cathode target, a ceramic target cathode is formed on the outer surface of a cylindrical target holder. After roughing the outer surface, a layer made of a metal or alloy having a thermal expansion coefficient intermediate between the thermal expansion coefficient of the ceramic layer and the thermal expansion coefficient of the target holder on the outer surface,andThe thermal expansion coefficient of the ceramic layer is ± 2 × 10^-6A layer of a metal or alloy having a coefficient of thermal expansion in the range of / ° C.In this orderA ceramic rotating cathode target formed as an undercoat and then transported and adhered to the undercoat with the high-temperature gas while the ceramic powder is in a semi-molten state in a high-temperature gas to form the ceramic layer A manufacturing method is provided.
[0015]
  The present invention also relates to a ceramic rotating cathode target in which a ceramic layer serving as a target to be sputtered is formed on a roughened outer surface of a cylindrical target holder.On the outer surface of the target holder as an undercoat between the ceramic layer and the target holderA layer made of a metal or alloy having a thermal expansion coefficient intermediate between the thermal expansion coefficient of the ceramic layer and the thermal expansion coefficient of the target holder,andThe thermal expansion coefficient of the ceramic layer is ± 2 × 10^-6A layer of a metal or alloy having a coefficient of thermal expansion in the range of / ° C.In orderA ceramic rotary cathode target (hereinafter simply referred to as a rotary cathode target) is provided.
[0016]
In the method of the present invention, ceramic powder is made into a semi-molten state using, for example, a plasma spraying apparatus, and thermally sprayed and adhered to a target holder to form a ceramic layer directly serving as a target. This is the process of filling the mold with powder and press molding, sintering it in an electric furnace, sintering it by hot pressing, modifying it into an appropriate shape, and joining the ceramic and the holder Do not need. When obtaining a thermal spray powder, in the case of a complex compound that is not easily available, it is prepared using chemical synthesis or solid phase reaction. The thermal spray powder can be used by pulverizing and classifying it so as to have a particle size suitable for thermal spraying and easy to flow.
[0017]
The ceramic powder used in the present invention is produced, for example, by the following method. Zr, B, Si, ZrB₂ , ZrSi₂ , ZrO₂ (Y₂ O_Three , CaO, MgO, etc. added 3 to 8 mol% ZrO₂ ), B₂ O_Three , SiO₂ High temperature using chemical synthesis or solid-phase reaction of powder or mixed powder (mixed with carbon powder to reduce oxide if necessary) By firing in an atmospheric furnace, a lump single or composite powder is obtained. The same applies to borides and silicides of metals such as Ti, Ta, Hf, Mo, W, Nb, Sn, La, In, and Cr.
[0018]
It is preferable to obtain a ceramic powder to be thermally sprayed by pulverizing this powder and classifying it to a particle size of about 10 to 75 μm. If it is larger than 75 μm, it is difficult to be in a semi-molten state in a high-temperature gas, and if it is smaller than 10 μm, it is dispersed in the gas at the time of thermal spraying and is difficult to adhere on the target holder.
The aforementioned ceramic powder may contain Fe, Al, Mg, Y, Mn, and H in total of 3 wt% or less, and C is CO during film formation.₂ Therefore, it may disappear, so C may be contained in an amount of 20 wt% or less. Furthermore, impurities such as Cu, V, Co, Rh, Ir, etc. may be included.
[0019]
As the cylindrical target holder, it is possible to use stainless steel, copper, Ti, Mo having a thermal expansion coefficient approximate to that of a ceramic layer, or the like. Prior to thermal spraying of ceramic powder, the outer surface of the cylindrical target holder is made of Al to improve adhesion.₂ O_Three It is necessary to roughen it by sandblasting using SiC abrasive grains. Prior to thermal spraying of ceramic powder, the outer surface of the cylindrical target holder is processed into a V-groove shape or screw shape, and then Al₂ O_Three It is also preferable that the surface is roughened so as to improve the adhesion by sandblasting using SiC abrasive grains.
[0020]
  The cylindrical target holder with a roughened outer surface is coated with an undercoat to reduce the thermal expansion difference between the ceramic layer and the target holder and to increase the adhesion so that peeling due to heat shock during sputtering does not occur. Form. As such an undercoat, a layer made of a metal or alloy having a thermal expansion coefficient intermediate between the target holder and the ceramic layer (hereinafter referred to as A layer), or a layer made of a metal or alloy having a thermal expansion coefficient close to that of the ceramic layer (Hereinafter referred to as B layer) is formed (preferably formed by plasma spraying the powder).Is preferable.In the present invention,Both layers are formed and the structure of target holder / A layer / B layer / ceramic layerYouThe
[0021]
Even if the undercoat is only the B layer, the metal or alloy has high elasticity and small brittleness, so that the adhesion between the ceramic layer and the target holder of the target material can be increased. The thermal expansion coefficient of the B layer is the thermal expansion coefficient ± 2 × 10 of the ceramic layer.^-6Value within the range of / ℃The
[0022]
Undercoat materials include Mo, Ti, Ni, Nb, Ta, W, Ni-Al, Ni-Cr, Ni-Cr-Al, Ni-Cr-Al-Y, Ni-Co-Cr-Al-Y. A conductive powder such as can be used. The thickness of the undercoat is preferably about 30 to 100 μm.
[0023]
The material of the undercoat varies depending on the thermal expansion coefficient of the ceramic layer (the thermal expansion coefficient such as Cu or SUS304 that can be used for the target holder is 17 to 18 × 10^-6/ ° C. ).
[0024]
For example, the ceramic layer may be Zr-B, Zr-B-Si, Hf-Si, Ti-B, Cr-Si, Sn-Si, Zr-Si (Zr: Si (atomic ratio)). = When Zr is less than 33:67), etc. (thermal expansion coefficient 5-6 × 10^-6/ ° C.), the preferred coefficient of thermal expansion of the undercoat A layer is 12 to 15 × 10^-6The material includes Ni, Ni—Al, Ni—Cr, Ni—Cr—Al, Ni—Cr—Al—Y, Ni—Co—Cr—Al—Y, and the like. Moreover, the preferable thermal expansion coefficient of the undercoat B layer is 5 to 8 × 10.^-6The material includes Mo, W, Ta, Nb and the like.
[0025]
The ceramic layer is Ta-B, Ta-Si, Ti-Si (when Ti is less than Ti: Si (atomic ratio) = 33: 67), Zr-Si (Zr: Si (atomic ratio)) = 33:67 or when there is more Zr, ZrSi₂ (Including thermal expansion coefficient) 8-9 × 10^-6/ ° C.), the preferred coefficient of thermal expansion of the undercoat A layer is 12 to 15 × 10^-6The material includes Ni, Ni—Al, Ni—Cr, Ni—Cr—Al, Ni—Cr—Al—Y, Ni—Co—Cr—Al—Y, and the like. Moreover, the preferable thermal expansion coefficient of the undercoat B layer is 8 to 10 × 10.^-6The material includes Ti, Nb, and the like.
[0026]
  When the ceramic layer is Cr-B, Ti-Si (Ti: Si (atomic ratio) = 33: 67 or more Ti than this, TiSi₂System) (including thermal expansion coefficient 10-13 × 10)^-6/ ° C), the preferred coefficient of thermal expansion of the undercoat (B layer) is 10 to 13 × 10.^-6The material includes Ni, Ni—Al, Ni—Cr, Ni—Cr—Al, Ni—Cr—Al—Y, Ni—Co—Cr—Al—Y, and the like.. OrAmong such undercoat materials, the composition ratio may be changed to provide two layers having a thermal expansion coefficient layer close to the target holder and a thermal expansion coefficient layer close to the ceramic layer.
[0027]
On top of that, the above ceramic powder is put in a high-temperature gas, preferably Ar, N₂ Semi-molten in a high-temperature gas in a non-oxidizing atmosphere such as He or the like (“in a high-temperature gas in a non-oxidizing atmosphere” means a high-temperature gas shielded in a non-oxidizing atmosphere; the same applies hereinafter) The ceramic layer serving as a target to be sputtered is formed by transporting and adhering onto the undercoat with a high-temperature gas while maintaining the state. In particular, it is preferably formed by a plasma spraying method performed in high temperature gas plasma (further, in high temperature gas plasma in a non-oxidizing atmosphere). By inserting the undercoat, a stable ceramic layer having a thickness of 2 to 5 mm can be formed.
[0028]
Further, when forming the above-described undercoat, it is preferable to form the undercoat by a plasma spraying method in a high-temperature gas plasma (particularly in a high-temperature gas plasma in a non-oxidizing atmosphere).
[0029]
When a ceramic layer is formed by adhering the ceramic powder to the undercoat in a high-temperature gas in a non-oxidizing atmosphere while adhering it to the undercoat, there is little oxidation of the ceramic powder during the formation of the ceramic layer, and the chemical composition A uniform ceramic layer can be formed without variation.
[0030]
The rotating cathode target produced in this way has good heat conduction from the target material to the target holder and further to the cathode electrode, and because it is firmly attached to the target holder, a high sputtering power is applied to increase the deposition rate. In this case, the cooling is sufficiently performed, and a large amount of electric power can be supplied per unit area without the target peeling or cracking due to a sudden heat shock.
[0031]
Furthermore, in the production method of the present invention, when the ceramic layer is formed in a non-oxidizing atmosphere, a homogeneous target can be formed with little oxidation during the formation of the ceramic layer and no change in chemical composition.
[0032]
Further, since the erosion zone of the ceramic layer becomes the entire surface, there is an advantage that the utilization efficiency of the target is higher than that of the planar type. It is also possible to regenerate the original state by spraying a sprayed powder of the same material on the portion where the ceramic layer is reduced. Furthermore, it is easy to give the thickness of the ceramic layer a distribution depending on the location, whereby the thickness distribution of the thin film to be generated can be controlled by giving the magnetic field strength and temperature distribution on the surface of the ceramic layer.
[0033]
[0034]
Furthermore, the rotating cathode target of the present invention can be used in both DC (direct current) and RF (high frequency) sputtering apparatuses by magnetron sputtering, and high-speed film formation and target utilization efficiency are large, so that film formation can be performed stably. .
[0035]
A thin film formed using a rotating cathode target in which B and / or Si is added to an oxide such as Zr, Ti, Ta, Hf, Mo, W, Nb, Sn, La, In, and Cr is amorphous. It becomes quality. This is presumably because B and / or Si breaks the lattice of the oxide, prevents the growth of the crystal grains of the oxide, and makes the film more amorphous. It is considered that the amorphous film has a lower friction coefficient as a result of the fact that the amorphous film has fewer irregularities on the film surface than the film that is a collection of microcrystals.
[0036]
For this reason, it is considered that the amorphous film is very excellent in lubricity and has few scratches, so that it is difficult to be scratched by friction, and has high scratch resistance and high wear resistance.
[0037]
【Example】
[referenceExample 1] (Example of undercoat 1 layer, Ar gas plasma)
  In this example, a transparent amorphous oxide film having excellent durability can be stably formed at high speed.₂A method of manufacturing a rotating cathode target for ceramics magnetron sputtering will be described.
  ZrO as a ceramic powder material for thermal spraying₂, B₂O₃The carbon mixture was reacted at a high temperature in a non-oxidizing atmosphere to obtain a massive sintered product. This bulk powder was pulverized and classified, and ZrB having a particle size of 20 to 45 μm having a purity of 99.5% was obtained.₂A powder was obtained.
[0038]
A copper cylindrical target holder with an inner diameter of 50.5 mmφ x outer diameter of 67.5 mmφ x length of 406 mm is mounted on a lathe, and the outer surface side is made of Al.₂ O_Three The surface was roughened by sandblasting using abrasive grains to roughen the surface to a roughened surface. Next, as an undercoat, Ni—Al (9: 1) alloy powder was plasma sprayed (using a Metco sprayer) to give a coating having a thickness of 50 μm.
This plasma spraying is performed using Ar gas as the plasma gas, applying a power of 700 A / 35 KV at a flow rate of 42.5 liters per minute, and Ni—Al (9: 1) by using Ar gas plasma at 10,000 to 20000 ° C. The alloy powder was heated instantaneously and transported with the gas to the target holder where it was agglomerated. The operation of moving the plasma spray gun left and right while rotating the target holder on a lathe was repeated many times to form an undercoat.
[0039]
Next, the above ZrB₂ ZrB with a final thickness of 3 mm using the same plasma spraying method with powder₂ A rotating cathode target coated with was obtained.
ZrB obtained in this way₂ A rotating cathode target made of magnet is loaded into a magnetron sputtering device and ZrB is placed on a glass substrate._x O_y A film (Zr: B: O = 1: 2: 5 (atomic ratio)) was formed. Sputtering is Ar and O₂ 1 × 10 in a mixed atmosphere^-3~ 1x10^-2A vacuum of about Torr was performed to obtain a transparent amorphous oxide film having a thickness of 1000 mm.
[0040]
The above-mentioned target was more robust against damage due to heat shock than a planar target in which ceramics were made by a conventional ceramic technique and attached to a target holder. In the above-mentioned conventional planar target, cracks occur and some peeling occurs when the sputtering power is about 2.5 kW. However, the rotating cathode target according to the present invention shows no cracks even at 5 kW and is stable without arcing. The film formation rate of 25 速度 / sec with the conventional planar target was about 4 times as high as the film formation rate of 100 Å / sec with the rotating cathode target of the present invention.
[0041]
[referenceExample 2] (Example of undercoat 1 layer, Ar gas plasma)
  ZrO as a ceramic powder material for thermal spraying₂, SiO₂The carbon powder mixture was reacted at a high temperature in a non-oxidizing atmosphere to obtain a massive sintered product. This bulk powder was pulverized and classified, and ZrSi having a particle size of 20 to 75 μm with a purity of 99.5%.₂A powder was obtained. With this powderreferenceA rotating cathode target was prepared in the same manner as in Example 1, and a film was formed using a magnetron sputtering apparatus. As a result, ZrSi with a thickness of 1000 mm_xO_yA transparent thin film (Zr: Si: O = 1: 2: 6 (atomic ratio)) was obtained. In addition, the film formation rate was about four times as high as that of the conventional planar target by the ceramic technique, and no damage was observed even after power-up.
[0042]
[referenceExample 3] (Example of undercoat 1 layer, Ar gas plasma)
  ZrO as a raw material for thermal spraying₂, SiO₂, B₂O₃The carbon powder mixture was reacted at a high temperature in a non-oxidizing atmosphere to obtain a massive sintered product. This massive powder was pulverized and classified to obtain a Zr-B-Si (atomic ratio of 1: 1: 8) powder having a purity of 99.5% and a particle diameter of 20 to 75 μm. With this powderreferenceA rotating cathode target was prepared in the same manner as in Example 1, and a film was formed using a magnetron sputtering apparatus. As a result, ZrB with a thickness of 1000 mm_xSi_yO_zA transparent thin film of the film (Zr: B: Si: O = 1: 1: 8: 18.5 (atomic ratio)) was obtained. In addition, the film formation rate was about 3.5 times that of the conventional planar target by the ceramic technique, and no cracks or breakage was observed even when the power was increased, and stable high-speed film formation was achieved.
[0043]
[Example1] (Example of two undercoat layers and Ar gas shield atmosphere)
  ZrO as a ceramic powder material for thermal spraying₂, B₂O₃The carbon mixture was reacted at a high temperature in a non-oxidizing atmosphere to obtain a massive sintered product. This bulk powder was pulverized and classified, and ZrB having a particle size of 20 to 45 μm having a purity of 99.5% was obtained.₂A powder was obtained.
[0044]
A copper cylindrical target holder having an inner diameter of 50.5 mmφ, an outer diameter of 67.5 mmφ, and a length of 406 mm is mounted on a lathe, and the outer surface side is machined into a screw shape.₂ O_Three The surface was roughened by sand blasting using abrasive grains to make it rough. Next, as an undercoat, Ni—Al (compounding weight ratio 8: 2) alloy powder was plasma sprayed (using a Metco sprayer) in an Ar gas shield atmosphere to give a coating having a thickness of 50 μm.
On top of this, ZrB₂ Mo metal powder that approximated the thermal expansion coefficient was plasma sprayed in an Ar gas shield atmosphere to obtain a coating having a thickness of 50 μm.
[0045]
This plasma spraying in an Ar gas shield atmosphere is performed in an atmosphere in which a plasma spray gun and a cylindrical target holder are surrounded by a metal shield box and Ar gas is flowed in a spiral shape therein, and Ar gas is converted into plasma. It is used as a gas at a flow rate of 42.5 liters per minute by applying a power of 700 A and 35 KV. Ar gas plasma of 10,000 to 20000 ° C. is used to produce alloy powder of Ni—Al (compounding weight ratio 8: 2) or Mo. The metal powder was heated instantaneously and transported with the gas to the target holder where it was agglomerated. The operation of moving the plasma spray gun left and right while rotating the target holder on a lathe was repeated many times to form an undercoat.
[0046]
Next, the above ZrB₂ ZrB with a final thickness of 3 mm using the same plasma spraying method with powder₂ A rotating cathode target coated with was obtained.
The relative density of the ceramic layer was 90%. O in the ceramic layer₂ The content was 1.1 wt%.
[0047]
ZrB obtained in this way₂ A rotating cathode target made of magnet is loaded into a magnetron sputtering device and ZrB is placed on a glass substrate._x O_y A film (Zr: B: O = 1: 2: 5 (atomic ratio)) was formed. Sputtering is Ar and O₂ 1 × 10 in a mixed atmosphere^-3~ 1x10^-2A vacuum of about Torr was performed to obtain a transparent amorphous oxide film having a thickness of 1000 mm. The chemical composition (Zr / B ratio) of this amorphous film was the same as that of the target (Zr / B ratio).
[0048]
The above-mentioned target was more robust against damage due to heat shock than a planar target in which ceramics were made by a conventional ceramic technique and attached to a target holder. In the above-mentioned conventional planar target, cracks occur and some peeling occurs when the sputtering power is about 2.5 kW. However, the rotating cathode target according to the present invention shows no cracks even at 5 kW and is stable without arcing. The conventional planar target had a film formation rate of 25 Å / sec, and the rotary cathode target of the present invention had a high film formation rate of 100 Å / sec, which is about four times.
[0049]
[Example2] (Example of two undercoat layers and Ar gas shield atmosphere)
  ZrO as a ceramic powder material for thermal spraying₂, SiO₂The carbon powder mixture was reacted at a high temperature in a non-oxidizing atmosphere to obtain a massive sintered product. This bulk powder was pulverized and classified, and ZrSi having a particle size of 20 to 75 μm with a purity of 99.5%.₂A powder was obtained. ZrB₂Example except that this powder was used instead of the powder, and Ti metal powder was used instead of the Mo metal powder.1A rotating cathode target was prepared in the same manner as described above. The relative density of the ceramic layer is 92% and O₂The content was 0.9 wt%.
[0050]
  Using this rotating cathode target, a film was formed by a magnetron sputtering apparatus. As a result, ZrSi with a thickness of 1000 mm_xO_yA transparent thin film (Zr: Si: O = 1: 2: 6 (atomic ratio)) was obtained. Example1ZrB₂As in the case of the target, there was no change in the chemical composition of the target, and a film formation rate of about 4 times that of the conventional planar target by the ceramic method was obtained, and no damage was observed even when the power was increased.
[0051]
[Example3] (Example of two undercoat layers and Ar gas shield atmosphere)
  ZrO as a raw material for thermal spraying₂, SiO₂, B₂O₃The carbon powder mixture was reacted at a high temperature in a non-oxidizing atmosphere to obtain a massive sintered product. This massive powder was pulverized and classified to obtain a Zr-B-Si (atomic ratio of 1: 1: 8) powder having a purity of 99.5% and a particle diameter of 20 to 75 μm. Except for using this powder1A rotating cathode target was prepared in the same manner as described above. The relative density of the ceramic layer is 91.5% and O₂The content was 0.85 wt%.
[0052]
  Using this rotating cathode target, a film was formed by a magnetron sputtering apparatus. As a result, ZrB with a thickness of 1000 mm_xSi_yO_zA transparent thin film of the film (Zr: B: Si: O = 1: 1: 8: 18.5 (atomic ratio)) was obtained. Example1ZrB₂Targets and examples2ZrSi₂As with the target, there is no change in the chemical composition of the target, and the film formation speed is approximately 3.5 times that of a conventional planar type target. The film could be stably formed at a high speed.
[0053]
【The invention's effect】
According to the method of the present invention, since the rotating cathode target is prepared using a thermal spraying method, a conventional ceramic production facility is not required, and it can be easily produced at a low cost in a short time without a work joining process. Applicable to inorganic materials. In particular, high melting point materials and high melting point metals that are difficult to be made into ceramics are cheaper in powder form, and are particularly effective when such materials are targeted.
[0054]
In addition, when the ceramic layer is formed in a non-oxidizing atmosphere in the method of the present invention, a homogeneous target can be formed without changing the chemical composition even when targeting a metal that easily oxidizes or a compound of two or more components. .
[0055]
Further, according to the method of the present invention, the bonding between the ceramic layer and the target holder is unnecessary, the target can be easily manufactured, and the eroded portion of the ceramic layer can be regenerated.
[0056]
If the rotating cathode target of the present invention is used, the cooling efficiency at the time of sputtering is high, and even if the sputtering power is increased, there is no cracking or breakage of the target. The industrial value is enormous, such as significantly improving the productivity of large area glass and increasing the efficiency of target utilization.
[0057]
In addition, if a rotating cathode target having a specific composition is used, an amorphous oxide film having high durability and having a degree of freedom in optical design that can control the refractive index by the addition amount of B and / or Si can be provided. .
An amorphous oxide film has high scratch resistance, high wear resistance, and high chemical durability, and therefore can be widely used as an overcoat for various articles. For example, it is most suitable for outermost layers such as heat ray reflective glass for buildings and vehicles, a protective plate for a reading part of a barcode reader, an antireflection film, and a lens for spectacles. It can also be used as a coating material for sliding members.

Claims (5)

In a method for manufacturing a ceramic rotating cathode target in which a ceramic layer serving as a target to be sputtered is formed on the outer surface of a cylindrical target holder, after roughening the outer surface of the cylindrical target holder, A layer made of a metal or an alloy having a thermal expansion coefficient intermediate between the thermal expansion coefficient of the ceramic layer and the thermal expansion coefficient of the target holder, and ± 2 × 10 ⁻⁶ / ° C. with respect to the thermal expansion coefficient of the ceramic layer A layer made of a metal or alloy having a thermal expansion coefficient within a range is formed as an undercoat in this order, and then the ceramic powder is transported onto the undercoat by the high temperature gas while being in a semi-molten state in the high temperature gas. The ceramic rotating cathode is characterized in that the ceramic layer is formed by attaching Manufacturing method of de target. The ceramic powder is a powder mainly composed of at least one of Zr, Ti, Ta, Hf, Mo, W, Nb, Sn, La, In, and Cr and at least one of B, Si, and O. The manufacturing method according to claim 1 . In a ceramic rotating cathode target in which a ceramic layer to be a target to be sputtered is formed on the roughened outer surface of the cylindrical target holder, an undercoat is provided between the ceramic layer and the target holder as described above. on the outer surface of the target holder, a layer made of a metal or alloy having a thermal expansion coefficient intermediate between the thermal expansion coefficient of the thermal expansion coefficient of the ceramic layer and the target holder, and, with respect to the thermal expansion coefficient of the ceramic layer A ceramic rotary cathode target comprising a layer made of a metal or an alloy having a thermal expansion coefficient in a range of ± 2 × 10 ⁻⁶ / ° C. in order . The ceramic layer is mainly composed of at least one of Zr, Ti, Ta, Hf, Mo, W, Nb, Sn, La, In, and Cr and at least one of B, Si, and O. ceramic rotary cathode target according to 3. A film forming method comprising forming a film by sputtering the ceramic rotating cathode target according to claim 3 .