U.S. patent number 3,706,582 [Application Number 04/761,164] was granted by the patent office on 1972-12-19 for glass frit-ceramic powder composition.
This patent grant is currently assigned to GTE Sylvania Incorporated. Invention is credited to Edward Meyer.
United States Patent |
3,706,582 |
Meyer |
December 19, 1972 |
GLASS FRIT-CERAMIC POWDER COMPOSITION
Abstract
Disclosed are techniques for fabricating metal-ceramic articles
wherein a hermetic seal is desired between the metal-ceramic
jointure. The technique involves utilization of a powdered ceramic
containing a binding material which is compressed in a mould around
the metal part or parts to be incorporated therein. The green part
so formed exhibits superior strength and the article is much easier
to handle for subsequent firing. Also disclosed is a glass-ceramic
powder composition ideally suited to this process, together with
methods for treating the metal parts to insure a hermetic seal.
Inventors: |
Meyer; Edward (Russell,
PA) |
Assignee: |
GTE Sylvania Incorporated
(Seneca Falls, NY)
|
Family
ID: |
25061361 |
Appl.
No.: |
04/761,164 |
Filed: |
September 20, 1968 |
Current U.S.
Class: |
501/15; 501/17;
501/79; 252/519.51; 428/406; 501/26; 264/618; 264/619 |
Current CPC
Class: |
C03C
10/0054 (20130101); H01L 2924/09701 (20130101); Y10T
428/2996 (20150115) |
Current International
Class: |
C03C
10/00 (20060101); C04b 033/00 () |
Field of
Search: |
;106/313,54,48,53,39R,39DV ;252/62.3,63.5,520 ;264/61 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Volf, M.B; Glasses for Discharge Lamps, in Technical Glasses,
London (Pitman's) 1961 pp 392-393. .
Ingerson, E. et al; The Systems K.sub.2 O-ZnO-SiO.sub.2,
ZnO-B.sub.2 O.sub.3 -SiO.sub.2, and Zn.sub.2 SiO.sub.4 -Zn.sub.2
GeO.sub.4, in Amer. Journ. of Sci., 246, (1) pp 31-40
(1948)..
|
Primary Examiner: Bizot; Hyland
Assistant Examiner: Satterfield; W. R.
Claims
I claim:
1. A composition of matter consisting essentially of, by weight:
from 34 to 40 percent Al.sub.2 O.sub.3 ; from 0.5 to 2 percent BaO;
from 12 to 16 percent ZnO; from 1 to 3 percent K.sub.2 O; from 28
to 36 percent SiO.sub.2 ; from 12 to 18 percent B.sub.2 O.sub.3 ;
from 0.5 to 1.5 percent Na.sub.2 O; and from 0 to 2 percent of
oxides selected from the group consisting of MgO, Li.sub.2 O, SrO,
and CaO.
Description
BACKGROUND OF THE INVENTION
This invention relates to the fabrication of metal-ceramic articles
by a powder technique and to a ceramic powder ideally suited for
use therewith. More particularly, it relates to methods and
apparatus for making integrated circuit (I.C.) packages; to the
ceramic used therewith; and to methods of treating the metal parts
to be sealed therein.
Packages for I.C. components generally comprise metal-ceramic
composite having a ceramic body portion with metallic leads
imbedded therein and a metal base which defines a bed for the
relatively small component. Inserted in the ceramic body portion
are multiple metallic connectors which project into the bed area so
that connections to the I.C. component may be made, and extend
outwardly from the ceramic body to allow for connection of the
package into a circuit.
These packages are currently fabricated by an assembly technique.
Ceramic rectangular washers are fabricated and fired to form dense
ceramic parts. These parts are placed adjacent to each other and to
the metal inserts which will form the leads and the base of the
package and are placed in a graphite or similar mould. The mould is
placed in a firing chamber and, while being fired, pressure is
applied and the ceramic parts are joined together and to the metal
parts.
In more detail, present fabrication techniques employ the following
steps:
A ceramic powder is formulated generally of a glass frit blended
together with alumina and various binders which, when dried,
produces a powder which can easily be handled.
These powders are compressed into parts of various shapes and
configurations depending upon the type of pack being made. They may
be rectangular, round or any other desirable geometric
configuration. After the formation the parts are processed through
the usual pre-firing step for binder removal and a subsequent
firing step to convert the part into a fairly dense ceramic
article.
These parts together with the metal frames which will ultimately
form the leads and the metal part which forms the base are now
placed in a graphite mould containing an upper and lower graphite
die and three graphite rectangles, or other geometric shape as
noted above -- which depend upon the geometric configuration of the
pack being formed, are fitted in the various positions within the
part being formed. A small weight is placed on one of the graphite
parts to supply pressure during the next firing cycle.
This portion of the process depends upon the characteristic of the
ceramic material to assume fluid characteristics that flow during
heating. The graphite dies with the various parts in position are
now fed through a furnace which is heated to the temperature
required for the ceramic to assume the fluid state. This portion of
the process, therefore, causes the ceramic to flow around the leads
of the frame and form a ceramic-metal bond with these leads and the
base. When sufficient time has elapsed for this to take place, the
part is removed from the furnace and is ready for further
processing to make the finished article.
OBJECTS AND SUMMARY OF THE INVENTION
It is an object of the invention to enhance the fabrication of
metal-ceramic articles.
It is another object of the invention to reduce the cost of such
articles.
It is a further object of the invention to enhance the hermetic
seal between the metal-ceramic jointure.
These objects are achieved in one aspect of the invention by
formulating a ceramic powder from glass frit and various amounts of
alumina as a new composition of matter, blending them together with
necessary binders and drying the powder. The powders are placed
into a multiple die having various movable and stationary members
and the metal frame forming the leads and the base are placed in
proper position. A pressing operation is next performed and is
carried out at a temperature of about 150 to 180.degree. Centigrade
and at a pressure of about 4,000 lbs. per square inch, which causes
the powders and the metal parts to bond into a single green part.
This part has sufficient strength to be handled without fear of
breaking. In order to facilitate the bonding between the metal and
the ceramic, the metal part is coated with a glass-suspension in a
binder before insertion into the die.
The green-formed part is next placed in a furnace and fired, first
at a relatively low temperature; that is, about 600.degree. C. for
one hour and then moved into a relatively hotter zone; that is,
about 950.degree. C. where a final conversion of the powder to a
ceramic and the bonding of the ceramic to the metal takes place.
After removal from the furnace and necessary cooling, the article
is cleaned and other similar operations are performed to complete
the handling of the part and it is now ready for use .
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an exploded sectional view of a prior art device;
FIG. 2 is a perspective view of the device made in accordance with
this invention;
FIG. 3 is a flow diagram of a method of preparing the metal parts
to be joined to the ceramic;
FIG. 4 is a sectional perspective view of a portion of the mould
used in fabricating an article in accordance with the
invention;
FIG. 5 is a sectional perspective view of the mould in a secondary
position;
FIG. 6 is a plan view of the mould of FIG. 4; and
FIGS. 7-18 are diagrammatic sectional views of various stages in
the formulation of an article in accordance with this
invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
For a better understanding of the present invention, together with
other and further objects, advantages and capabilities thereof,
reference is made to the following disclosure and appended claims
in connection with the above-described drawings.
Referring now to the drawings with greater particularity, in FIG. 1
is shown an I.C. packaging device, as made by prior art techniques,
designated generally as 20 and which comprises a first ceramic
washer 22 having a substantially rectangular configuration.
Positioned over the ceramic washer is a lead frame 24 which
contains a plurality of inwardly projecting leads 26 only several
of which are shown. The leads are maintained in their desired
location by attachment to a frame 28 which will subsequently be
removed when the package is completed. Placed atop the lead frame
24 is a second ceramic washer 30 which is also substantially
rectangular and whose outer configuration matches that of washer
22. The washer 30 defines a smaller opening 31 which will
subsequently provide the bed for the I.C. Placed atop washer 30 is
a base plate 32 which is also of metal and which has a depression
formed therein and which depression conforms to opening 31 in
washer 30. This assembly, after all of the parts have been
formulated, is completed by stacking together in an appropriate
mould and heating as described above, thus forming the completed
package.
In FIG. 2 is shown a perspective view of a completed device formed
in accordance with the invention to be herein described. It is to
be noted that the prior art device of FIG. 1 is shown in an
inverted position, that is, with the apertures facing downward,
while the device of FIG. 2 is shown with the apertures uppermost.
The device shown in FIG. 2 and designated generally as 40 is formed
in accordance with the invention and comprises a ceramic body
portion 42 which rests upon a metallic base plate 44 of a suitable
material such, for example, as Kovar. It is, of course, essential
that the metallic members and the ceramic portions have
substantially the same thermal coefficient of expansion. Leads 46
are shown projecting from a side wall of the ceramic body 42 and
projecting inwardly to a substantially rectangular opening 48.
Within opening 48 is a second smaller rectangular opening 50 which
actually forms the bed for the I.C. The floor of bed 50 is formed
as a protruding portion on the base plate 44. The package 40 is
fabricated in four general steps, viz.:
1. Preparation of the metal parts.
2. Preparation of the powder for the glass-ceramic portion.
3. Assembly of the metal ceramic package into a green-formed
part.
4. Firing to remove the binder and further firing to completely
form the ceramic member and to complete the seal.
The metal parts, which consist of the lead frame with the leads 46
attached and the base 44, may be fabricated in strips or in
separate pieces. The parts are prepared by first cleaning with a
degreasing agent such, for example, as trichlorethylene. After the
cleaning, the part is sandblasted to furnish an etched surface for
the glass-ceramic material. After the sandblasting the metal parts
are oxidized by heating in an oxidizing atmosphere at a temperature
of about 900.degree. to 1,000.degree. C. for about 100 to 110
seconds. After the oxidizing, at least the oxidized portions are
coated with a suitable flux to facilitate movement of the
glass-ceramic composition therearound during the final steps in
forming the seal. The flux comprises a fluid carrier and a
suspension contained therein with the carrier comprising, by
weight, about 99.64 percent water, about 0.11 percent concentrated
hydrochloric acid, and about 0.25 percent dodecyl alcohol; and the
suspension comprises by weight from 58 to 61 percent ZnO, from 18
to 21 percent B.sub.2 O.sub.3, from 10 to 12 percent SiO.sub.2,
from 0.1 to 0.2 percent Al.sub.2 O.sub.3, from 0.040 to 0.070
percent MgO, from 0.010 to 0.020 percent Na.sub.2 O, from 4 to 5
percent polyvinyl alcohol, from 2 to 4 percent triethylene glycol
and from 0.1 to 0.22 percent hydrodyne. The coating of the part may
be done by spraying on a layer sufficient to give a gray to white
coating on the metal. The coated metal parts are then completely
dried in warm air to fix the suspension on the part.
The new powder formulation, that is, the glass-ceramic composition
which will form the ceramic body portion, comprises by weight from
34 to 40 percent Al.sub.2 O.sub.3, from 0.5 to 2 percent BaO, from
12 to 16 percent ZnO, from 1 to 3 percent K.sub.2 O, from 28 to 36
percent SiO.sub.2, from 12 18 percent B.sub.2 O.sub.3, from 0.5 to
1.5 percent Na.sub.2 O, and from 0 to 2 percent of oxides selected
from the group consisting of MgO, Li.sub.2 O, SrO, and CaO.
The glass-ceramic composition is prepared by mixing the above
ingredients in either a ball mill or "V" type blender depending
upon the amount being prepared. The blending takes from four to
twelve hours. No balls or other objects are present in the mill or
blender as no attrition is required.
After the materials have been blended, a binder material to improve
flow characteristics is added. The binder consists of 2.4 grams of
polyvinyl alcohol, 1.6 grams triethylene glycol, 0.41 grams
concentrated hydrochloric acid, 0.1 gram hydrodyne, and 3 to 4
drops of dodecyl alcohol. These ingredients are made up in about a
50 cc. solution of water. The binder material is added to the
glass-ceramic composition in an amount to make a 3.5 percent
polyvinyl alcohol addition. The binder addition may be made in any
ball mill, blender or similar container to which a few ceramic
balls have been added to aid in the mixing process. The binder
should be present in an amount sufficient to coat all particles of
the glass-ceramic composition. After the mixing of the composition
and the addition of the binder, the entire suspension is removed
from the mill or blender and spray dried to remove all volatile
materials. The resulting powder produced by this method is
spherical, free-flowing and dry.
It will be obvious to those skilled in the art that various
applications for this ceramic material may require different
binders, fluxes and metallic inserts.
Referring now to FIG. 4, there is shown therein diagram-matically a
multiple die in which the green-formed part is fabricated. The die,
designated generally as 52, comprises a first stationary die 54
which defines therein a first geometric opening 56, in this
instance the opening is shown as being rectangular; however, it is
to be noted that any suitable geometric shape may be utilized
depending upon circumstances. Positioned substantially
symmetrically within the first geometric opening 56 is a smaller
second stationary die 58 which also has a substantially rectangular
configuration. A substantially symmetrically located second
geometric opening 60 is positioned within second stationary die 58.
A first movable die 62 having a substantially rectangular washer
configuration is positioned between the first and second stationary
dies and substantially conforms to the first geometric opening. The
upper surface 64 of the first movable die forms the bottom of the
rectangular cavity defined by the first geometric opening.
Positioned within the second geometric opening 60 and substantially
conforming thereto is a second movable die 66. The upper surface 68
of die 66 is aligned with the upper surfaces of first stationary
die 54 and second stationary die 62.
To complete the multiple die, a third movable die 70 defining a
third geometric opening 72 is provided to overlie the first
stationary die 54. Third die 70 is shown in FIG. 3. In the instant
figure, the third die is shown as laying upon the leads 46 of a
lead-in frame and second movable die 68 is shown in a raised
position wherein the upper surface 68 thereof is now planar with
the upper surface of third movable die 70. It will be seen that the
thickness of second movable die 68 is such as to fit between the
innermost ends of leads 46.
Referring now to FIGS. 7 through 18, there is shown a diagrammatic
sequence of the green part forming operation. FIG. 7 shows the
position of the stationary and movable members of the die prior to
the addition of any ceramic material. With the dies in this
position, the first cavity which is formed by the first and second
stationary dies and the upper surface of the first movable die 64
is filled with a first quantity of the previously prepared powdered
ceramic material 74. The powdered material 74 is leveled off to
coincide with the upper surfaces of first and second stationary
dies. In FIG. 9 is shown the addition of a first metallic member 76
which comprises the leads 46 and a frame, not shown, but similar to
frame 28 of FIG. 1. The inner opening defined by the innermost ends
of leads 46 is aligned with the second geometric opening which is
formed in second stationary die 58. FIG. 10 shows the addition of
third movable die 70 which is positioned on top of the first
metallic member 76 and which has its geometric opening 72 aligned
with the first geometric opening 56. FIG. 11 shows the next step in
the operation which is that of raising second movable die 66 until
its upper surface 68 is planar with the upper surface of third
movable die 70. FIG. 12 shows the next step which is the filling of
the cavity 72 with a second given quantity of ceramic material 76
to the level of the upper surface of the third movable die. The
next step in the operation is the addition of a second metallic
member which, in this instance, is the base plate 44. The
protuberance 78 which is formed on base plate 44 is aligned with
the upper surface of second movable die 66. With the proper
alignment being maintained, the green part is now formed by the
application of a suitable force in two different directions, viz.:
downwardly upon the base plate and upwardly by first movable die
62. The force involved is about 4,000 lbs. per square inch. It is
to be noted that, to avoid bending or distortion of the first
metallic member 76, it is essential that this member define a fixed
plane about which the two substantially equal forces are exerted.
Further, to achieve a flowing and semibonding of the ceramic
material to the metal members, the die at least prior to the
application of the force is heated to a temperature of about
150.degree. to 180.degree. C. After the force has been applied and
the compression of the ceramic powder has taken place, the second
movable die 66 is withdrawn to its first position as shown in FIG.
15, and the third movable die is removed. After the removal of the
third movable die, first movable die 62 is raised to push the
completed green-formed article from the mould as shown in FIG.
18.
The green-formed part may now be stored or sent to final processing
since it is found to have exceptional strength characteristics. For
the final processing, the green-formed part is fired in a two-step
operation. The first step is a firing in air at a temperature of
about 600.degree. C. for about one hour. The first firing step
assures the completion of binder removal. The second step is a
firing for about 20 minutes at a temperature of 900.degree. to
975.degree. C. The second firing is done in an inert atmosphere,
for example, nitrogen. After the final firing, the part is cleaned
and it is ready for the insertion and wiring of an I.C.
component.
An exact understanding of the mechanics of the firing operation is
not completely understood at this time. During the firing cycle, it
is or would be expected that the part would shrink and that
cracking or distortion of the frame would occur. While some
shrinkage of the material does occur, there is no cracking or
distortion present. It appears that, during the period of change in
physical size, the ceramic material actually moves along the metal
frame without breaking the seal. When both parts are at the
elevated temperature, that is, in the 900.degree. to 975.degree. C.
range, the change in physical size seems to have been completed and
the parts cool with the same coefficient of expansion. This in turn
forms an article which meets all of the necessary size, shape, and
hermeticity requirements of an I.C. package.
Thus, it will be seen that there has been provided a new and novel
method for fabricating metal-ceramic composite articles. With
particular application to I.C. packages, the fabrication is greatly
enhanced. Many unnecessary firing steps are eliminated and thus the
cost is greatly reduced from the prior art methods of manufacture.
A green part is formed which has exceptional strength
characteristics and which may be handled and stored prior to the
final firing operations.
While there have been shown and described what are at present
considered the preferred embodiments of the invention, it will be
obvious to those skilled in the art that various changes and
modifications may be made therein without departing from the scope
of the invention as defined by the appended claims.
* * * * *