U.S. patent number 3,882,033 [Application Number 05/321,388] was granted by the patent office on 1975-05-06 for silicone grease for semiconductors.
This patent grant is currently assigned to General Electric Company. Invention is credited to John H. Wright.
United States Patent |
3,882,033 |
Wright |
May 6, 1975 |
Silicone grease for semiconductors
Abstract
A neutral, dielectric, strong desiccant, free of material which
might change the semiconductor junction doping, is added to a
silicone grease. The grease is used to surround semiconductor
junctions as a heat transfer media. The presence of the desiccant
in the grease reduces the noise background which is generated in
semiconductors in the presence of small amounts of water.
Inventors: |
Wright; John H. (Elnora,
NY) |
Assignee: |
General Electric Company
(Waterford, NY)
|
Family
ID: |
26856652 |
Appl.
No.: |
05/321,388 |
Filed: |
January 5, 1973 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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160163 |
Jul 6, 1971 |
|
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|
764999 |
Oct 4, 1968 |
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Current U.S.
Class: |
252/572; 252/194;
257/E23.107; 252/75; 257/682 |
Current CPC
Class: |
H01L
23/3737 (20130101); H01L 23/42 (20130101); H01L
23/3157 (20130101); H01L 2924/0002 (20130101); H01L
2924/0002 (20130101); H01L 2924/00 (20130101) |
Current International
Class: |
H01L
23/42 (20060101); H01L 23/373 (20060101); H01L
23/28 (20060101); H01L 23/34 (20060101); H01L
23/31 (20060101); H01b 003/46 () |
Field of
Search: |
;252/63.5,63.7,62,28,49.6,194,75,78 ;317/234D,234E |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Condensed Chemical Dictionary, Sixth Ed., 1966, pp. 207 and
1241..
|
Primary Examiner: Padgett; Benjamin R.
Assistant Examiner: Gluck; Irwin
Attorney, Agent or Firm: Voss, Esq.; Donald J. Koltos, Esq.;
E. Philip Neuhauser, Esq.; Frank L.
Parent Case Text
This application is a continuation of application Ser. No. 160,163,
filed Jul. 6, 1971 and now abandoned which was a
continuation-in-part of copending application Ser. No. 764,999,
filed Oct. 4, 1968 and now abandoned.
Claims
What I claim is:
1. A silicone grease composition consisting essentially of on a
weight basis:
1. from 15 to 97.9 percent of a polysiloxane fluid of the
formula:
(R).sub.n SiO.sub.4.sub.-n/2
where
R represents a member selected from the class consisting of alkyl
radicals having from one to 22 carbon atoms, lower alkenyl radicals
having two to eight carbon atoms, cycloalkyl radicals having from
five to seven carbon atoms; mononuclear and binuclear aryl
radicals; mononuclear aryl lower alkyl radicals; cyano lower alkyl
radicals and up to 50 percent of the R radicals can also be
hydrogen; and n has a value of from 0.002 to 3.0,
2. from 0.1 percent of a neutral, dielectric desiccant being at
least one selected from the class consisting of anhydrous calcium
sulfate and synthetic zeolites being at least one selected from the
class consisting of:
0.95+0.25M.sub.2/m O.Al.sub.2 O.sub.3 :2.175+0.825SiO.sub.2
:YH.sub.2 O
wherein
m represents at least one of the materials in the groups consisting
of hydrogen, ammonium, metals in Groups I and II of the periodic
table and the transition metals of the periodic table, m represents
the valence of M, and Y may be any value up to about 6, and
0.9+0.2M'.sub.2/m O:Al.sub.2 O.sub.3 ;2.5+0.5SiO.sub.2 Y'H.sub.2
O
wherein
M' represents at least one cation having a valence of not more than
3, m' represents the valence of M', and Y' may be any value up to
about 8, and
3. from 2 percent to 84.9 percent of a grease thickening agent
being at least one selected from the class consisting of finely
divided, non-conducting inert oxides of metallic and glass-metallic
materials and inert organic thickening materials and mixtures
thereof substantially free of interfering water.
2. A composition of claim 1 wherein the neutral, dielectric
desiccant is anhydrous calcium sulfate.
3. The composition of claim 1 wherein the dielectric desiccant is a
synthetic zeolite within the scope of the formula:
0.95+0.25M.sub.2/m O.Al.sub. 2 O.sub.3 :2.075+0.825SiO.sub.2
:YH.sub.2 O
wherein
M represents at least one of the materials in the groups consisting
of metals in Groups I and II of the periodic table.
4. The composition of claim 1 wherein the dielectric desiccant is
anhydrous calcium sulfate made by the dehydration of hydrated
calcium sulfate.
5. A composition within the scope of claim 1, consisting
essentially of on a weight basis:
1. from 15 to 97.9 percent of a polysiloxane fluid of the
formula
(CH.sub.3).sub.n SiO.sub.4.sub.-n/2
2. from 0.1 percent to 35 percent of a neutral dielectric desiccant
selected from the class consisting of:
0.9+0.2Na.sub.2 O:Al.sub.2 O.sub.3 :2.5+0.5SiO.sub.2 :YH.sub.2
O
and
0.9+0.2CaO:Al.sub.2 O.sub.3 :2.5+0.5SiO.sub.2 :YH.sub.2 O
3. from 2 percent to 84.9 percent of zinc oxide.
6. The composition of claim 5 wherein the dielectric desiccant
is:
0.9+0.2Na.sub.2 O:Al.sub.2 O.sub.3 :2.5+0.5SiO.sub.2 :YH.sub.2
O
7. The composition of claim 5 wherein the dielectric desiccant
is:
0.9+2CaO:Al.sub.2 O.sub.3 :2.5+0.5SiO.sub.2 :YH.sub.2 O
8. A composition within the scope of claim 1 wherein R represents a
member selected from the class consisting of alkyl radicals having
from one to 22 carbon atoms and mononuclear aryl radicals.
9. The composition of claim 1 wherein the grease thickening agent
is zinc oxide.
Description
This invention relates to improved organopoly-siloxane grease
compositions. More particularly, the present invention is concerned
with organopolysiloxane grease compositions which provide a much
lower noise level when used as heat transfer media surrounding the
junction of a semiconductor.
Organopolysiloxane greases and grease compositions are well known
in the art and have been used as lubricants, dielectric compounds,
sealing compounds, high vacuum greases, and as heat transfer media
in the manufacture of semiconductors. These organopolysiloxane
greases have been particularly valuable in the manufacture of
semiconductors because of their high degree of heat stability,
their water repellency, their high-low temperature viscosity flow
characteristics, dielectric properties, heat transfer properties,
and their ability to surround a semiconductor junction without
chemically contaminating the semiconductor junction. While the
greases themselves do not cause background noise when used in the
fabrication of semiconductors, it has been found that when the
greases employed contain trace amounts of water, that a background
noise develops due to this water contamination.
In an attempt to solve the problem of background noise in
semiconductors due to water present in the silicone grease, various
desiccants were added to the grease to absorb the water present.
While many of the desiccants served their purpose as far as water
pickup was concerned, they produced fatal side affects. Some would
absorb water, become dissolved in the water, and become conductive,
destroying the semiconductor operation. Others, such as apparently
neutral clays apparently contained internally trapped acids or
bases, which degraded the silicone grease, causing separation of
the components and a partial destruction of the heat transfer
capabilities of the grease. Boron oxide caused a hardening of the
grease upon water pickup resulting in a destruction of the flow
properties of the grease which decreased the heat transfer
capabilities.
It was found in order to be effective, the desiccant must be
non-conductive, neutral, non-abrasive, non-catalytic, non-reactive
with the semiconductor junction and free of small amounts of
impurities which destroy its capabilities. The abrasive character
of the desiccant will not interfere with the semiconductor
operation but does damage the milling equipment used to manufacture
the grease.
It is an objective of the present invention to provide improved
organopolysiloxane grease compositions which retain all the highly
beneficial properties of heretofore known organopolysiloxane grease
compositions used in the manufacture of semiconductors and which,
in addition, reduce the noise level produced by a semiconductor.
The grease compositions of the present invention contain a neutral,
dielectric, strong desiccant free of materials which might change
the semiconductor junction doping. The presence of the desiccant
provides lowered noise levels when the grease composition is used
in the manufacture of semiconductors.
The grease compositions of the present invention comprise on a
weight basis:
1. from 15 to 97.9 percent of a polysiloxane fluid containing
silicon-bonded organo groups selected from the class consisting of
alkyl radicals having from one to 22 carbon atoms, lower alkenyl
radicals having from two to eight carbon atoms, cycloalkyl radicals
having from five to seven carbon atoms in the ring, mononuclear and
binuclear aryl radicals, mononuclear aryl lower alkyl radicals,
cyano lower alkyl radicals and up to 50 percent of the R radicals
can also be hydrogen;
2. from 0.1 to 33 percent and preferably from 1 to 10 percent of a
neutral, dielectric desiccant selected from the class consisting of
anhydrous calcium sulfate and synthetic zeolites;
3. from 2 to 84.9 percent of a grease thickening and thermal
conducting agent; and
4. optionally from 0.01 to 5 percent of a grease stabilizer such as
the polyether and boron compounds disclosed in U.S. Pat. Nos.
3,037,933 and 3,103,491 of Wright.
The fluid organopolysiloxanes employed in the practice of the
present invention are known in the art. The organopolysiloxane
fluids may be characterized as organopolysiloxane fluids in which
all of the valences of silicon other than those satisfied by oxygen
atoms are satisfied by monovalent organic radicals attached to
silicon through a silicon carbon linkage. This type of
organopolysiloxane can be characterized as having the average
formula:
R.sub.n SiO.sub.4.sub.-n/2 ( 1)
where R represents a member selected from the class consisting of
alkyl radicals having from one to 22 carbon atoms, cycloalkyl
radicals having from 5 to 7 carbon atoms in the ring, mononuclear
and binuclear aryl radicals, mononuclear aryl lower alkyl radicals,
cyano lower alkyl radicals and lower alkenyl radicals having form
two to eight carbon atoms and n has a value of from 2.002 to 3.0.
Up to 50 percent of the R radical can also be hydrogen in which
case the formula also embraces organohydrogenpolysiloxanes. For the
purposes of the present application, these materials too will be
referred to as organopolysiloxanes. It is preferred, however, that
R be an organo group as above defined as the reactivity of the
silanic hydrogen may interfere with the simiconductor
operation.
Among the specific radicals represented by R in formula (1) are
alkyl radicals having from one to 22 carbon atoms, e.g., methyl,
ethyl, propyl, octyl, decyl, dodecyl, tetradecyl, etc., radicals;
cycloalkyl radicals having five to one carbon atoms in the ring,
e.g., cyclopentyl, cyclohexyl, cycloheptyl, etc.; mononuclear and
binuclear aryl radicals, e.g., phenyl, naphthyl, biphenyl, tolyl,
xylyl, etc. radicals; mononuclear aralkyl radicals having up to 16
carbon atoms in the alkyl group, e.g., benzyl, phenylethyl,
phenyloctyl, etc. radicals; lower alkenyl radicals having from two
to eight carbon atoms, e.g., vinyl, allyl, pentenyl, etc. radicals;
and cyano lower alkyl radicals having two to five carbon atoms,
e.g., cyanomethyl, alpha-cyanopropyl, etc., radicals.
The preparation of methyl alkyl polysiloxanes within the scope of
formula (1) involves an SiH-olefin addition reaction. This reaction
simply involves the addition of an alpha-olefin having from two to
22 carbon atoms to some type of methylhydrogenpolysiloxane. For
example, the preparation of a trimethylsilyl chain-stopped methyl
higher alkylpolysiloxanes of formula (1) involves the reaction
between a methylhydrogenpolysiloxane having the formula:
(CH.sub.3).sub.n-p (H).sub.p (R").sub.q SiO.sub.4.sub.-n/2
where n is as above defined and p has a value of from 0.01 to 1
with an alpha-olefin. The reaction of the alpha-olefin and the
methylhydrogen polysiloxane can take place in the presence of one
of the elemental platinum or platinum compound catalysts. The
platinum compound catalyst can be selected from that group of
platinum compound catalysts which are operative to catalyze the
addition of silicon-hydrogen bonds across olefinic bonds.
Among the may useful catalysts for this addition reaction are
chloroplatinic acid as described in U.S. Pat. No. 2,823,218 --
Speier et al., the reaction product of chloroplatinic acid with
either an alcohol, an ether or an aldehyde as described in U.S.
Pat. No. 3,220,972 -- Lamoreaux, trimethylplatinum iodide and
hexamethyldiplatinum as described in U.S. Pat. No. 3,313,713 --
Lamoreaux, the platinum olefin complex catalysts as described in
U.S. Pat. No. 3,159,601 of Ashby and the platinum cyclopropane
complex catalyst as described in U.S. Pat. No. 3,159,662 of
Ashby.
The SiH-olefin addition reaction may be run at room temperature or
at temperatures up to 200.degree.C, depending upon catalyst
concentration. The catalyst concentration can vary from
10.sup..sup.-7 to 10.sup..sup.-3 and preferably 10.sup..sup.-5 to
10.sup..sup.-4 moles of platinum as metal per mole of olefin
containing molecules present. Generally, the
methylhydrogenpoly-siloxane is mixed with a portion of the
alpha-olefin, all of the catalyst is added, and then the remaining
alphaolefin is added at a rate sufficient to maintain the reaction
temperature in the neighborhood of from about 50.degree. to
120.degree.C and, at the end of the addition of the alpha-olefin,
the reaction is completed.
The addition reaction is effected by adding to the
methylhydrogenpolysiloxane a platinum catalyst of one of the types
previously described. The appropriate amount of alpha-olefin is
then added and reacted via the aforedescribed SiH-olefin addition
reaction.
When preparing a linear copolymer of the type described in formula
(1), the general procedure as described earlier is followed. The
methylhydrogenpolysiloxane is reacted with the appropriate amount
of alpha-olefin.
It should be understood that the viscosity of the
organopolysiloxane fluid within the scope of formula (1) will vary
with the molecular weight of the fluid and with the nature of the
silicon-bonded organic groups in the fluid. Although any organic
polysiloxane fluid within the scope of formula (1) is applicable,
in the practice of the present invention, it is preferred that the
fluid have a viscosity of from about 10 centistokes to 100,000
centistokes when measured at 25.degree.C.
It should also be understood that the organopolysiloxane fluids of
formula (1) can include siloxane units of varied types and
formulations such as triorganosiloxane units and diorganosiloxane
units alone or in combination with monoorganosiloxane units. The
only requirement is that the ratio of the various siloxane units
employed be selected so that the average composition of the
copolymeric fluid is within the scope of formula (1). These various
siloxane units may contain the same or different siliconbonded
organic radicals. For example, the siloxane units employed in
preparing the fluid for formula (1) can contain trimethylsiloxane
units, methylphenylsiloxane units, diphenylsiloxane units,
triphenylsiloxane units, methyl-beta-cyanoethylsiloxane units,
methylsiloxane units, methyloctylsiloxane units, phenylsiloxane
units, beta-cyanoethylsiloxane units, etc.
The dielectric desiccants employed in the practice of the present
invention are selected from the class consisting of anhydrous
calcium sulfate and synthetic zeolites otherwise known as molecular
sieves. The molecular sieves that can be used in this invention are
the zeolites encompassed by the average formula:
0.95.+-.0.25M.sub.2/m O:A1.sub. 2 O.sub.3 :XSiO.sub.2 :YH.sub.2
O
where M is a cation having a valence of not more than 3 (such as
calcium, strontium, barium, sodium, potassium and lithium, but
preferably sodium), m is the valence of cation M and has a value of
1 to 3, X has a value of 1.35 to about 9 and preferably a value of
2.175.+-.0.825 and y has a value of from 0 to about 6, preferably
from 0 to 3. The molecular sieves and processes for their
production are disclosed in numerous publications and patents
including U.S. Pat. Nos. 2,882,243 and 2,882,244 -- Milton, U.S.
Pat. No. 3,130,006 -- Rabo and U.S. Pat. No. 3,130,007 -- Breck. In
U.S. Pat. No. 2,882,243 of Milton, the cation M of the zeolites is
defined as monovalent and divalent actions, such as lithium and
magnesium; metal ions in group I of the periodic table such as
potassium and silver; group II metal ions such as calcium, and
strontium; metal ions of the transition metals such as nickel; and
other ions, for example, hydrogen and ammonium - - - . The
transition metals are those whose atomic numbers are from 21 to 28,
from 39 to 46 and from 72 to 78 inclusive, namely, scandium,
titanium, vanadium, chromium, manganese, iron, cobalt, nickel,
yttrium, zirconium, niobium, molybdenum, ruthium, rhodium,
palladium, halfium, tantalum, tungsten, rhenium, osmium, iridium
and platinum. In U.S. Pat. No. 2,882,244 the zeolites are defined
by the formula
0.9.+-.0.2M'.sub.2/m.sub.' 0:Al.sub.2 O.sub.3 :2.5.+-.0.5SiO.sub.2
Y'H.sub.2 O
wherein M' represents a cation having a valence of not more than 3,
m' represents the valence of M', and Y' may be any value up to 8.
The molecular sieves that have been found particularly useful in
this invention are the sodium forms of the molecular sieves and the
calcium forms of the molecular sieves which are encompassed by the
following formulas:
0.9.+-.0.2Na.sub.2 O:Al.sub.2 O.sub.3 : 2.5.+-.0.5SiO.sub.2 :
YH.sub.2 O
and
0.9.+-.0.2CaO:Al.sub.2 O.sub.3 :2.5.+-.0.5SiO.sub.2 :YH.sub.2 O
wherein y has the above defined meaning. These molecular sieves
have openings capable of absorbing materials having molecular
diameters in the range of 5A or less. The preferred particle size
of the molecular sieves is in the neighborhood of a 5 micron
diameter assuming the molecular sieve particles are generally
spherical.
The preferred form of calcium sulfate to be used in the practice of
the present invention is an anhydrous calcium sulfate formed by the
dehydration of CaSO.sub.4.2H.sub.2 O by heat. In the preferred form
of my invention these calcium sulfate particles are also in the
neighborhood of a 5 micron particle size.
The dielectric desiccants employed in the practice of the present
invention should be relatively pure materials. They should not
contain impurities such as acids or bases since acids and bases
affect the molecular structure of silicone molecules employed in
the grease formulation. A water slurry of the dielectric desiccants
employed should have a pH of between 5 and 10. The dielectric
desiccants in addition should contain no foreign materials which
would contaminate the semiconductor. They should also not contain
any materials that are conductive as this would result in current
flow in the semiconductor which is the reverse of the design
current flow path.
The third component of the grease compositions of the present
invention are the grease thickening agents which are well known in
the art. This invention contemplates the use of many of these well
known thickening agents to form a grease composition of the desired
consistency. Stability is important in the manufacture of the
present greases in that the thickening agent must remain suspended
in the grease composition. If the thickening agent were to settle
out after application, this would result in a change in the
electrical characteristics of the semiconductor.
In many applications heat transfer is also important such as in
power transistors. The filler in such cases must be one which will
allow the grease to conduct the heat away from the transistor
junction fairly rapidly. Excessive heat build up will destroy the
transistor.
Examples of suitable thickening agents include finely divided inert
oxides of metallic and quasi-metallic materials such as silica,
alumina, iron oxide, titania, zinc oxides, glass fibers and clays.
Silica, when used as a thickening agent, is preferably employed as
an aerogel but may also be employed as fumed silica, precipitated
silica or natural deposits such as diatomaceous earth. Other
thickening agents include polyethylene, polypropylene,
polymethylmethacrylate and other inert organic thickeners. Zinc
oxide is the preferred thickener. One of the primary reasons for
this preference is its excellent heat transfer properties.
The term "grease" as employed in the present application is
intended to refer to grease-like materials which may have
consistencies varying from readily flowable materials to materials
which exhibit almost no flow. The consistency of the greases of the
present invention depend on the amount of thickening agent
employed, the type of thickening agent employed and the particular
polysiloxane fluids in the grease.
As it is the water in the grease compositions used in semiconductor
manufacture that causes increased noise levels, it is, of course,
understood that the thickening agents used in the manufacture of
such greases be substantially free from such interferring water.
While the amounts of thickening agent employed in the grease
compositions of the present invention are not critical and may vary
within wide limits depending on the particular consistency desired
in the final product, it has been found that the amount of
thickening agent usually varies from about 2 to about 80 percent
and preferably from about 5 to 65 percent by weight based on the
weight of the grease composition.
The grease compositions of the present invention can be prepared in
conventional fashion by merely mixing the polysiloxane fluid as a
thickening agent and the dielectric desiccant in conventional
mixing and/or milling equipment. Especially satisfactory results
have been obtained when the compositions have been mixed on a
conventional paint mill or on a conventional colloid mill.
The following examples are illustrative of my invention and are not
intended for purposes of limitation. All parts are by weight unless
otherwise indicated.
EXAMPLE 1 1
To 87 parts of a trimethylsilyl end-stopped dimethylsilicone fluid
having a viscosity of 350 centistokes were added 25 parts of
molecular sieves having a pore diameter of 5A and a particle size
of 5 microns, 9 parts of finely divided precipitated silica (dry)
and 1 part of trimethoxyboroxine. The composition was mixed in a
grease kettle and then milled three passes on a three roll mill.
The resulting grease had a penetration of 269 and a water content
of less than 50 PPM. A comparable grease made without the molecular
sieves had a penetration of 274 and a water content of over 280
PPM.
EXAMPLE 2
To 29 parts of a trimethylsilyl end-stopped dimethylsilicone fluid
having a viscosity of 350 centistokes were added 1 part of
molecular sieves having a pore diameter of 5A and a particle size
of 5 microns, and 70 parts of finely divided zinc oxide. The
composition was mixed in a grease kettle and then milled three
passes on a three roll mill. The same composition was prepared
without the addition of the molecular sieves and used as control.
Semiconductors made using the grease composition containing the
molecular sieves to surround the semiconductor junction and to fill
the semiconductor case for heat transfer purposes had a very low
noise level as compared with control.
EXAMPLE 3
To 27 parts of a trimethylsilyl end-stopped dimethylsilicone fluid
having a viscosity of 1,000 centistokes was added 5 parts of finely
divided anhydrous calcium sulfate and 68 parts of zinc oxide. The
composition was mixed in a grease kettle and then milled three
passes on a three roll mill. The same composition was made without
employing the calcium sulfate and used as control. A semiconductor
made utilizing the grease containing the calcium sulfate had a much
lower noise level than a semiconductor used without employing
anhydrous calcium sulfate. The grease containing the calcium
sulfate had a water content of less than 50 PPM and the grease
prepared without the calcium sulfate had a water content of over
200 PPM.
While the foregoing examples and discussions have illustrated many
of the variations and compositions possible within the scope of the
present invention, it should be understood that this invention
relates broadly to a silicone grease to be used in a semiconductor
manufacture which contains a dielectric desiccant selected from the
class consisting of synthetic molecular sieves and anhydrous
calcium sulfate.
* * * * *