JPH0987051A - Joined body of ceramics and method for joining ceramics - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance bonding strength by interposing a metallic film and a metallic binder between a 1st member made of Al compd. ceramics and a 2nd member made of a metal or ceramics so that the film is positioned on the 1st member side and the binder on the 2nd member side and heating them. SOLUTION: A metallic film 52 of 0.1-20μm thickness is formed on the joining face 50a of a 1st member 50 made of Al compd. ceramics. The 1st member 50 and a 2nd member 51 made of a metal or ceramics are placed oppositely to each other, a metallic binder 53 different from the metallic film 52 in the kind of metal is interposed between the film 52 and the joining face 51a of the 2nd member 51, and they are heated to form a joining layer 54 with a continuous phase made of the binder 53 and a dispersed phase made of an intermetallic compd. formed in the continuous phase between the 1st and 2nd members 50, 51.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a joined body of ceramics made of an aluminum compound and another member made of metal or ceramics, and a joining method.

[0002]

2. Description of the Related Art Conventionally, a method of joining ceramics in which a ceramic member and a metal member are joined by a brazing material is
Various configurations are used for various purposes. In particular, the following methods are known as methods for joining alumina and aluminum nitride to other members. (1) Bonding with an active metal brazing material. (2) Molybdenum-manganese paste is applied to the surface of aluminum nitride, and the paste is baked to form a paste baking layer. Nickel plating is performed on the paste baking layer. A brazing material is interposed on the nickel plating for brazing. .

[0003]

However, (1),
In the method (2), active metals such as titanium and molybdenum remain in the joint portion. Therefore, particularly in the presence of plasma of a halogen-based corrosive gas, the active metals (Ti, Zn, etc.), Mn, Mo, glass, etc. present in this joint portion are susceptible to corrosion. Also,
In the method (1), the active metal braze is brought into direct contact with the surface of the ceramic member to melt the braze,
In many cases, the wettability of alumina and aluminum nitride was poor, and there was room for improvement in order to stably obtain high strength.

The method (2) is intended to solve the problem of wettability with respect to the ceramics, and a paste containing powders of molybdenum, manganese and glass is applied to the surface of the ceramic member, Bake the paste. At this time, the glass component is solidified on the surface of the ceramic to form a glass layer, and a molybdenum-manganese layer is formed on the glass layer. Here, the bonding strength between the ceramic member and the glass layer is relatively high, and the molybdenum-manganese layer and the metal brazing material are firmly bonded. As described above, since it is difficult to directly and firmly bond the metal braze to the surface of the ceramic member, an attempt is made to improve the bonding strength by interposing the glass layer and the molybdenum-manganese layer therebetween.
However, the number of layers interposed between the ceramic member and the other members was large, and the strength of the bonded portion was not always stable. Further, in order to bake such a glass-containing paste on the surface of the ceramic member, it is usually 800
Since a high temperature of not less than ℃ is required, the residual stress due to the difference in thermal expansion between the ceramic member and the metal member is large, and it is likely to cause breakage.

An object of the present invention is to provide a new method for joining ceramics containing aluminum to other members made of metal or ceramics. Moreover, the subject of this invention is improving this joining strength. Another object of the present invention is to provide a microstructure of a bonded body having high strength at the bonded interface.

[0006]

The present invention relates to a joined body of a first member made of a ceramic made of an aluminum compound and a second member made of a ceramic or a metal, which comprises a first member and a second member. A joining layer is formed between the member and the member, and the joining layer is a continuous phase made of a metal joining material,
The present invention relates to a bonded body of ceramics, characterized in that it is provided with a dispersed phase composed of an intermetallic compound generated between the continuous phases.

Further, the present invention is a method for joining a ceramics first member made of an aluminum compound and a second member made of ceramics or a metal,
A metal film is formed so that the metal film directly contacts the bonding surface of the first member, and a metal bonding material made of a material different from the metal film is interposed between the metal film and the second member. The present invention relates to a method for joining ceramics, wherein the first member and the second member are joined together by heating at least the metal joining material and the metal film in such a state.

The inventor of the present invention has conducted research to develop a method for firmly joining a ceramic member such as aluminum nitride to another member at a temperature as low as possible. In this process, a vapor deposition layer or a plating layer of nickel was formed on the surface of the ceramic member. At this stage, the bonding force between the nickel vapor deposition layer and the plating layer and the ceramic member was weak, and they were easily peeled off. However, when a brazing material was placed directly on the surface of this nickel vapor deposition layer or plating layer, the brazing material was brought into contact with another metal or ceramics member, and heat treatment was performed, the ceramics member and the other member unexpectedly appeared. We have found that they bond strongly.

When the state of the joint interface of the obtained joint body is analyzed, the nickel vapor deposition layer and the plating layer disappear, and nickel reacts with the brazing material to form a dispersion layer made of an intermetallic compound. I have confirmed that. From this,
The joining mechanism was estimated as follows. It is considered that during the process of heating the brazing material, the aluminum brazing material was first wetted with nickel, the nickel was dissolved in the brazing material, and an intermetallic compound of nickel and aluminum was generated. Thus, the reaction that produces an intermetallic compound of nickel and aluminum is
Since it is an exothermic reaction, it is considered that the reaction heat causes a local temperature rise, which causes the aluminum and the aluminum nitride to get wet and bond.

This point will be further described. When a metal film made of nickel and a metal bonding material containing aluminum as a main component are used, heating is usually performed at 600 ° C. At this time, an aluminum-nickel intermetallic compound is generated,
Since this production reaction is an exothermic reaction, it is expected that the temperature locally rises. In general, ceramics and metals have good wettability at high temperatures, and in this case also, it is considered that the wettability of aluminum and ceramics is improved due to the temperature rise due to the exothermic reaction, and both are strongly bonded.

The bonded body of the present invention thus obtained includes a continuous layer made of a metal bonding material and a dispersion layer made of an intermetallic compound dispersed in the continuous layer. The coefficient of thermal expansion of the intermetallic compound is usually smaller than the coefficient of thermal expansion of the main component of the metal bonding material, and is close to the coefficient of thermal expansion of ceramics, particularly nitride ceramics. By adopting the structure in which such a dispersion layer is dispersed in the continuous layer of the metal bonding material, the residual stress after the bonding is remarkably alleviated.

Further, in particular, the bonded body of the present invention is manufactured by using NF ₃ , C
When used for applications exposed to halogen-based corrosive gases such as F ₄ , the permeation of this halogen-based corrosive gas into the inside of the bonding layer is caused at the location of the dispersion layer composed of the intermetallic compound. It was found that it was stopped and the penetration of corrosion was suppressed. Therefore, the present invention is most suitable for this application.

Although the above-mentioned joining was most useful when joining an aluminum nitride member to another member, it was confirmed that it can also be applied to an alumina member.

A metal brazing material can be used as the material of the metal joining material. As the form of the bonding material,
Any of a sheet, a powder, and a paste in which a powder and a binder are mixed may be used. Further, in the above description, “forming a metal film so that the metal film directly contacts the bonding surface of the first member” means that another material is interposed between the metal film and the first member. It means to join so as not to. If another material is interposed between the metal film and the first member, the bonding force of the metal bonding material to the first member cannot be improved.

Specifically, a metal film is formed on the surface of the first member by a vapor phase method (chemical vapor deposition method, sputtering method), a liquid phase method (electrolytic plating method, electroless plating method, etc.). Can be formed. In particular, the electroless plating method can easily coat the surface of the ceramic. The thickness of the metal film is preferably 0.1 to 20 μm.

On the surface of the first member, a paste obtained by dispersing a powder of nickel or the like in an organic binder is applied, the applied layer is dried, and the organic binder is scattered to form a metal film. Can be formed. Further, the metal film can be formed by bringing the metal foil into contact with the surface of the first member.

Among these methods, the gas phase method, the liquid phase method,
Further, when the metal film was provided by the method of drying the paste, the bonding strength and the residual stress were particularly good.

Next, at least the metal bonding material and the metal film are heated with the metal bonding material interposed between the metal film and the second member. At the time of this heating, it is preferable to melt and braze the metal bonding material. However, it is not always necessary to melt the entire metal bonding material, as long as it is possible to partially melt at least the vicinity of the interface between the metal bonding material and the metal film. Further, "to heat at least the metal bonding material and the metal film" means that only the region where the metal film and the metal bonding material are present, in addition to the case where the first member and the second member are heat-treated including them. Including the case where the is heated by a local heating means such as high frequency or laser light.

As the material of the metal film, in addition to nickel,
Copper, aluminum, etc. can be illustrated.

[0020]

1 (a) to 1 (c) are cross-sectional views showing a process of joining a first member 50 and a second member 51 together. There is no particular limitation on the overall shape of each of these members 50, 51. The first member 50 is made of aluminum compound ceramics, and the second member 51 is made of other ceramics or metal. Examples of this ceramic include aluminum nitride, and examples of this metal include nickel, aluminum, copper, molybdenum, and kovar. As shown in FIG. 1A, the first member 5
The metal film 52 is formed on the bonding surface 50 a of 0. Next, as shown in FIG. 1B, the first member 50 and the second member 5
1, and the metal bonding material 53 is interposed between the metal film 52 and the bonding surface 51a of the second member 51. Then
When the first member and the second member are heat-treated, FIG.
As shown in (c), the members 50 and 51 are joined, and the joining layer 54 is formed between these members.

2A to 2C show a first member 50A.
It is sectional drawing which shows the process of joining and the 2nd member 50B. The first member 50A and the second member 50B are each made of aluminum compound ceramics. Therefore, as shown in FIG. 2A, the metal film 52A is formed on the bonding surface 50a of the first member 50A, and the metal film 52B is similarly formed on the surface of the second member 50B.
Next, as shown in FIG. 2B, the first member 50A and the second member 50B are opposed to each other, and the metal films 52A and 52B are formed.
The metal bonding material 53 is interposed between the metal bonding material and the metal bonding material. Next, when the first member and the second member are subjected to heat treatment, the members 50A and 50B are joined together as shown in FIG. 2C, and the joining layer 55 is formed between these members.

As described with reference to FIGS. 1 (a) to 1 (c), when the second member made of ceramics or metal other than the ceramic made of aluminum compound is joined to the first member, As shown in the schematic cross-sectional view of FIG. 3A, the bonding layer 54 is generated. In this bonding layer 54, the metal film 52 (see FIG. 1A) disappeared, and the particles or dispersion layer 57 made of the intermetallic compound was dispersed in the continuous layer 56 made of the metal bonding material. That is, the components of the metal film move into the metal bonding material as the reaction between the material of the metal film and the metal bonding material progresses. Further, a continuous layer 60 made of an intermetallic compound may be formed on the surface of the second member 51 made of a metal in particular.
Especially when the metal member is nickel, the continuous layer 6
0 was easy to generate. The continuous layer 60 may be composed of a plurality of layers made of intermetallic compounds having different compositions, but may be made of an intermetallic compound having a single composition.

On the other hand, as described with reference to FIGS. 2A to 2C, the member 5 both made of an aluminum compound.
When 0A and 50B are joined, a joining layer 55 is formed as shown in the schematic cross-sectional view of FIG. That is,
In the bonding layer 55, the metal films 52A and 52B (see FIG. 2A) disappear, and instead the surface 5 of each member is replaced.
0a along with particles 59A, 59 made of an intermetallic compound.
B was generated. This is probably because the solidification starts from a position close to each surface 50a. Each particle 5
9A and 59B were continuous along the interface, and regions 71 and 72 rich in intermetallic compounds were formed.

Next, preferable metal bonding materials that can be used in the present invention will be described. The metal bonding material is not particularly limited as long as it can form an intermetallic compound with the material of the metal film, and an alloy containing copper, nickel, silver, or aluminum as a main component, or a pure metal thereof. Can be used.
However, in order to reduce the residual stress between the first member and the second member to the maximum, a brazing material containing aluminum as a main component, which can be bonded at a low temperature, is preferable. Further, in the present invention, it was possible to form a strong joint without particularly containing an active metal in the metal joint material. This means that diffusion of the active metal component into the ceramic member is not particularly necessary.

Therefore, it is not necessary to contain an active metal in the aluminum braze, but 0.3 to 20% by weight of Mg can be contained. Further, it is possible to further contain 50% by weight or less of the third component. As the third component, one or more components selected from the group consisting of Si and Cu can be used.

From the viewpoint of durability against halogen-based corrosive gas, a metal bonding material containing nickel, copper or aluminum as a main component is preferable. Further, in the case of Si as an alloy component, since it is easily corroded by a halogen-based corrosive gas, 20 wt. % Or less is desirable.

Hereinafter, preferred examples of embodiments in which the forms of the first member and the second member are variously modified will be sequentially described. FIG. 4A is a diagram showing an example of the structure of a susceptor having a high-frequency electrode, and FIG. 4B is a sectional view taken along line IVb-IVb showing the susceptor of FIG. 4A. A high frequency electrode 12 is embedded in a disk-shaped substrate 1 made of aluminum compound ceramics. This high frequency electrode 1
2 is a net-like bulk material in this embodiment. Reference numeral 2 is an alumina flange for attaching the base material 1, 4 is a joint portion of a power supply member, 5 is a joint portion of a thermocouple, and 6 is a base material 1 of the susceptor and an alumina flange 2. It is a support part. Of these, the details of the structure of the joint portion 4 of the power supply member and the joint portion 5 of the thermocouple are shown in FIG.

Hub 1 whose flange 2 is made of aluminum nitride
1 and the hub 11 is attached to the back surface 1 of the substrate 1.
It is joined to b. A high-frequency electrode 12 is embedded inside the surface of the base material 1 near the surface 1a. This material is preferably a refractory metal such as molybdenum or tungsten. The substrate 1 has a hole 1 opened on the back surface 1b side.
3 is formed, and the mesh electrode 12 is formed on the bottom of the hole 13.
Is exposed. An elongated power supply member 14 is housed in the inner space of the flange 2, and the tip portion 1 of the member 14 is housed.
4a is joined to the bottom portion 13a of the hole 13 via the joining layer 15 and the insert material 16 for relaxing the residual stress.
The joint portion 4 is configured by these.

In the electrode joint portion 4, as shown in an example in FIG. 5, the joint layer 1 is attached to the bottom portion 13a of the hole 13 of the base material 1.
5 are in contact with each other, and the mesh electrode 12 is exposed at the bottom 13a. Then, the bonding layer 15 and the mesh electrode 12 that is the metal exposed portion are bonded, and the bonding layer 15 and the base material 1 are bonded. In particular, when the mesh electrode 12 is used as the metal exposed portion, the bonding portion between the bonding layer 15 and the mesh electrode 12 exists in a mesh shape, and at this stitch, the bonding portion between the bonding layer 15 and the base material 1 is generated. To do. In this way, since the joints between the mesh electrode and the brazing filler metal and the joints between the base material and the brazing filler metal are alternately present, extremely strong joints can be achieved.

A hole 17 is formed in the base material 1, and this hole 17 is opened in the back surface 1b of the base material 1,
The hole 17 is shallower than the hole 13, and the base ceramics is exposed at the bottom of the hole 17. In addition, a hollow sheath 18 containing a thermocouple is accommodated in the flange 2, and a cap 19 made of a refractory metal for protecting the thermocouple is covered around the distal end portion 18a of the hollow sheath 18. ing. The outer diameter of the cap 19 is slightly smaller than the inner diameter of the hole 17. Then, the cap 19 is attached to the hole 1
7 to the bottom portion 17a of the bonding layer 20 and the insert material 21.
The thermocouple junction 5 is formed by joining the thermocouples.

The present invention can be applied to joining the flange 2 made of alumina and the hub 11 made of aluminum nitride, and joining the hub 11 and the base material 1 made of aluminum nitride. In this case, either one can be the first member and the other can be the second member. Also,
The present invention can be applied to the joint portion between the insert material 16 and the base material 1. In this case, the base material 1 exposed in the hole 13 is used as the first member, and the insert material 16
Is the second member.

FIGS. 6A, 6B, 6C, 7A, 7B, 8A and 8B are respectively shown in FIG. It is sectional drawing which shows the periphery of the joining part of the electric power supply member in the same plasma generation electrode device as the example shown to a) and (b). In these drawings, the same members as those shown in FIG. 4 are designated by the same reference numerals, and the description thereof may be omitted.

In the example shown in FIG. 6A, the through hole 4 is formed at the center.
1a is formed in the tube-shaped terminal 41 and the hole 13 is formed.
Housed within. The terminal 41 is made of Ni or Al. The lower end surface of the terminal 41 is bonded to the bottom portion 13a by the bonding layer 15a, and the lower side surface of the terminal 41 is bonded to the peripheral surface of the hole 13 by the bonding layer 15b. The bonding layer 15b acts so that the corrosive gas in the semiconductor manufacturing apparatus does not come into direct contact with the mesh electrode 12.

In the example shown in FIG. 6B, the hole 57 is tapered, and the similarly tapered Ni or Al terminal 44 is housed in the hole 57. Then, the bottom surface of the terminal 44 and the bottom portion 57a of the hole 57 are bonded via the bonding layer 22a, and the side peripheral surface of the terminal 44 and the side peripheral surface 57b of the hole 57 are bonded via the bonding layer 22b. After this, Ni or A
The power supply member 45 made of l is welded to the terminal 44.

In the example shown in FIG. 6B, the hole 57 is further tapered, and the side peripheral surface 57b and the terminal 44 are formed.
By joining according to the present invention between and, the joining area can be increased and the airtightness with respect to the bottom portion 57a is further enhanced. Further, by inserting the terminal 44 into the hole 57, the metal bonding material can be heated while pressing the side peripheral surface of the hole 57 along the tapered surface of the tip portion 44.

The joining structure shown in FIG. 6C is different from the joining structure shown in FIG. 6A in that the stress relaxation material 24 made of aluminum nitride is further housed in the through hole 41a. A bottom surface of the hole 13 and a bottom surface 13a of the hole 13 are also joined according to the present invention. That is, the joint and its periphery are exposed to temperature rise and processing,
In this case, due to the difference in thermal expansion between the ceramics and the metal, thermal stress is applied particularly to the bonding interface between the bonding layers 15a and 15b and the ceramics. However, by adopting the structure in which the terminal 41 is sandwiched by the ceramic stress relaxation material 24, the stress applied from the terminal 41 to the bonding layer is dispersed and relieved. In particular, the bonding layer 15
It has a great effect on the relaxation of stress at the bonding interface between a and ceramics. Note that FIG. 6A, FIG. 6B, and FIG.
In the above, the base material 1 exposed in the hole 13 is used as the first member, and the terminals 41, 44 made of corrosion-resistant metal to be joined to the first member.
Is the second member.

In the example shown in FIG. 7A, a through hole 46 is provided at the center of the bush 58 having a taper.
A convex pressing portion 45 a is provided at the tip of the power supply member 45. Then, the member 45 is inserted into the through hole 46, and the metal bonding material is attached to the bottom portion 57a by the pressing portion 45a.
Heat while pressing in the direction of. Further, the bush 58 heats the metal bonding material while pressing it toward the side peripheral surface 57b.

In this example, the bottom portion 5 of the hole 57 is further added.
Since pressure can be applied by the pressing portion 45a when joining to 7a, the joining strength of the joining portion can be further improved along the bottom portion 57a.
In this embodiment, the base member 1 is used as the first member, and the bush 58 and the pressing portion 4 made of a corrosion resistant metal and joined to the first member.
5a is the second member.

In the example shown in FIG. 7B, a thin disk 47 made of Ni or Al having an inner diameter and shape substantially the same as the inner diameter and shape of the hole 13 is provided on the bottom portion 13a of the hole 13 according to the present invention. According to the above, bonding is performed via the bonding layer 15. Next, the Ni or Al power supply member 45 is integrated with the disk 47 by welding or the like. In this embodiment, by using the disc 47, it is possible to further reduce the thermal stress during manufacturing and during use. In this embodiment, the base material 1 is the first member, and the disk 47 joined thereto is the second member.

In the example shown in FIG. 8A, in the hole 13, a ring-shaped intermediate member 48 made of aluminum nitride and N
Each end face of the power supply member 45 made of i or Al is joined to the bottom portion 13 a via the joining layer 15. In this embodiment, at the same time as the member 45 that actually supplies power, the intermediate member 48 made of aluminum nitride is also included in the bottom portion 13a.
Since they are bonded to each other, the thermal stress can be further reduced. In this embodiment, the base material 1 is the first member, and the power supply member 45 and the intermediate member 48 are the second member.

In the embodiment shown in FIG. 8B, a part of the mesh electrode 12 is cut, and the remaining cut part is used as the substrate 1.
The base material 1 was integrally sintered in a state of being extended toward the back surface of the base material. As a result, the cut portion 58 is extended from the mesh electrode 12 toward the back surface, and the end face of the thin wire 58 forming the cut portion is exposed to the back surface 1b. The power supply member 45 is bonded to the back surface 1b of the base material 1 via the bonding layer 15, and the power supply member 45 is connected to the thin wire 58. In this embodiment, the substrate 1
Is the first member, and the power supply member 45 is the second member. In each of the embodiments shown in FIG. 8B, it is not necessary to form the holes 13 and 57 in the portion of the mesh 12 that is difficult to form.

FIG. 9 shows a metal flange 6 of a semiconductor manufacturing apparatus.
3 is a cross-sectional view schematically showing a joint structure between 0 and a ceramic heater 62. FIG. The flange 60 is an attachment portion 60a for attaching to the chamber of the semiconductor manufacturing apparatus.
And an extension portion 60b extending into the inside of the device. A space 61 isolated from the atmosphere inside the device is formed inside the extended portion 60b. The back surface 66b of the ceramic base material 66 of the ceramic heater 62 is joined to the end surface 60c of the extended portion 60b via the joining layer 70 according to the method of the present invention. The resistance heating element 63 is embedded inside the base material 66, and the end portion of the resistance heating element 63 is connected to the terminal 64. Each terminal 64 is exposed on the back surface 66b, and a rod-shaped member 67 for power supply is joined to each terminal. Further, a concave portion 65 is formed on the rear surface 66b side of the base 66, and a thermal contact at the end of the thermocouple 68 is accommodated in the concave portion 65.

While observing the temperature of the substrate with the thermocouple 68, the power supplied to the resistance heating element 63 is adjusted to adjust the temperature of the wafer heating surface 66a. Of course, the method of measuring the temperature, the configuration of the resistance heating element, the connection structure of the terminals, and the like are not particularly limited. With such a configuration, it is possible to provide a heating device in which the portions of the ceramic heater such as the terminals and thermocouples that are susceptible to corrosion are not exposed in the semiconductor manufacturing apparatus.

In FIG. 9, functional members such as an electrostatic chuck electrode and a high frequency electrode can be embedded inside the base body to which the flange 60 is to be joined. The terminal for supplying the space 61
Can be exposed to the inside and not exposed in the semiconductor manufacturing apparatus.

In each of the embodiments shown in FIGS. 4 to 8,
The reticulated electrode, which is a high-frequency electrode, can be punched metal or non-woven fabric. Further, instead of the high frequency electrode, an electrostatic chuck electrode or a resistance heating element (as in FIG. 9) can be embedded inside the base material.

[0046]

Example (Example 1) A joined body was manufactured according to the method shown in FIG. Flat plate-shaped members made of aluminum nitride ceramics were prepared as the first member and the second member. The size of each member was 8 mm × 40 mm × 20 mm. In Examples 1-1 to 1-4 in Table 1, plating was performed by contacting the surface 50a of each member with the nickel plating solution for a predetermined time. And between both members,
An object to be processed is manufactured by sandwiching a sheet 53 of a brazing material having each component ratio shown in Table 1, the object to be processed is housed in an electric furnace, and this is heated in vacuum to a temperature equal to or higher than the melting point of each brazing material. Each joined body was manufactured by heating to room temperature and then lowering the temperature to room temperature. The size of the sheet is 8 mm × 40 mm × 0.1
It was set to 2 mm. During heating, a pressure of 70 g / cm ² was applied in a direction perpendicular to the sheet. Further, in Comparative Examples 1-1 and 1-2, the surface treatment of each member was not performed.

For each bonded body, a 4-point bending test piece was cut out in accordance with JIS Z2204 and the 4-point bending strength was measured. In addition, each bonded body was immersed in CF ₄ plasma at 400 ° C.
Exposed for 192 hours. Regarding the conjugate after this exposure,
The four-point bending strength was measured as described above. In addition, the discoloration of the joint interface of the joined body was investigated, this discolored portion was considered as the eroded portion, and the length from the surface of this eroded portion was measured and displayed as the erosion distance.

[0048]

[Table 1]

As shown in Table 1, according to the present invention, it is possible to provide a joined body having a high four-point bending strength and a high corrosion resistance against a corrosive gas such as a halogen-based corrosive gas plasma. This joining can be easily performed with a brazing material made of various aluminum alloys or a brazing material made of pure aluminum.

On the other hand, in Comparative Example 1-1,
The joint strength was relatively low and the corrosion resistance was also poor. This is probably because the brazing material has low wettability with respect to aluminum nitride. Further, in Comparative Example 1-2, a method of improving the wettability of the brazing material to aluminum nitride was taken by significantly increasing the ratio of the active metal in the brazing material. Therefore, the initial strength is high, but when the joint body is exposed to a corrosive gas, the corrosion of the joint portion extremely progresses.

Further, the joint interface of the joint body of Example 1-1 was photographed by a scanning electron microscope and is shown in FIG. As shown in FIG. 10, particles of another substance were formed in rows along the interfaces on both sides of the joining layer made of a brazing material. When the elements in each part of the bonding layer were measured by EDAX, it was found that a region rich in the dispersion layer of the aluminum-nickel intermetallic compound remained on both sides of the layer mainly composed of the brazing material. The composition of the intermetallic compound forming this dispersion layer was Al ₃ Ni.

Example 2 A joined body was manufactured according to the method shown in FIG. That is, two first members made of aluminum nitride are prepared, one second member made of metal is prepared,
One first member was sandwiched between two first members and joined. Here, the material of the second member was changed as shown in Table 2. The size of the first member is 8mm x 40mm x 20
mm, and the dimensions of the second member are 8 mm x 40 mm x 2 m
m.

In Examples 2-1 to 2-7 in Table 2, plating was performed by bringing the surface 50a of the first member 50 into contact with the nickel plating solution for a predetermined time. Then, between the first member 50 and the second member 51, a brazing filler metal sheet 53 having the respective component ratios shown in Table 2 is formed.
The object to be treated is sandwiched between the two, and the object to be treated is housed in an electric furnace, heated in a vacuum to a temperature above the melting point of each brazing filler metal, and then cooled to room temperature for each joining. Manufactured body. The size of the sheet is 8 mm x 40 mm x
It was set to 0.12 mm. During heating, a pressure of 70 g / cm ² was applied in a direction perpendicular to the sheet. Moreover, in Comparative Examples 2-1 to 2-4, the surface treatment of each member was not performed.

With respect to each bonded body, a 4-point bending test piece was cut out in accordance with JIS Z2204 and the 4-point bending strength was measured.

[0055]

[Table 2]

As shown in Table 2, according to the present invention, it is possible to provide a joined body having a high four-point bending strength, and this joining can be performed by a brazing material made of various aluminum alloys or a brazing material made of pure aluminum. , Easy to do. Further, high strength was obtained when any of nickel, molybdenum, copper, kovar, and aluminum was used as the material of the second member.

On the other hand, in Comparative Examples 2-1 and 2-2, the joint strength was relatively low. This is probably because the brazing material has low wettability with respect to aluminum nitride. Further, in Comparative Example 2-3, the method of improving the wettability of the brazing material to aluminum nitride was taken by significantly increasing the ratio of the active metal in the brazing material. However, in this case, the bonding temperature is A
While the 1-based brazing filler metal has a temperature of 600 ° C. to 670 ° C., Comparative Example 2-3 has a temperature of 850 ° C. and Comparative Example 2-4 has a temperature of 1050 ° C.
Therefore, the thermal stress due to the difference in thermal expansion between the second member, which is a metal, and the first member, which is a ceramic, is significant, and the strength is low.

The joint interface of the joint body of Example 2-1 was photographed by a scanning electron microscope and is shown in FIG. As can be seen from FIG. 11, in the joining layer made of the brazing material,
Particles of another substance were present everywhere. Therefore, when the elements in each part of the bonding layer were measured by EDAX, it was found that a large number of particles made of an aluminum-nickel intermetallic compound were generated in the continuous layer made of the brazing material. The composition of this intermetallic compound is Al
It was ₃ Ni.

In the photograph of FIG. 11, it was found that the continuous phase composed of the nickel-aluminum intermetallic compound extended in layers along the interface between the joining layer and the nickel member. Of this continuous phase, Al ₃ Ni was mainly formed in a region far from the nickel member, and Al ₃ Ni ₂ was mainly formed in a region near the nickel member.

[0060]

As described above, according to the present invention, it is possible to provide a new method for joining a ceramic containing aluminum to another member made of metal or ceramics. This makes it possible to easily bond the ceramics and improve the bonding strength. Therefore, the bonded body of the present invention can be suitably applied to various semiconductor manufacturing apparatuses and semiconductor devices in addition to ceramic heaters, electrostatic chucks, susceptors with high-frequency electrodes.

[Brief description of drawings]

1A is a cross-sectional view showing a state in which a metal film 52 is formed on a surface 50a of a first member 50, and FIG.
It is sectional drawing which shows the state which laminated | stacked the 1st member 50 and the 2nd member 51 which oppose, (c) shows the joined body obtained by joining the 1st member and the 2nd member. It is sectional drawing shown.

FIG. 2 (a) is a cross-sectional view showing a state in which a metal film is formed on each surface of the first member 50A and the second member 50B, and FIG. 2 (b) shows the members 50A and 50B facing each other. It is sectional drawing which shows the state laminated | stacked, and (c) is sectional drawing which shows the joined body obtained by joining the 1st member and the 2nd member.

FIG. 3A is a cross-sectional view schematically showing an enlarged joint interface between a first member 50 and a second member 51,
(B) is sectional drawing which expands and shows the joining interface of the member 50A and the member 50B typically.

FIG. 4 (a) is a plan view showing an example of a plasma generating electrode device incorporating a high frequency electrode as an example in which the ceramic bonding structure of the present invention is used;
[Fig. 4] is a sectional view showing a state of a joint portion of a power supply member in the plasma generating electrode device shown in (a).

FIG. 5 is a view showing the mesh electrode 12 and the bonding layer 15 in FIG. 4B.
It is sectional drawing which expands the periphery of the interface with and and shows it typically.

6 (A), (B), and (C) are embodiments in which the joining method and the joined body of the present invention are applied to a joining portion between a power supply member and a mesh electrode of a plasma generating electrode device, respectively. It is sectional drawing shown.

7A and 7B are cross-sectional views showing an embodiment in which the joining method and the joined body of the present invention are applied to a joining portion between a power supply member of a plasma generating electrode device and a mesh electrode, respectively. is there.

8A and 8B are cross-sectional views showing an embodiment in which the joining method and the joined body of the present invention are applied to a joining portion between a power supply member and a mesh electrode of a plasma generating electrode device, respectively. is there.

FIG. 9 is a cross-sectional view schematically showing a state in which a ceramics heater 62 is joined and integrated with a flange portion 60 of a semiconductor manufacturing apparatus.

FIG. 10 is a scanning electron micrograph corresponding to FIG. 3B, showing a ceramic structure of a bonded interface of a bonded body.

FIG. 11 is a scanning electron micrograph corresponding to FIG. 3A, showing a ceramic structure of a bonded interface of a bonded body.

[Explanation of symbols]

1 Base Material 11 Hub 12 Reticulated Electrode 14
Power supply member 15, 20 Bonding layer 16, 21
Insert material 19 Cap 44 Power supply member terminal 45 Power supply member
50, 50A First member 50a made of aluminum compound ceramics Surface of first member 50a
B, 51 Second member 52, 52A, 52B Metal film 53 Metal bonding material 54, 55 Bonding layer 5
6,58 Metal bonding material 57, 59A, 59B Dispersed phase composed of intermetallic compound 60 Continuous phase composed of intermetallic compound 71-72 Area rich in intermetallic compound

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Claims (8)

[Claims] 1. A bonded body of a ceramics first member made of an aluminum compound and a second member made of ceramics or a metal, which is provided between the first member and the second member. A bonding layer is formed, and this bonding layer is characterized by comprising a continuous phase made of a metal bonding material and a dispersed phase made of an intermetallic compound generated between the continuous phases. Ceramic bonded body. 2. The ceramic bonded body according to claim 1, wherein a layered region rich in the dispersed phase is formed along an interface of the bonding layer with the first member. . 3. The second member is ceramics, and a layered region rich in the dispersed phase is formed along an interface of the bonding layer with the second member. The joined body of ceramics according to claim 2. 4. The second member is a metal, and an interface layer composed of a continuous layer of an intermetallic compound is formed along the interface of the bonding layer with the second member. The joined body of ceramics according to claim 1, wherein the dispersion layer is formed in the joint layer between the first member and the second member. 5. A method of joining a first member made of ceramics made of an aluminum compound and a second member made of ceramics or a metal, wherein a metal film is formed on the joining surface of the first member. The metal film is formed so as to be in direct contact, and at least the metal bonding material in a state in which a metal bonding material made of a material different from the metal film is interposed between the metal film and the second member. A method for joining ceramics, characterized in that the first member and the second member are joined by heating the metal film. 6. The method for joining ceramics according to claim 5, wherein the metal film is a nickel film. 7. The method for joining ceramics according to claim 5 or 6, wherein the metal joining material is made of a metal selected from the group consisting of pure aluminum and an aluminum alloy. 8. The method according to claim 5, wherein the ceramic constituting the first member is a ceramic selected from the group consisting of aluminum nitride and alumina. A method for joining the ceramics described.