U.S. patent number 3,854,892 [Application Number 05/337,143] was granted by the patent office on 1974-12-17 for direct bonding of metals with a metal-gas eutectic.
This patent grant is currently assigned to General Electric Company. Invention is credited to James F. Burgess, Constantine A. Neugebauer.
United States Patent |
3,854,892 |
Burgess , et al. |
December 17, 1974 |
DIRECT BONDING OF METALS WITH A METAL-GAS EUTECTIC
Abstract
A method is described for direct bonding of metallic members to
other metallic members with a metal-gas eutectic. The method
comprises placing a metal member such as copper, for example, in
contact with another metal member, such as nickel, for example,
heating the metal members to a temperature slightly below the
melting point of the lower melting point metal, e.g., approximately
1072.degree.C. for copper, the heating being performed in a
reactive atmosphere, such as an oxidizing atmosphere, for a
sufficient time to create a metal-gas eutectic melt which, upon
cooling, bonds the metal members together. Various metals and
reactive gases are described for direct bonding.
Inventors: |
Burgess; James F. (Schenectady,
NY), Neugebauer; Constantine A. (Schenectady, NY) |
Assignee: |
General Electric Company
(Schenectady, NY)
|
Family
ID: |
26937539 |
Appl.
No.: |
05/337,143 |
Filed: |
March 1, 1973 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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245890 |
Apr 20, 1972 |
3744120 |
|
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|
Current U.S.
Class: |
428/629; 428/620;
428/639; 428/640; 428/652; 428/654; 428/656; 428/675; 428/677;
428/685 |
Current CPC
Class: |
B23K
35/302 (20130101); B23K 35/38 (20130101); Y10T
428/12924 (20150115); Y10T 428/12778 (20150115); Y10T
428/1259 (20150115); Y10T 428/12667 (20150115); Y10T
428/1266 (20150115); Y10T 428/1275 (20150115); Y10T
428/12979 (20150115); Y10T 428/1291 (20150115); Y10T
428/12528 (20150115); Y10T 428/12764 (20150115) |
Current International
Class: |
B23K
35/30 (20060101); B23K 35/38 (20060101); B23K
35/22 (20060101); B32b 015/00 (); B32b
015/20 () |
Field of
Search: |
;29/494,196.1,196.2,196.3,196.6,197.5,199,194 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Lovell; C.
Assistant Examiner: Steiner; Arthur J.
Attorney, Agent or Firm: Wille; Paul F. Cohen; Joseph T.
Squillaro; Jerome C.
Parent Case Text
This is a division, of application Ser. No. 245,890, filed Apr. 20,
1972 now U.S. Pat. No. 3,744,120.
Claims
What we claim as new and desire to secure by Letters Patent of the
United States is:
1. A bonded metal-to-metal structure comprising:
a first metal member;
a second metal member;
a eutectic bond between said first and second metal members said
eutectic bond consisting essentially of a mixture of atoms of at
least said first metal member and one of the group consisting of
oxides, sulfides, phosphides and silicides of said metal.
2. The structure of claim 1 wherein said metal members are selected
from the group consisting of copper, nickel, cobalt, chromium,
iron, silver, aluminum, alloys thereof and stainless steel.
3. The structure of claim 2 wherein at least one of said metal
members is copper.
4. The structure of claim 1 wherein at least said first metal
members is copper and said eutectic bond is copper-copper
oxide.
5. The structure of claim 4 wherein said second metal member is
selected from the group consisting of copper, nickel, cobalt,
chromium, iron and alloys thereof.
6. The structure of claim 4 wherein said second metal member is
stainless steel.
7. The structure of claim 1 wherein said first metal member is
aluminum and said eutectic is aluminum-aluminum silicide.
Description
The present invention relates to improved bonds and methods of
directly bonding two or more metallic members together. This
application relates to our concurrently filed application Ser. No.
245,889, now U.S. Pat. No. 3,766,634, of common assignee. The
entire disclosure of which is incorporated herein by reference
thereto.
The formation of bonds between metallic members is achieved in
various ways. For example, certain metals can be bonded together
with the use of solders. Other metals are bonded together by welds,
such as arc welds or spot welds. Where certain metals can not be
directly bonded to each other, generally intermediate metallic
members are used to form the bond. The need for simple methods of
forming bonds between similar and dissimilar metals still exists.
For example, in the fabrication of semiconductor integrated
circuits, tenacious bonds between various metals are required. In
addition, it is desirable to provide low ohmic contact between such
metals. The foregoing methods are frequently not compatible with
integrated circuit fabrication and even if compatible are
frequently economically unacceptable. Accordingly, a need for a
simple and economically acceptable method of forming bonds between
metallic members is still desired.
It is therefore an object of this invention to provide a method of
forming bonds between metallic members with a metal-gas eutectic
composition.
It is yet another object of this invention to provide a method of
bonding metallic members together without the use of intermediate
metal layers.
Another object of this invention is to provide a method of bonding
metallic members together in a simple heating step without the need
for intermediate flux.
Yet another object of this invention is to provide a tenacious bond
and a method of forming this bond between metallic members which
bond exhibits low ohmic resistance and is compatible with the
fabrication of semiconductor integrated circuit modules.
Briefly, our invention relates to bonds and methods of bonding
together metallic members by placing at least two metallic members
in contact with each other and elevating the temperature of the
members in a reactive atmosphere of selected gases and at
controlled partial pressures for a sufficient time to produce a
metal-gas eutectic composition on the surface of at least one of
the metallic members. This eutectic composition or melt forms at a
temperature below the melting point of one of the metallic members
and wets both metallic members so that upon cooling, a tenacious
bond is formed between the metallic members. By way of example,
useful metallic materials include copper, nickel, cobalt, chromium,
iron, silver, aluminum, alloys thereof, and stainless steel. Useful
reactive gases include oxygen-bearing gases, phosphorus-bearing
gases and sulfur-bearing gases, for example. In general, the amount
of reactive gas necessary to produce tenacious bonds is dependent,
in part, upon the thickness of the metallic members and the times
and temperatures required to form the eutectic melt.
Other objects and advantages of our invention will become more
apparent to those skilled in the art from the following detailed
description taken in connection with the accompanying drawings in
which:
FIG. 1 illustrates a typical bond between two metallic members
formed in accord with our invention;
FIG. 2 is a flow diagram illustrating the process steps for forming
tenacious metal-to-metal bonds in accord with our invention;
and
FIG. 3 schematically illustrates a horizontal furnace useful in
practicing our invention.
FIG. 1 illustrates, by way of example, a typical bond 11 between
metallic members 12 and 13. The bond 11 comprises a eutectic
composition formed with at least one of the metallic members and a
reactive gas in accord with the novel aspects of our invention.
As used herein, the term metallic member or material is intended to
include such materials as copper, nickel, iron, cobalt, chromium,
silver, aluminum, alloys of the aforementioned elemental materials,
and stainless steel. As will become more apparent from the
following description, still other metallic materials, such as
beryllium-copper, for example, may also be advantageously employed,
if desired.
The term eutectic or metal-gas eutectic composition as used herein
means a mixture of atoms of the metallic member and the reactive
gas or compound formed between the metal and the reactive gas; but
does not include eutectics formed by the reaction or mixing of two
metals rather than a reaction between a metal and a component of a
gas. For example, where the metallic member is copper and the
reactive gas is oxygen, the metal-gas eutectic is a mixture of
copper and copper oxide. Where the metal is nickel and the reactive
gas is phosphorous, the eutectic is a mixture of nickel and nickel
phosphide. Still further, where the metallic member is cobalt and
the reactive gas is a sulfur-bearing gas, the eutectic is formed
between cobalt and cobalt sulfide.
The novel process for making tenacious bonds between metallic
members 12 and 13 is illustrated in the flow chart of FIG. 2. More
specifically, FIG. 2 illustrates the practice of our invention by
placing two metallic members in contact with each other, such as
one member overlying another. These members are then placed in a
suitable furnace, such as is described below, which includes a
reactive atmosphere such that upon heating of the metallic members,
a metal-gas eutectic composition forms. The temperature at which
the desired eutectic composition forms and the partial pressure of
the reactive gas necessary to form the desired eutectic composition
depend upon the selected metallic members and the reactive gas. In
general, however, the partial pressure of the reactive gas must
exceed the equilibrium partial pressure of the reactive gas in the
metal at or above the eutectic temperature. For example, when
bonding copper members together, a reactive atmosphere including
oxygen, for example, requires a partial pressure of oxygen in
excess of 1.5 .times. 10.sup..sup.-6 atmospheres at the eutectic
temperature of 1065.degree.C. Other metallic materials and other
reactive gases require different partial pressures and different
temperatures to form the desired eutectic.
Table I is a representative listing of typical eutectic
compositions which are useful in practicing our invention. These
eutectics are formed by reacting the metallic members to be bonded
with a reactive gas controllably introduced into an oven or
furnace.
TABLE I
__________________________________________________________________________
Per Cent by Weight Metal-Gas Eutectic of Reactive Gas Eutectic
Temperature, .degree.C. at Eutectic Composition
__________________________________________________________________________
Iron-Oxygen 1523.degree. 0.16 O.sub.2 Copper-Oxygen 1065.degree.
0.39 O.sub.2 Chromium-Oxygen 1800.degree. 0.6 O.sub.2
Chromium-Sulfur 1550.degree. 2.2 S Copper-Phosphorus 714.degree.
8.4 P Nickel-Oxygen 1438.degree. 0.24 O.sub.2 Nickel-Phosphorus
880.degree. 11.0 P Molybdenum-Silicon 2070.degree. 5.5 Si
Silver-Sulfur 906.degree. 1.8 S Silver-Phosphorus 878.degree. 1.0 P
Copper-Sulfur 1067.degree. 0.77 S Cobalt-Oxygen 1451.degree. 0.23
O.sub.2 Aluminum-Silicon 577.degree. 11.7 Si
__________________________________________________________________________
The eutectics listed in Table I are formed by reacting the metallic
members in an oxygen-bearing gas, such as oxygen, a sulfur-bearing
gas, such as hydrogen sulfide, a phosphorus-bearing gas, such as
phosphine, or a silicon-bearing gas, such as silane. At the
eutectic temperature of the selected metallic member and the
reactive gas, such as those temperatures listed in Table I, the
eutectic composition becomes a liquid and wets the adjoining member
so that upon cooling, the metallic members become tenaciously
bonded together.
Table II illustrates, by way of example, typical metal-to-metal
bonds formed in accord with our invention and the conditions under
which the bonds are formed. For these conditions, the reactive gas
is oxygen.
TABLE II ______________________________________ Time at
Temperature, Elevated Metals Thickness .degree.C Temperature
______________________________________ Cu -- Cu 5 mils
1072.degree.C 0.5 hrs. Cu -- Ni 5 mils 1072.degree.C 1.0 hrs.
Cu-Stainless Steel 5 mils 1072.degree.C 1.0 hrs. Ni -- Ni 10 mils
1445.degree.C 1.0 hrs. Fe -- Fe 10 mils 1530.degree.C 1.0 hrs. Co
-- Co 15 mils 1458.degree.C 1.0 hrs. Cr -- Cr 15 mils 1557.degree.C
1.5 hrs. ______________________________________
The examples of metal-to-metal bonding illustrated in Table II are
by way of example, and not by way of limitation. In general, most
metals which form a metal-gas eutectic in a reactive atmosphere are
useful in forming metal-to-metal bonds. The bonding can be between
like metals, dissimilar metals, or even alloys. For example, where
like metals are bonded together, the eutectic forms on both
surfaces of the members. Where dissimilar metals are bonded
together, the eutectic generally forms on at least one surface of
the metal having the lower eutectic-forming temperature. For
example, as in the case of copper-nickel, the eutectic forms with
the copper. The eutectic then wets both metal surfaces thereby
forming the desired bond. Where alloys are employed, such as the
various alloys of nickel, iron, cobalt, copper, silver, chromium
and aluminum are employed, the eutectic composition is believed to
form with one of the elemental metals, generally the one with the
lower melting point.
One factor which appears to affect the tenacity and uniformity of
metal-to-metal bonds formed in accord with our invention is the
relationship between the melting point of the metallic member and
the eutectic temperature. Where the eutectic temperature is within
approximately 30.degree. to 50.degree.C. of the melting point of
the metallic member, for example, the metallic member tends to
plastically conform to the shape of the other member and thereby
produce better bonds than those eutectics which become liquids at
temperatures greater than approximately 50.degree.C. below the
melting point of the metallic member. The uniformity of the bond
therefore appears to be related to the "creep" of the metal which
becomes considerable only near the melting point. From Table I, for
example, it can be seen that the following eutectics meet this
requirement: copper-copper oxide, nickel-nickel oxide,
cobalt-cobalt oxide, iron-iron oxide and copper-copper sulfide.
Having thus described some useful embodiments of our invention and
the methods of forming metal-to-metal bonds, apparatus useful in
practicing our invention along with more specific details of the
process will now be described with reference to FIG. 3.
FIG. 3 illustrates a horizontal furnace comprising an elongated
quartz tube 22, for example, having a gas inlet 23 at one end
thereof and a gas outlet 24 at the other end. The quartz tube 22
also includes an opening or port 25 through which materials are
placed into and removed from the furnace. Materials are placed on a
holder 26 having a push rod 27 extending through one end of the
furnace so that the holder and materials placed thereon may be
introduced and removed from the furnace.
The furnace 21 is also provided with suitable heating elements,
illustrated in FIG. 3 as electrical wires 28 which surround the
quartz tube 22 in the region to be heated. The electrical wires 28
may, for example, be connected to a suitable current source, such
as a 220-volt alternating current source. The electrical wires 28
may then be surrounded by suitable insulating material 29 to
confine the heat generated by the electrical wires to the region
within the quartz tube. Obviously those skilled in the art can
appreciate that other heating means may also be employed, if
desired, and that FIG. 3 is merely illustrative of one such heating
means. The temperature of the furnace is detected by a suitable
thermocouple 29 which extends through an opening in the quartz tube
so that electrical connections can be made thereto. FIG. 3 also
illustrates a metallic member 12 positioned on the holder 26 and a
metallic member 13 overlying the member 12. These metallic members
are introduced into the quartz tube through the opening 25 which is
then sealed by suitable stopper means.
The quartz tube 22 is then purged with a reactive gas flow of
approximately 4 cubic feet per hour of nitrogen and 0.02 cubic feet
per hour of oxygen, for example. As used herein, reactive gas flow
or atmosphere means a mixture of an inert gas such as argon,
helium, or nitrogen, for example, with a controlled minor amount of
a reactive gas, such as oxygen, or an oxygen-bearing gas, a
phosphorus-containing gas such as phosphine, or a sulfur-containing
gas such as hydrogen sulfide, for example. The amount of reactive
gas in the total gas flow is dependent, in part, on the materials
to be bonded, the thickness of the materials, and the gas flow
rate, in a manner more fully described below. In general, however,
the partial pressure of the reactive gas must exceed the
equilibrium partial pressure of the reactive gas in the metal at or
above the eutectic temperature. As pointed out above, when bonding
copper members together, a reactive atmosphere including oxygen,
for example, the partial pressure of oxygen must be in excess of
1.5 .times. 10.sup..sup.-6 atmospheres at the eutectic temperature
of 1065.degree. C.
After purging the quartz tube, the furnace is then brought to a
temperature sufficient to form a eutectic melt at the
metal-to-metal interface. For example, for a copper-nickel bond
with oxygen as the reactive gas, the temperature of the furnace is
brought to approximately 1072.degree.C. At this temperature, a
copper-copper oxide eutectic forms on the copper member and wets
the copper member and the nickel member so that upon cooling, a
tenacious bond is formed between the two metals.
In general, the times necessary to form this eutectic melt range
between approximately 10 minutes for 1-mil-thick copper members and
approximately 60 minutes for 250-mil-thick copper members, for
example. For metallic members of other thicknesses and geometric
configurations, the times required to form the eutectic melt vary.
In general, the longer the metallic members are held at the
eutectic temperature, the thicker the eutectic will be. The
thickness of the eutectic also depends upon the partial pressure of
the reacting gas. As pointed out previously, a partial pressure
below the equilibrium partial pressure for the specific eutectic
will result in no eutectic formation. Hence partial pressures in
excess of this equilibrium value are required to produce the
desired eutectic. If the partial pressure of the reacting gas is
too high, however, all the metal reacts with the reactive gas and
forms, for example, an oxide, sulfide, phosphide, etc. which
prevents the formation of the eutectic melt. Thus, an intermediate
reacting gas partial pressure is required so that both the eutectic
melt phase and the metallic phase are present simultaneously. Tests
have illustrated that extremely strong bonds are achieved when both
phases are present. Accordingly, in practicing our invention the
partial pressure of the reacting gas must be sufficiently great to
permit the formation of a eutectic with the metal but not so great
as to completely convert the metal to the oxide, sulfide,
phosphide, etc. during the bonding time.
We have found that consistently good bonds are achieved between
metallic members so long as the aforementioned conditions are met.
However, no bonding occurs where the partial pressure of the
reactive gas is less than the equilibrium partial pressure at the
eutectic temperature and no bonding occurs where the partial
pressure of the reactive gas is such that all the metallic member
is converted to an oxide, phosphide, sulfide, etc.
Also, those skilled in the art can appreciate that the gas flow
rate is not critical to the practice of our invention and may be
varied over wide ranges without materially affecting the integrity
of the bonds. However, economic considerations will generally
control the acceptable gas flow rates. Further, the partial
pressure of the reactive gas in the inert gas also can be varied,
depending in part on the relative sizes of the materials to be
bonded. The gas flow rate and the presence of reactive elements in
the flow system, such as carbon susceptors, the presence of
residual oxygen or water in the bonding system and the bonding
time.
Table III illustrates useful ranges for partial pressures of
reactive gases at which bonding occurs between selected metals in
the presence of oxygen-bearing or sulfur-bearing gases. Only those
eutectics which exhibit exhibit a eutectic temperature within
50.degree. of the melting point of the metal are listed.
TABLE III ______________________________________ EUTECTIC %
REACTIVE GAS COMPOUND BY VOLUME
______________________________________ Cu -- CuO 0.01 -- 0.5 Cu --
CuS 0.01 -- 0.5 Ni -- NiO 0.01 -- 0.3 Co -- CoO 0.01 -- 0.4 Fe --
FeO 0.01 -- 0.3 ______________________________________
It is to be understood that Table III illustrates, by way of
example, selected metals and the percent of reactive gases in the
total gas flow which are useful in practicing our invention.
However, those skilled in the art can readily appreciate that other
materials and other reactive gases and gas flows may be employed
without departing from the spirit and scope of our invention. For
example, useful bonds are formed with binary metallic compositions,
such as copper-nickel, nickel-cobalt, copper-chromium,
copper-cobalt, iron-nickel and beryllium-copper, in reactive
atmospheres including oxygen-bearing gases. Also, ternary
compositions of iron, nickel and cobalt also form useful bonds in a
reactive atmosphere of oxygen. Additionally, useful bonds are
formed with molybdenum or aluminum in a reactive atmosphere
including silane. Accordingly, it is to be understood that Table
III is merely a partial listing of eutectic compounds and that our
invention is not limited solely to those eutectics set forth in
Table III.
Those skilled in the art can readily appreciate that the formation
of metal-to-metal bonds with a metal-gas eutectic provides an
extremely useful capibility in electrical and electronic systems.
For example, metal-to-metal bonds may be used for interconnections,
packaging of electronic components, formation of hermetic seals,
electrical crossoves in integrated circuits, to mention only a few.
These metal-to-metal bonds are formed without the use of
compressive forces on the metal members and do not require the
interdiffusion of metals to effect tenacious bonds. Additionally,
although the metallic members are illustrated as sheets or plates,
it is to be understood that other configurations may also be used
in the practice of our invention. Still other changes and
modifications will occur to those skilled in the art and hence, the
appended claims are intended to cover all such changes and
modifications as fall within the true spirit and scope of our
invention.
* * * * *