JPH05230645A - Ceramic rotary cathode target and its manufacture - Google Patents

Abstract

PURPOSE:To provide a rotary cathode target free from the need of the stage for joining with a target holder and high in a raw material yield at a high density. CONSTITUTION:The outer surface of a cylindrical target holder 2 is roughened, on which an undercoat of a layer constituted of a metal or an allay having a thermal expansion coefficient which is the medium between that of a ceramic layer and that of the target holder 2 or the like is formed. Then, the ceramic powder 4 is filled into the circumference of the outer surface of the cylindrical target holder 2, and hot isotropic pressing is executed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a ceramic rotating cathode target used for forming a ceramic film, particularly a transparent amorphous oxide film having excellent durability, by a sputtering method and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, a thin film is formed on a transparent substrate such as glass or plastic to add an optical function to a mirror, a heat ray reflecting glass, a low radiation glass, an interference filter, an antireflection coat for a camera lens or a spectacle lens. Etc. In a normal mirror, Ag is formed by an electroless plating method, and Al or Cr is formed by a vacuum deposition method, a sputtering method, or the like. Of these, the Cr film is relatively strong and is therefore used as a part of a surface mirror whose coated surface is exposed.

Titanium oxide, tin oxide and the like have been used to form the heat ray reflective glass by a spray method, a CVD method, an immersion method or the like.
Recently, a metal film, a nitride film, tin-doped indium oxide (ITO) or the like formed on the glass surface by a sputtering method has come to be used as a heat ray reflective glass. In the sputtering method, the film thickness can be easily controlled, a plurality of films can be continuously formed, and the transmittance, the reflectance, the color tone and the like can be designed in combination with the transparent oxide film. For this reason, demand is increasing for buildings that emphasize design.

Low-emissivity glass that reflects radiant heat from an indoor heater or wall to the indoor side is a ZnO / Ag / ZnO three-layer system in which silver is sandwiched by zinc oxide or Z.
5-layer system of nO / Ag / ZnO / Ag / ZnO
3-239043) and is used in the form of double glazing or laminated glass. In recent years, it has been remarkably popularized in cold regions of Europe. For the antireflection coating of a lens or the like, 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 are alternately laminated. Usually, a vacuum vapor deposition method is used, and the substrate is heated during film formation to improve scratch resistance.

Surface mirrors, single-plate heat ray-reflecting glass, and antireflection coatings such as lenses are used in a state where the coated film is exposed to the air. Therefore, it must have excellent chemical stability and abrasion resistance. On the other hand, even low-reflection glass may be defective due to scratches during transportation or handling before it becomes a double-glazing or laminated glass. Therefore, a protective film that is stable and has excellent wear resistance or an optical thin film that also serves as a protective film is desired.

To improve durability, a chemically stable and transparent oxide film is usually provided on the air side. As these oxide films, there are titanium oxide, tin oxide, tantalum oxide, zirconium oxide, silicon oxide, etc., which have been selected and used according to the required performance.

However, although titanium oxide and zirconium oxide are excellent in chemical stability, they tend to form a crystalline film and tend to have large irregularities on the surface. Therefore, when they are rubbed, friction is increased and wear resistance is increased. Inferior to. On the other hand, tin oxide,
Each of the silicon oxides is vulnerable to alkali acids and cannot withstand long-term immersion. Among these, tantalum oxide is wear resistant,
It has both chemical stability, but it is still insufficient in terms of wear resistance. In addition, titanium oxide, tin oxide,
Tantalum oxide and zirconium oxide have a relatively high refractive index, while silicon oxide has a relatively low refractive index, which limits the degree of freedom in optical design for providing various optical functions.

As described above, there is a demand for a thin film having high durability and a wide degree of freedom in optical design. The applicant of the present invention has disclosed in Japanese Patent Laid-Open No. 3-187733 that, as such a highly durable thin film, at least one of Zr, Ti, Hf, Sn, Ta, In and Cr and at least one of B, Si and O are used.
We proposed a target consisting mainly of seeds and an amorphous oxide film formed by sputtering this target.

[0009]

On the other hand, a planar target for sputtering is formed by mixing raw materials of an inorganic compound,
It is created through processing and bonding and a long process to obtain a shape suitable for the firing and sputtering device. Among these, the steps such as molding, firing, processing, and bonding do not require a large jig device when the target is small, but the large jig target requires a large jig device, and the bonding jig also requires ceramics. When the target is bonded to the target holder metal plate, it is manufactured by dividing and processing and joining, but it requires labor and cost such as using a large-scale device and a large amount of expensive In solder.

Further, in the case of sputtering large-area glass for construction, a high sputtering power is applied to increase the film forming speed in order to improve productivity, but in this case, the cooling of the target limits the film forming speed. There are problems such as cracking and peeling.

A new type of magnetron type rotating cathode target which is improved in these points is known (see Japanese Patent Publication No. 58-500174). This is because the magnetic field generating means is installed inside the cylindrical target, and the sputtering is performed while rotating the target while cooling from the inside of the target, so that a larger power can be input per unit area than the planar target. Therefore, high-speed film formation is possible. Most of such targets are cylindrical rotating cathodes made of a metal or alloy to be sputtered, and when the substance to be sputtered is a soft or brittle metal or alloy, it is manufactured on a cylindrical target holder.

However, in the case of a metal target, it is possible to coat a multilayer film of oxides, nitrides, carbides, etc. in various sputtering atmospheres, but the coating film is damaged by a different atmosphere and the desired composition cannot be obtained. Further, a low-melting-point metal target has a drawback that it melts when too much power is applied, and a ceramic target is desired.

A method for producing a sputter target by thermal spraying is proposed in Japanese Patent Laid-Open No. 60-181270, but the thermal spray film cannot be made thick due to a large difference in thermal expansion between ceramics and metal, and the thermal shock during use causes a close contact. There is a problem that the property is deteriorated and peeling occurs. There is also a method of manufacturing a ceramics sintered body into a cylindrical shape and joining it to a target holder metal with In metal, but it is difficult to manufacture and costly.

The applicant of the present invention, in Japanese Patent Application No. 3-242557, roughens the outer surface of the cylindrical target holder, and then,
A layer made of a metal or an alloy having a thermal expansion coefficient intermediate between the thermal expansion coefficient of the ceramic layer to be formed later and the thermal expansion coefficient of the target holder is formed as an undercoat, and then the ceramic powder is semi-exposed in high temperature gas. We proposed a method for producing a ceramic rotating cathode, which is characterized in that the gas is transported to and deposited on the undercoat while being in a molten state to form a ceramic layer as a target to be sputtered.

However, when the difference in the coefficient of thermal expansion between the ceramic layer and the target holder is large, problems such as cracks in the coating of the ceramic layer during plasma spraying or sputtering, and the chemical composition of the ceramic layer in the atmosphere However, there is a problem that it changes due to oxidation due to plasma spraying.

As a result of earnest research in view of the above-mentioned object, the present invention further improves the adhesion between the target holder and the ceramic layer, and the ceramic rotating cathode capable of uniform and stable sputtering without the change of the chemical composition of the ceramic layer. A target manufacturing method is proposed.

[0017]

The present invention has been made to solve the above-mentioned problems, and the outer surface of a cylindrical target holder is roughened, and the coefficient of thermal expansion of a ceramic layer to be formed later is formed on the outer surface of the cylindrical target holder. And at least one of a layer made of a metal or an alloy having a thermal expansion coefficient intermediate between those of the target holder and a layer of a metal or an alloy having a thermal expansion coefficient close to that of the ceramic layer. Is formed as an undercoat by plasma spraying, and then ceramic powder or a molded body of such powder is placed around the outer surface of the cylindrical target holder, and hot isostatic pressing is performed. A method of manufacturing a rotating cathode target is provided.

Further, a ceramic layer serving as a target to be sputtered is formed on the outer surface of the cylindrical target holder, and a coefficient of thermal expansion intermediate between the coefficient of thermal expansion of the ceramic layer and the coefficient of thermal expansion of the target holder is set. At least one layer selected from the group consisting of the metal or alloy and the layer consisting of the metal or alloy having a coefficient of thermal expansion close to that of the ceramic layer serves as an undercoat between the ceramic layer and the target holder. Provided is a ceramic rotating cathode target characterized by being formed.

The method of the present invention is basically a method for hot isostatic pressing (hereinafter, referred to as "ceramic powder").
It is sintered and bonded to a target holder by HIP) to directly form a ceramic layer as a target. By this, the process of packing powder in a conventional mold and press-molding, the process of sintering it in an electric furnace,
Alternatively, there is no need for a step of sintering by hot pressing, a step of processing and modifying into an appropriate shape, and a step of joining ceramics and a holder.

The method of the present invention comprises a step of obtaining a raw material powder, a surface treatment step for closely bonding the outer surface of a cylindrical target holder to a ceramic layer, and a step of sintering and bonding by HIP processing. ing.

The ceramic powder used in the present invention is produced by utilizing chemical synthesis or solid-state reaction, particularly in the case of a complex compound which is not easily available. This powder can be used by pulverizing it, granulating it, and flowing it into the HIP-treated capsule to make it into a secondary particle size that facilitates vibration filling.

The ceramic powder used in the present invention can be produced, for example, by the following method. That is, Zr,
B, Si, ZrB ₂ , ZrSi ₂ , ZrO ₂ (Y ₂ O
₃ , CaO, MgO, etc. added 3-8 mol% stabilized or partially stabilized ZrO ₂ ), B ₂ O ₃ , SiO
_In the case of forming a powder or a mixed powder of _{2 and the} like and a non-oxide target, if necessary, a mixture of carbon powder for reducing the oxide was used for chemical synthesis or solid phase reaction. By firing in a high temperature non-oxidizing atmosphere furnace, a lumpy single-type or complex-type powder is obtained. Ti, La, Mo, Hf, W, Nb, Sn, T
The same applies to borides and silicides of metals such as a, In and Cr. Note that these ceramic powders are Fe, A
The total amount of l, Mg, Y, Mn, and H may be 3 wt% or less, and C may be 20 wt% or less because it disappears as CO ₂ during film formation. Further, it may contain Cu, V, Co, Rh, Ir and the like in the amount of impurities.

A binder is added to a powder obtained by crushing the powder to an average particle size of 1 μm or less, and made into a slurry, and the powder is granulated into secondary particles by a spray dryer. The granulated powder preferably has a particle size of 150 μm or less, and particularly, an average particle size of about 80 μm is suitable and a packed compact having good fluidity and packing density can be obtained.

For the cylindrical target holder, stainless steel, Ti, Mo, or the like having a coefficient of thermal expansion similar to that of copper or a ceramic layer can be used. Before the HIP treatment of the ceramic powder, its outer surface is made of Al ₂ O ₃ or S
Roughening by sandblasting using iC abrasive grains is also optimal for improving adhesion. Alternatively, prior to the HIP treatment of the ceramic powder, the outer surface of the ceramic powder is processed into a V-groove shape or a screw shape, and then sandblasted with Al ₂ O ₃ or SiC abrasive grains to roughen it so that the adhesion is improved. Is also preferable.

In order to reduce the difference in thermal expansion between the ceramic layer and the target holder in the cylindrical target holder whose outer surface is roughened, and to increase the adhesion so as to withstand peeling due to heat shock during sputtering, It is preferable to form an undercoat. As such an undercoat, a layer made of a metal or an alloy having a thermal expansion coefficient intermediate between the thermal expansion coefficient of the target holder and the thermal expansion coefficient of the target material (hereinafter referred to as A layer) and the thermal expansion coefficient of the target material are close to each other. It is preferable that at least one layer out of layers (hereinafter, referred to as B layer) made of a metal or an alloy having a thermal expansion coefficient, and its powder are formed by plasma spraying. In particular, forming both layers, target holder / A
It is optimal to have a structure of layer / B layer / target material.

Even if the undercoat is only the B layer, since the metal and the alloy have high elasticity and small brittleness, the adhesion of the target material to the target holder can be enhanced. The thermal expansion coefficient of the B layer is preferably a value within the range of ± 2 × 10 ⁻⁶ / ° C. of the thermal expansion coefficient of the ceramic layer.

The material of the undercoat is Mo, T
i, Ni, Nb, Ta, W, Ni-Al, Ni-Cr,
Ni-Cr-Al, Ni-Cr-Al-Y, Ni-Co
A conductive powder such as -Cr-Al-Y can be used. The thickness of the undercoat is 30 to 100 μm, respectively
A degree is preferable.

[0028] Specifically, the undercoat material will vary depending on the thermal expansion coefficient of the ceramic layer (which can be used in the target holder, the thermal expansion coefficient such as Cu or SUS304 is 17-18 × 10 ^{- 6} / ° C.).

For example, the ceramic layer is a Zr-B type,
Zr-B-Si system, Hf-Si system, Ti-B system, Cr-
In the case of Si-based, Sn-Si-based, Zr-Si-based (when Zr is less than Zr: Si (atomic ratio) = 33:67) and the like (coefficient of thermal expansion 5 to 6 x 10 ^-6 / ° C), under Coat A
The preferred coefficient of thermal expansion of the layer is 12 to 15 × 10 ⁻⁶ / ° C., and its material is Ni, Ni—Al, Ni—C.
r, Ni-Cr-Al, Ni-Cr-Al-Y, Ni-
Co-Cr-Al-Y etc. are mentioned. The preferred thermal expansion coefficient of the undercoat B layer is 5 to 8 × 10 ^-6 / ° C.
And examples of the material include Mo, W, Ta, Nb and the like.

The ceramic layers are Ta-B type and Ta-S type.
i system, Ti-Si system (Ti: Si (atomic ratio) = 33: 6
7 and less Ti), Zr-Si system (Zr: Si
(Atomic ratio) = 33: 67 or when Zr is larger than this,
(Including ZrSi ₂ ), etc. (coefficient of thermal expansion 8-9 × 10 ⁻⁶ /
C), the preferable thermal expansion coefficient of the undercoat A layer is 12 to 15 × 10 ⁻⁶ / ° C., and its material is Ni, Ni—Al, Ni—Cr, Ni—Cr—A.
1, Ni-Cr-Al-Y, Ni-Co-Cr-Al-
Y etc. are mentioned. The preferable thermal expansion coefficient of the undercoat B layer is 8 to 10 × 10 ⁻⁶ / ° C., and its material includes Ti, Nb and the like.

The ceramic layer is made of Cr-B, Ti-S.
i-based (Ti: Si (atomic ratio) = 33: 67 or when Ti is larger than this, TiSi ₂ is included), etc. (coefficient of thermal expansion 1
In the case of 0 to 13 × 10 ⁻⁶ / ° C.), the preferable thermal expansion coefficient of the undercoat is 10 to 13 × 10 ⁻⁶ / ° C., and its material is Ni, Ni—Al, Ni—Cr, Ni.
-Cr-Al, Ni-Cr-Al-Y, Ni-Co-C
r-Al-Y etc. are mentioned. When the difference in the coefficient of thermal expansion between the ceramic layer and the target holder is small as described above, the undercoat may be a single layer. Further, among such undercoat materials, the composition ratio may be changed to provide two layers, a layer having a thermal expansion coefficient close to that of the target holder and a layer having a thermal expansion coefficient close to that of the ceramics layer.

Next, the above-mentioned target holder subjected to the undercoat treatment is placed in the HIP-treated capsule of FIG. 1, the above-mentioned ceramic granulated powder is filled, and sintered and joined by the HIP treatment.

FIG. 1 shows a HIP processing capsule. HI
The P treatment capsule is composed of a bottomed stainless steel capsule 1 and a cylindrical target holder 2 arranged therein, and these are welded to a predetermined position, that is, at the center of the bottom of the bottomed stainless steel capsule 1 by welding the cylindrical target holder. Joined and fixed. This HIP processing capsule is preferably made of steel or stainless steel, and the thickness of the capsule is 4 m.
m or less is desirable.

Further, the HIP-treated capsule 1 suppresses a reaction during sintering of the HIP-treated ceramic layer filled in the capsule in the HIP-treatment step and facilitates release from the HIP-treated ceramic layer. For HIP
Alumina fiber paper (0.5 mm to 1 mm thick) or a sheet may be attached to the inner surface of the treated stainless steel capsule 1.

The ceramic powder is filled in a gap between the stainless steel capsule 1 and the cylindrical target holder 2. Alternatively, by using the cylindrical target holder 2 which has been surface-treated in advance, the cylindrical target holder 2 is placed in a CIP (cold isostatic pressing) molding rubber mold, and the ceramic powder is filled in the gap between the cylindrical target holder 2 and the preliminary CIP. A molding method can also be adopted.

According to the above method, the ceramic powder filled in the HIP-processed stainless capsule or the ceramic molded body preliminarily CIP-molded on the cylindrical target holder device is placed in the HIP-processed capsule and the HIP-processed capsule is prepared. 10 ^-3 Torr stainless steel capsule
It is vacuum-sealed below. This vacuum seal is 10 ^-3 Torr
This is because the gas and components adhering to the ceramic raw material powder will not be sufficiently removed if it exceeds the limit.

The vacuum-sealed HIP capsule made of stainless steel is placed in a HIP device for HIP treatment. The HIP process is a process in which an inert gas (Ar) under high temperature and high pressure is used as a pressure medium to simultaneously sinter the ceramic powder inside the capsule and the preformed ceramic compact and bond the ceramic layer and the target holder at the same time. At this time, it is desirable that the HIP treatment conditions are a temperature of 900 to 1200 ° C. and a pressure of 50 MPa or more for 1 hour or more. HIP condition is temperature less than 900 ° C or pressure 50M
When it is less than Pa, the density of the ceramic layer is low and the adhesion to the target holder is low, and when the temperature exceeds 1200 ° C., the reaction with the target holder becomes vigorous, which is not preferable.

The HIP-processed stainless steel HIP-treated capsule thus obtained is taken out from the HIP device, and the stainless-steel capsule on the outer surface is peeled off to obtain a ceramic rotating cathode target. In this way, it is possible to obtain a dense ceramic rotating cathode having a ceramic layer of 2 mm or more and 10 mm or less and having high adhesion to the target holder.

The thus produced rotary cathode target is homogeneous without any oxidation of the target material and no change in chemical composition, and also has good heat conduction from the target material to the target holder and further to the cathode electrode, and is a solid target. Since it is in close contact with the holder, it is sufficiently cooled even when high sputtering power is applied to increase the film formation rate, and there is no peeling or cracking of the target due to sudden heat shock, and a large amount of power is applied per unit area. It is possible to

Further, since the erosion zone of the target is the entire surface, there is an advantage that the utilization efficiency of the target is higher than that of the planar type. Further, even if the eroded portion of the target becomes thin, it is also possible to regenerate the original state by subjecting the portion where the target material is reduced to the HIP treatment with the ceramic powder of the same material by the same method. Further, it is possible to easily give the distribution of the thickness of the target depending on the location, and thereby it is possible to control the strength distribution of the magnetic field and the distribution of the temperature on the target surface to control the thickness distribution of the thin film formed.

The method of the present invention can also be applied to a conventional planar type target, the bonding between the target and the target holder is unnecessary, and a homogeneous and highly adherent target can be easily manufactured and regenerated. ..

Further, the ceramic rotating cathode target of the present invention is DC, RF by magnetron sputtering.
It can be used for both sputtering devices, high-speed film formation, high target use efficiency, and stable film formation.

Thin films formed by using these ceramic rotating cathode targets are Zr, Ti, Hf, and T.
Since B and / or Si is added to an oxide such as a, In, or Sn, it becomes amorphous. It is considered that this is because B and / or Si destroys the lattice of such an oxide, hinders the growth of crystal grains of such an oxide, and makes the film more amorphous. It is considered that the unevenness of the film surface is smaller in the amorphous film than in the film that is an aggregate of microcrystals, and as a result, it is considered that the amorphous film of the present invention has a reduced friction coefficient.

Therefore, the amorphous film formed by using the target of the present invention has very excellent lubricity and is less likely to be scratched by friction, and thus has high scratch resistance and high abrasion resistance. It is thought to be done.

[0045]

【Example】

[Embodiment 1] In this embodiment, a method for producing a rotating cathode for ZrB ₂ ceramics magnetron sputtering, which enables stable formation of a transparent and highly durable amorphous oxide film at a high speed, will be described.

First, ZrO is used as a ceramic powder raw material.
A mixture of ₂ , B ₂ O ₃ and carbon was reacted in a high temperature non-oxidizing atmosphere to obtain a lump-shaped sinter. The lumpy powder was placed in a nylon pot mill to produce ZrO ₂ (partially stabilized ZrO _2
2 ) A ball was used to grind for 24 hours in an ethanol solvent. A vinyl acetate / acrylic copolymer binder was added to and mixed with this slurry, and the purity was adjusted to 9 by an explosion-proof spray dryer.
A ZrB ₂ granulated powder having 9.5% and an average particle diameter of 80 μm was obtained.

The cylindrical target holder is made of copper having an outer diameter of 67.5 mm and a length of 406 mm and is attached to a lathe. The outer surface of the target holder is processed into a screw shape, and Al ₂ O is formed on the outer surface.
_{3 The} surface was roughened by sandblasting with abrasive grains to make it rough. Next, as an undercoat, the first layer Ni-Al
Alloy powder (mixing weight ratio 8: 2) and Mo as second layer
Plasma spraying the metal powder of (using Metco spraying machine),
A coating having a film thickness of 50 μm was formed.

The surface-treated cylindrical target holder was placed in a stainless steel capsule for HIP treatment, the inner surface of which was previously adhered with Al ₂ O ₃ fiber paper (1 mm thick), and the bottom was welded and joined. A HIP-treated capsule was prepared. The gap between the capsule and the cylindrical target holder was vibration-filled with the above ZrB ₂ granulated powder using a vibrator. Then, the inside of the stainless steel capsule is depressurized to 10 ^-3 Torr or less and sealed, and HI
It was inserted into a P processing device and subjected to HIP processing.

As the HIP treatment conditions, Ar gas (purity 99.9%) having a temperature of 1130 ° C. and a pressure of 200 MPa was used as a pressure medium, and the treatment was carried out for 1 hour. After the HIP process, the stainless capsule was removed and the outer surface of the ZrB ₂ ceramic cylindrical target was processed to be smooth, and the inner surface of the target holder was machined with a lathe to an inner diameter of 50.5 mm, and the ZrB ₂ ceramic and target were processed. ZrB ₂ ceramics film thickness that firmly adheres to the holder integrally 5
A mm rotating cathode target was obtained. The obtained ZrB
The relative density of the _two ceramic layers was 99.5%, and the oxygen content in the ceramic layer was 0.15% by weight.

The ZrB ₂ rotating cathode target thus obtained was loaded into a magnetron sputtering apparatus, and a ZrB _x O _y film (Zr: B: O = 1: 1 was formed on a glass substrate.
2: 5 (atomic ratio)) was formed. The formation conditions are Ar + O ₂
Sputtering was performed in a mixed atmosphere of 1 × 10 ⁻³ to 1 × 10 ⁻² Torr in a vacuum to obtain a transparent amorphous oxide film of 1000 Å. The chemical composition Zr: B atomic ratio of this amorphous film was the same as the chemical composition Zr: B ratio of the target.

The above target was more robust against damage due to heat shock than a planar type target in which ceramics were made by a conventional ceramic method and attached to a target holder. In the above-mentioned conventional method, cracks occur at a sputtering power of about 2.5 kW and some peeling occurs, but in the rotating cathode of the present invention, no crack is observed even at 5 kW, arcing does not occur, and stable film formation is possible. With the conventional method, a high film forming rate of 100 Å / sec, which is about four times as high as that of 25 Å / sec, was obtained.

Example 2 A mixture of ZrO ₂ , SiO ₂ and carbon powder as a ceramic powder raw material was reacted in a high temperature non-oxidizing atmosphere to obtain a lump-shaped sintered product. This agglomerated powder was pulverized and classified in the same manner as in Example 1 to obtain a purity of 9
A ZrSi ₂ powder having 9.5% and an average particle size of 80 μm was obtained.
Using this powder, a rotary target was produced in the same procedure as in Example 1. The relative density of the ZrSi ₂ ceramic layer was 99.5% and the oxygen content was 0.2% by weight.

A film was formed by a magnetron sputtering apparatus using this rotating target. As a result, Z with a thickness of 1000Å
A transparent thin film of rSi _x O _y (Zr: Si: O = 1: 2: 6 (atomic ratio)) was obtained. As in the case of the ZrB ₂ target of Example 1, there was no change in the chemical composition of the target, and a film formation rate of about 4 times was obtained compared to the planar type target by the conventional ceramic method, and there was no damage even when the power was increased. I was not able to admit.

[Example 3] Zr as a ceramic raw material
A mixture of O ₂ , SiO ₂ , B ₂ O ₃ and carbon powder was reacted in a high temperature non-oxidizing atmosphere to obtain a lump-shaped sintered product.
The agglomerated powder was pulverized and granulated in the same manner as in Example 1 to obtain a Zr-B-Si (atomic ratio 1: 1: 8) powder having a purity of 99.5% and an average particle diameter of 80 μm. Using this powder, a rotary target was produced in the same procedure as in Example 1. The relative density of the ZrBSi ₈ ceramic layer was 99.5% and the oxygen content was 0.13% by weight. Then, a film was formed by a sputtering device using this rotating target.

As a result, ZrB _x Si having a thickness of 1000 Å
_y O _z film (Zr: B: Si: O = 1: 1: 8: 18.5
(Atomic ratio)) was obtained. ZrB of Examples 1 and 2
Similar to the case of ₂ and ZrSi ₂ targets, the chemical composition of the target does not change, and the film formation rate is about 3.5 times that of the conventional planar type target with a sintered body joined, and cracking occurs even when the power is increased. No damage was observed, and stable high-speed film formation was possible.

[Comparative Example 1] ZrO ₂ having a purity of 99.5% and a particle size of 20 to 45 μm as a ceramic powder material for thermal spraying.
Using a powder, a copper cylindrical target holder having an inner diameter of 50.5 mm, an outer diameter of 67.5 mm, and a length of 406 mm was attached to a lathe, the outer surface of which was processed into a screw shape, and then Al ₂ O _{3 was used.}
The surface was roughened and roughened by sandblasting using abrasive grains.

Next, as an undercoat, Ni-Al
The alloy powder (blending weight ratio 8: 2) was plasma sprayed in the atmosphere to form a coating having a film thickness of 50 μm. On top of this, Mo metal powder is sprayed in the atmosphere by plasma spraying to a film thickness of 50
A μm coating was obtained.

Next, the ZrB ₂ powder described above was used to perform the same plasma spraying in the atmosphere as described above to obtain Z having a final thickness of 3 mm.
A rotating cathode coated with rB ₂ was obtained. At this time, the relative density of the ceramic layer was 88%, and the oxygen content was 3.05% by weight.

The ZrB ₂ rotating cathode target thus obtained was loaded into a magnetron sputtering apparatus to form a ZrB _x O _y film on a glass substrate, and a 1000 Å transparent amorphous oxide film was obtained. Regarding the chemical composition atomic ratio Zr: B ratio of this amorphous film, B was smaller than the chemical composition of the ceramic layer.

During sputtering, arcing at the beginning of use is rather vigorous and pre-sputtering for about 30 minutes is required.
Although high-speed film formation at 5 kW caused a small arcing, a film formation rate of 100 Å / sec which was about four times that of the first arc was obtained. No cracking or peeling of the target ceramics layer was observed during sputtering, but fine arcing was formed here and there on the target surface.

[0061]

According to the method of the present invention, the target is HI
Since it is manufactured by simultaneously performing sintering and bonding using the P treatment method, it does not require conventional ceramics manufacturing equipment, and can be easily manufactured at low cost and in a short time without a processing and bonding process. Can be applied to.
In particular, powders of refractory substances and refractory metals which are difficult to be made into ceramics are cheaper, and it is particularly effective when such substances are targeted.

When the rotating cathode target of the present invention is used, the cooling efficiency during sputtering is also high, and even if the sputtering power is increased, there is no cracking or damage to the target, and stable high-speed film formation at low temperatures is possible. The industrial value is enormous because the productivity of large-area glass for automobiles and automobiles is remarkably improved and the target use efficiency is increased.

According to the present invention, it is possible to provide a thin film having high durability and also having a degree of freedom in optical design in which the refractive index can be controlled by the addition amount of B and / or Si. Since the amorphous oxide film of the present invention has high scratch resistance, high abrasion resistance, and high chemical durability, it can be widely used as an overcoat for various articles. For example, it is most suitable for the outermost layer of heat ray-reflecting glass for buildings and vehicles, a protective plate of the reading part of a bar code reader, an antireflection film, and a lens for spectacles.
In addition, it can be widely used as a mechanical element and can be used as a coating material for sliding members.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of an example of a HIP processing capsule used in the present invention.

[Explanation of symbols]

1: Stainless steel capsule 2: Surface-treated copper cylindrical target holder 3: Al ₂ O ₃ ceramics fiber paper 4: Filled ceramics powder

Claims (5)

[Claims] 1. A metal or alloy having a roughened outer surface of a cylindrical target holder and having a thermal expansion coefficient intermediate between the thermal expansion coefficient of a ceramic layer to be formed later and the thermal expansion coefficient of the target holder. And at least one layer of a metal or an alloy having a coefficient of thermal expansion close to that of the ceramic layer as an undercoat by plasma spraying, and then the outer surface of the cylindrical target holder. A method of manufacturing a ceramic rotating cathode target, which comprises arranging a ceramic powder or a molded body of such a powder around and performing hot isostatic pressing. 2. A ceramic powder comprising Zr, Ti, Hf,
At least one of Sn, Ta, In, and Cr, and B
The method for producing a ceramic rotating cathode target according to claim 1, wherein the powder is a powder containing (boron), Si (silicon), and O (oxygen) as a main component. 3. On the outer surface of the cylindrical target holder,
A ceramic layer serving as a target to be sputtered is formed, 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 the thermal expansion of the ceramic layer. A ceramic rotating cathode target, wherein at least one layer of a metal or an alloy having a coefficient of thermal expansion close to a coefficient is formed as an undercoat between the ceramic layer and the target holder. 4. The ceramic layer is Zr, Ti, Hf, S.
4. The ceramic rotating body according to claim 3, wherein at least one of n, Ta, In and Cr and at least one of B (boron), Si (silicon) and O (oxygen) are contained as main components. Cathode target. 5. A film forming method by sputtering, which comprises forming a film by sputtering the ceramic rotating cathode target according to claim 3 or 4.