U.S. patent application number 09/918821 was filed with the patent office on 2002-03-07 for sheet for a thermal conductive substrate, a method for manufacturing the same, a thermal conductive substrate using the sheet and a method for manufacturing the same.
Invention is credited to Handa, Hiroyuki, Nakatani, Seiichi.
Application Number | 20020026980 09/918821 |
Document ID | / |
Family ID | 17457405 |
Filed Date | 2002-03-07 |
United States Patent
Application |
20020026980 |
Kind Code |
A1 |
Nakatani, Seiichi ; et
al. |
March 7, 2002 |
Sheet for a thermal conductive substrate, a method for
manufacturing the same, a thermal conductive substrate using the
sheet and a method for manufacturing the same
Abstract
A thermally conductive substrate having a structure in which
inorganic filler for improving the thermal conductivity and
thermosetting resin composition are included. The thermosetting
resin composition has a flexibility in the not-hardened state, and
becomes rigid after hardening. The thermally conductive substrate
has excellent thermal radiation characteristics. The method of
manufacturing the thermally conductive substrate includes: piling
up (a) the thermally conductive sheets comprising 70 to 95 weight
parts of an inorganic filler, and 4.9 to 28 weight parts of a
thermosetting resin composition, the thermosetting resin
composition comprising at least one thermosetting resin, a hardener
and a hardening accelerator, and (b) lead frame on which a wiring
is formed; thermal pressing the pile; filling the thermally
conductive sheet to the surface of the lead frame; hardening the
thermosetting resin; cutting excess sections of the thermally
conductive substrate; and processing the bending perpendicularly
for making a removable electrode.
Inventors: |
Nakatani, Seiichi; (Osaka,
JP) ; Handa, Hiroyuki; (Osaka, JP) |
Correspondence
Address: |
Barry E. Bretschneider
Morrison & Foerster LLP
2000 Pennsylvania Ave., N.W.
Washington
DC
20006-1888
US
|
Family ID: |
17457405 |
Appl. No.: |
09/918821 |
Filed: |
August 1, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09918821 |
Aug 1, 2001 |
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09495902 |
Feb 2, 2000 |
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09495902 |
Feb 2, 2000 |
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08944799 |
Oct 6, 1997 |
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6060150 |
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Current U.S.
Class: |
156/252 ;
257/E23.007; 257/E23.063; 257/E23.066 |
Current CPC
Class: |
B32B 2307/302 20130101;
H05K 3/4614 20130101; H05K 1/0373 20130101; H05K 2201/0355
20130101; B32B 2457/08 20130101; H01L 23/49833 20130101; H01L
2924/0002 20130101; Y10T 428/265 20150115; Y10T 428/257 20150115;
Y10T 428/258 20150115; H01L 2924/3011 20130101; Y10T 156/1056
20150115; H05K 3/202 20130101; H05K 1/056 20130101; H05K 3/4092
20130101; Y10T 156/1057 20150115; Y10T 428/31681 20150401; B32B
27/20 20130101; H01L 2924/0002 20130101; H05K 3/4069 20130101; Y10T
428/25 20150115; Y10T 156/1034 20150115; H05K 2201/0209 20130101;
H01L 2924/00 20130101; Y10T 156/1092 20150115; Y10T 156/109
20150115; H05K 3/0058 20130101; Y10T 428/252 20150115; B32B 15/08
20130101; Y10T 428/31692 20150401; Y10T 428/24917 20150115; Y10S
428/901 20130101; H01L 23/49861 20130101; B32B 2311/12 20130101;
B32B 2305/74 20130101; H01L 23/145 20130101; H05K 3/4652
20130101 |
Class at
Publication: |
156/252 |
International
Class: |
B32B 031/00 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 9, 1996 |
JP |
8-268357 |
Claims
What is claimed is:
1. A sheet mixture for a thermally conductive substrate comprising
70 to 95 weight parts of an inorganic filler and 5 to 30 weight
parts of a thermosetting resin composition comprising at least one
thermosetting resin, a hardener and a hardening accelerator: said
sheet mixture having flexibility in a half hardened state or
partially hardened state.
2. A sheet mixture for a thermally conductive substrate according
to claim 1, wherein the half hardened state or partially hardened
state has viscosity in the range of 10.sup.2 to 10.sup.5
(Pa.multidot.s).
3. A sheet mixture for a thermally conductive substrate according
to claim 1, wherein the half hardened state or partially hardened
state has viscosity in the range of 10.sup.3 to 10.sup.4
(Pa.multidot.s).
4. A sheet mixture for a thermally conductive substrate according
to claim 1, wherein 0.1 to 2 weight parts of a solvent having a
boiling point of not less than 150.degree. C. is further added to
100 weight parts of a mixture of an inorganic filler and solid
thermosetting resin composition.
5. A sheet mixture for a thermally conductive substrate according
to claim 4, wherein said solvent having a boiling point of not less
than 150.degree. C. is at least one solvent selected from the group
consisting of ethyl carbitol, butyl carbitol and butyl carbitol
acetate.
6. A sheet mixture for a thermally conductive substrate according
to claim 1, wherein said thermosetting resin composition comprises:
1) 0 to 45 weight parts of a first resin that is solid at room
temperature, 2) 5 to 50 weight parts of a second resin that is
liquid at room temperature, 3) 4.9 to 45 weight parts of said
hardener, and 4) 0.1 to 5 weight parts of said hardening
accelerator in 100 weight parts of said thermosetting resin
composition.
7. A sheet mixture for a thermally conductive substrate according
to claim 6, wherein said first resin contains one or more
components selected from the group consisting of bisphenol A epoxy
resin, bisphenol F epoxy resin and liquid phenol resin.
8. A sheet mixture for a thermally conductive substrate according
to claim 1, wherein said thermosetting resin composition is at
least one resin selected from the group consisting of epoxy resin,
phenol resin and cyanate resin.
9. A sheet mixture for a thermally conductive substrate according
to claim 1, wherein said thermosetting resin is a brominated
multifunctional epoxy resin, said hardener is a bisphenol A novolak
resin, and said hardening accelerator is an imidazole.
10. A sheet mixture for a thermally conductive substrates according
to claim 9, wherein said brominated multifunctional epoxy resin is
in the range of 60 to 80 weight parts; said bisphenol A novolak
resin is in the range of 18 to 39.9 weight parts, and said
imidazole is in the range of 0.1 to 2 weight parts, in 100 weight
parts of said thermosetting resin composition.
11. A sheet mixture for a thermally conductive substrate according
to claim 1, wherein said inorganic filler is at least one kind of
filler selected from the group consisting of Al.sub.2O.sub.3, MgO,
BN and AlN.
12. A sheet mixture for a thermally conductive substrate according
to calim 1, further comprising at least one additives selected from
the group consisting of coupling agent, dispersing agent, coloring
agent and tack free agent.
13. A thermally conductive substrate, comprising said thermosetting
resin according to claim 1 in a hardened state, wherein the
coefficient of thermal expansion is in the range of 8 to 20
ppm/.degree. C. and the thermal conductivity is in the range of 1
to 10 W/mK and the electrical resistance is in the range of an
electric insulator.
14. A thermally conductive substrate according to claim 13, wherein
the flexural strength of said thermally conductive substrate is not
less than 10 Kgf/mm.sup.2.
15. A thermally conductive substrate according to claim 13, wherein
the flexural strength of said thermally conductive substrate is in
the range of 10 to 20 Kgf/mm.sup.2.
16. A thermally conductive substrate according to claim 13, wherein
a lead frame is further integrated to the thermally conductive
substrate, and said thermally conductive substrate is filled to the
surface of the lead frame.
17. A thermally conductive substrate according to claim 16, wherein
a metal substrate for thermal radiation is further formed on the
face opposite to the face to which the lead frame is adhered of the
thermally conductive substrate.
18. A thermally conductive substrate according to claim 16, wherein
a printed circuit board having two or more wiring layers is
integrated into one part of the thermally conductive substrate near
the face to which the lead frame is adhered to the thermally
conductive substrate, said thermally conductive substrate is filled
to the surface of the lead frame and said printed circuit board has
two or more wiring layers.
19. A thermally conductive substrate according to claim 13, wherein
the thermally conductive substrate has a through hole, said through
hole is filled with conductive resin composition or is plated with
copper, and a metallic foil wiring pattern is further formed and
integrated on both sides of the substrate.
20. A thermally conductive substrate according to claim 13, wherein
a plurality of the thermally conductive substrates are layered and
each thermally conductive substrate has a through hole, said
through hole is filled with a conductive resin composition and an
internal wiring pattern is composed of said conductive resin
composition, and a metallic foil wiring pattern is further formed
and integrated on both sides of the substrate.
21. A thermally conductive substrate according to claim 20. wherein
said metallic foil is a copper foil having a thickness of 12 to 200
.mu.m and having faces at least one surface of which is a rough
surface.
22. A thermally conductive substrate according to claim 20, wherein
said conductive resin composition comprises: (1) 70 to 95 weight
parts of at least one metallic powder selected from the group
consisting of silver, copper and nickel; and (2) 5 to 30 weight
parts of a thermosetting resin composition comprising a
thermosetting resin and a and hardener.
23. A thermally conductive substrate according to claim 13, wherein
said inorganic filler has a particle diameter of 0.1 to 100 .mu.m
on the average.
24. A method for manufacturing the sheet for the thermally
conductive substrate, which comprises: (1) forming a slurry mixture
comprising 70 to 95 weight parts of inorganic filler, 4.9 to 28
weight parts of thermosetting resin composition and 0.1 to 2 weight
parts of solvent having a boiling point of not less than
150.degree. C. and solvent having a boiling point not more than
100.degree. C.; (2) forming said slurry mixture into a film having
a desired thickness; and (3) drying the solvent having a boiling
point of not more than 100.degree. C. of said film slurry.
25. A method for manufacturing a sheet for a thermally conductive
substrate according to claim 24, wherein said thermosetting resin
composition comprises a brominated multifunctional epoxy resin as a
main component, a bisphenol A novolak resin as a hardener, and an
imidazole as a hardening accelerator.
26. A method for manufacturing a sheet for a thermally conductive
substrate according to claim 24, wherein said brominated
multifunctional epoxy resin is in the range of 60 to 80 weight
parts; bisphenol A novolak resin as a hardener is in the range of
18 to 39.9 weight parts, and said imidazole as a hardening
accelerator is in the range of 0.1 to 2 weight parts, in the 100
weight parts of said thermosetting resin.
27. A method for manufacturing a sheet for a thermally conductive
substrate according to claim 24, wherein said solvent having a
boiling point of not less than 150.degree. C. is at least one
solvent selected from the group consisting of ethyl carbitol, butyl
carbitol and butyl carbitol acetate.
28. A method for manufacturing a sheet for a thermally conductive
substrate according to claim 24, wherein said solvent having a
boiling point of not more than 100.degree. C. is one solvent
selected from the group consisting of methyl ethyl ketone,
isopropanol and toluene.
29. A method for manufacturing a sheet for a thermally conductive
substrate, which comprises: (1) forming a slurry mixture comprising
70 to 95 weight parts of inorganic filler, 5 to 30 weight parts in
total weight of thermosetting resin that is solid at room
temperature and a liquid thermosetting resin that is liquid at room
temperature and solvent having a boiling point not more than
100.degree. C.; (2) forming said slurry mixture into a film having
a desired thickness; and (3) drying the solvent having a boiling
point of not more than 100.degree. C. of the film slurry.
30. A method for manufacturing a sheet for a thermally conductive
substrate according to claim 29, wherein said thermosetting resin
mixture comprises: 1) 0 to 45 weight parts of said solid
thermosetting resin that is solid at room temperature, 2) 5 to 50
weight parts of said liquid thermosetting resin that is liquid at
room temperature, 3) 4.9 to 45 weight parts of a hardener, and 4)
0.1 to 5 weight parts of a hardening accelerator when the total
weight of said solid thermosetting resin and said liquid
thermosetting resin is 100 weight parts.
31. A method for manufacturing a sheet for a thermally conductive
substrate according to claim 29, wherein the main component of said
solid thermosetting resin is one or more components selected from
the group consisting of bisphenol A epoxy resin, bisphenol F epoxy
resin and liquid phenol resin.
32. A method for manufacturing a sheet for a thermally conductive
substrate according to claim 29, wherein said thermosetting resin
composition comprises a brominated multifunctional epoxy resin as a
main component, a bisphenol A novolak resin as a hardener and an
imidazole as a hardening accelerator.
33. A method for manufacturing a sheet for a thermally conductive
substrate according to claim 29, wherein said brominated
multifunctional epoxy resin is in the range of 60 to 80 weight
parts, said bisphenol A novolak resin is in the range of 18 to 39.9
weight parts, and said imidazole as a hardening accelerator is in
the range of 0.1 to 2 weight parts in 100 weight parts of said
thermosetting resin composition.
34. A method for manufacturing a sheet for a thermally conductive
substrates according to claim 29, wherein said solvent having a
boiling point of not more than 150.degree. C. is at least one
solvent selected from the group consisting of ethyl carbitol, butyl
carbitol and butyl carbitol acetate.
35. A method for manufacturing a sheet for a thermally conductive
substrate according to claim 29, wherein said solvent having a
boiling point of not more than 100.degree. C. is one solvent
selected from the group consisting of methyl ethyl ketone,
isopropanol and toluene.
36. A method for manufacturing a thermally conductive substrate,
which comprises: (1) piling up a lead frame on a face of the sheet
for the thermally conductive substrate manufactured by the method
according to claim 24; (2) molding the sheet at a temperature below
the hardening temperature of the thermosetting resin composition
and at the pressure in the range of 10 to 200 Kg/cm.sup.2; (3)
filling the sheet and integrating to the surface of the lead frame;
and (4) hardening said thermosetting resin by thermal pressing at
the pressure in the range of 0 to 200 Kg/cm.sup.2.
37. The method for manufacturing a thermally conductive substrate
according to claim 36, wherein a metal substrate for thermal
radiation is further formed on the face opposite to the face to
which the lead frame is adhered to the thermally conductive
substrate.
38. A method for manufacturing a thermally conductive substrate,
which comprises: (1) placing a lead frame and a printed circuit
board having two or more wiring layers on the sheet for the
thermally conductive substrate manufactured by the method according
to claim 24 in a way in which said lead frame and said printed
circuit board are not overlapped; (2) molding the sheet at the
temperature below the hardening temperature of the thermosetting
resin composition and at the pressure in the range of 10 to 200
Kg/cm.sup.2; (3) filling the sheet and integrating to the surface
of said lead frame and said printed circuit board having two or
more wiring layers; and (4) hardening said thermosetting resin by
thermal pressing at the pressure of 0 to 200 Kg/cm.sup.2.
39. A method for manufacturing a thermally conductive substrate,
which comprises: (1) processing through holes on the sheet for the
thermally conductive substrate manufactured by the method according
to claim 24; (2) filling a conductive resin composition into said
through holes; (3) piling up a metallic foil on both sides of said
sheet with which the conductive resin composition is filled in said
through holes; (4) hardening said thermosetting resin of said sheet
by thermal pressing at the pressure of 10 to 200 Kg/cm.sup.2; and
(5) forming a wiring pattern by processing said metallic foil.
40. A method for manufacturing a thermally conductive substrate,
which comprises: (1) piling up a metallic foil on the both sides of
the sheet for the thermally conductive substrate manufactured by
the method according to claim 24; (2) hardening said thermosetting
resin of said sheet of thermally conductive substrate by thermal
pressing at the pressure of 10 to 200 Kg/cm.sup.2; (3) processing
through holes on said hardened thermally conductive sheet; (4)
conducting a copper plating on the entire surface of said sheet on
which through holes are processed; and (5) forming a wiring pattern
by processing said metallic foil and said copper plating layer.
41. A method for manufacturing a thermally conductive substrate,
which comprises: (1) preparing a desired number of thermally
conductive substrates manufactured by the method according to claim
24; (2) processing through holes at desired locations on each of
said sheets; (3) filling a conductive resin composition to said
through holes; (4) forming a wiring pattern on one surface of said
filled sheet by using the conductive resin composition; (5) piling
up each sheet having said wiring pattern in a way in which the
surface having said wiring pattern is adjusted to face upward and
the sheet on which only the conductive resin composition is filled
to said through hole is adjusted to be the top face to form a pile;
(6) piling up metallic foil on both sides of said pile; (7)
hardening said thermosetting resin of said sheet for the thermally
conductive substrate by thermal pressing at the pressure of 10 to
200 Kg/cm.sup.2; and (8) forming a wiring pattern by processing
said metallic foil.
42. The method for manufacturing a thermally conductive substrate
according to claim 41, wherein said through holes are processed by
the method selected from the group consisting of laser beam
process, drilling process and punching process.
43. The method for manufacturing a thermally conductive substrate
according to claim 41, wherein the temperature for said thermal
pressing is in the range of 170 to 260.degree. C.
44. A method for manufacturing a thermally conductive substrate,
which comprises: (1) piling up a lead frame on the sheet for the
thermally conductive substrate manufactured by the method according
to claim 29; (2) molding the sheet at the temperature below the
hardening temperature of the thermosetting resin composition at the
pressure of 10 to 200 Kg/cm.sup.2; (3) filling the sheet and
integrating to the surface of the lead frame; and (4) hardening
said thermosetting resin by thermal pressing at the pressure in the
range of 0 to 200 Kg/cm.sup.2.
45. A method for manufacturing a thermally conductive substrate
further comprising: forming a metal substrate on the face opposite
to the face to which the lead frame is adhered of the thermally
conductive substrate according to claim 44.
46. A method for manufacturing a thermally conductive substrate,
which comprises: (1) placing a lead frame and a printed circuit
board having two or more wiring layers on the sheet for the
thermally conductive substrate manufactured by the method according
to claim 29 in a way in which said lead frame and said printed
circuit board are not overlapped; (2) molding the sheet at the
temperature below the hardening temperature of the thermosetting
resin composition and at the pressure in the range of 10 to 200
Kg/cm.sup.2; (3) filling the sheet and integrating to the surface
of said lead frame and said printed circuit board having two or
more wiring layers; and (4) hardening said thermosetting resin by
thermal pressing at the pressure of 0 to 200 Kg/cm.sup.2.
47. A method for manufacturing a thermally conductive substrate,
which comprises: (1) processing through holes on the sheet for the
thermally conductive substrate manufactured by the method according
to claim 29; (2) filling a conductive resin composition into said
through holes; (3) piling up the metallic foil on both sides of
said sheet with which the conductive resin composition is filled in
said through holes; (4) hardening said thermosetting resin of said
sheet by thermal pressing at the pressure of 10 to 200 Kg/cm.sup.2;
and (5) forming a wiring pattern by processing said metallic
foil.
48. A method for manufacturing a thermally conductive substrate,
which comprises: (1) piling up a metallic foil on both sides of the
sheet for the thermally conductive substrate manufactured by the
method according to claim 29; (2) hardening said thermosetting
resin of said sheet of thermally conductive substrate by thermal
pressing at the pressure of 10 to 200 Kg/cm.sup.2; (3) processing
through holes on said hardened thermally conductive sheet; (4)
conducting a copper plating on the entire surface of said sheet on
which through holes are processed; and (5) forming a wiring pattern
by processing said metallic foil and said copper plating layer.
49. A method for manufacturing a thermally conductive substrate,
which comprises: (1) preparing a desired number of thermally
conductive substrates manufactured by the method according to claim
29; (2) processing through holes at desired locations on each of
said sheets; (3) filling a conductive resin composition into said
through holes; (4) forming a wiring pattern on one surface of said
filled sheet by the use of said conductive resin composition; (5)
piling up each of said sheet having said wiring pattern in a way in
which the surface having said wiring pattern is adjusted to face
upward and the sheet on which only the conductive resin composition
is filled to said through hole is adjusted to be the top face to
form a pile; (6) piling up metallic foil on both sides of said
laminate; (7) hardening said thermosetting resin of said sheet for
the thermally conductive substrate by thermal pressing at the
pressure of 10 to 200 Kg/cm.sup.2; and (8) forming a wiring pattern
by processing said metallic foil.
50. A method for manufacturing a thermally conductive substrate
according to claim 49, wherein said through holes are processed by
the method selected from the group consisting of laser beam
process, drilling process and punching process.
51. A method for manufacturing a thermally conductive substrate
according to claim 49, wherein the temperature for said thermal
pressing is in the range of 170 to 260.degree. C.
Description
FIELD OF THE INVENTION
[0001] The invention relates to a circuit substrate whose thermal
radiation property is improved by a mixture of resin and inorganic
filler. In particular, it relates to a high thermal radiation
printed wiring board made of resin (thermally conductive substrate)
for mounting electronic power devices.
BACKGROUND OF THE INVENTION
[0002] Recently, as high performance and miniaturization of the
electronic apparatus have been required, high density and high
performance semiconductors have been sought. Consequently, circuit
substrates for mounting thereof have also been required to be small
and of high density. As a result, it is important to design circuit
substrates taking the thermal radiation property into
consideration. A well known technique for improving the thermal
radiation property of circuit substrates, while using a printed
circuit board made of glass-epoxy resin, is to use, a metal base
substrate having a metal, for example, aluminum etc. and form a
circuit pattern on one face or both faces of this metal substrate
with an insulating layer interposed in between the circuit pattern
and the metal substrate. Moreover, when higher thermal conductivity
is required, the metal base substrate is made of a copper plate,
which is directly bonded to a ceramic substrate made of, for
example, alumina or aluminum nitride. For an application requiring
relatively small electric power, a metal base substrate is
generally used. In this case, however, in order to improve the
thermal conduction, the insulating layer must be thin. Therefore.
as for the substrate of thin insulating layer, break down voltage
is low, and the influence by the noise, too, is big.
[0003] It is difficult for the metal base substrate and ceramic
substrate to satisfy both performance and cost requirements.
Recently, an injection molded thermally conductive module has been
suggested, where a thermoplastic resin composition containing
inorganic filler is integrated with the lead frame of an electrode.
This injection molded thermally conductive module has excellent
mechanical strength in comparion with a ceramic substrate. However,
due to the high viscosity of the thermoplastic resin, it is
difficult to injection mold such a module with a high filler
content, and so the thermal radiation property of module is poor.
In particular, at the time of melting the thermoplastic resin at
high temperature and kneading with filler, if there is too much
filler, the melting viscosity is rapidly increased in a point that
not only kneading but also injection molding is made impossible.
Moreover, the filler serves as an abrasives to abrade the metallic
mold, and, thus, reduces the life of the mold. Consequently, the
content of the filler is limited, so that only lower thermal
conductivity can be obtained as compared with the thermal
conductivity of the ceramic substrate.
SUMMARY OF THE INVENTION
[0004] The object of the present invention is to overcome the above
mentioned problems and to provide a sheet for a thermally
conductive substrate in which an inorganic filler can be filled in
a resin at a high filler loading to form a thermally conductive
module by a simple method. having (a) approximately the same
coefficient of the thermal expansion in the plane direction of the
substrate as that of a semiconductor, and (b) excellent thermal
radiation property; a method for manufacturing the above mentioned
sheet for a thermally conductive substrate; a thermally conductive
substrate using the above mentioned sheet; and a method for
manufacturing this thermally conductive substrate.
[0005] In order to attain the objects, the sheet for the thermally
conductive substrate of the present invention is a sheet mixture
comprising 70 to 95 weight parts of inorganic filler and 5 to 30
weight parts of resin composition comprising at least thermosetting
resin, hardener and hardening accelerator. This sheet mixture has a
good flexibility in the half hardened state or partially hardened
state. (Hereinafter, "B stage" will be used for the half hardened
state or partially hardened state.) This sheet mixture of the
thermally conductive substrate can be molded and processed into a
predetermined shape due to the flexibility of the sheet. On
complete hardening of the resin composition, the substrate can be
made rigid with excellent mechanical strength.
[0006] It is preferable in the sheet for the thermally conductive
substrate of the present invention that the half hardened state or
partially hardened state has a viscosity in the range of 10.sup.2
to 10.sup.5 (Pa.multidot.s). By such a preferred embodiment,
excellent flexibility and processing property can be provided, so
that the sheet can be molded and processed into the predetermined
shape. More preferably, the half hardened state or partially
hardened state has a viscosity in the range of 10.sup.3 to 10.sup.4
(Pa.multidot.s). The viscosity of the sheet herein is measured by
the following method: the apparatus used for measuring the
elasto-viscosity was a "cone and plate" type dynamic measurement
apparatus, MR-500, the product of Rhelogy Co., Ltd.; the sheet was
processed into the predetermined size and sandwiched between the
cone and plate having a diameter of 17.97 mm and cone angle of 1.15
deg.; sinusoidal oscillation was given to the sample in the
twisting direction; and the difference in the phases of torque
which was generated by the sinusoidal oscillation was calculated.
Thus, the viscosity was measured. In the evaluation of the
elasto-viscosity of the sheet of the present invention, the
sinusoidal oscillation was a sine wave with a frequency of 1 Hz,
the strain was 0.1 deg., the load was 500 g and the temperature was
25.degree. C.
[0007] It is preferable in the sheet for the thermally conductive
substrate of the present invention that 0.1 to 2 weight parts of
solvent having a boiling point of not less than 150.degree. C. is
further added to 100 weight parts of total weight of inorganic
filler and thermosetting resin composition. By this preferred
embodiment, excellent flexibility and processing property can be
provided.
[0008] It is preferable in the sheet for the thermally conductive
substrate of the present invention that the solvent having a
boiling point of not less than 150.degree. C. is at least one
solvent selected from the group consisting of ethyl carbitol, butyl
carbitol and butyl carbitol acetate. By this preferred embodiment,
the processing of the sheet material is easy, flexibility can be
provided to the thermosetting resin at room temperature, and the
viscosity of the sheet material for molding and processing can
easily be controlled.
[0009] It is preferable in the thermosetting resin composition in
the sheet for the thermally conductive substrate of the present
invention to comprise:
[0010] 1) 0 to 45 weight parts of a first resin that is solid at
room temperature,
[0011] 2) 5 to 50 weight parts of a second resin that is liquid at
room temperature,
[0012] 3) 4.9 to 45 weight parts of the hardener, and
[0013] 4) 0.1 to 5 weight parts of the hardening accelerator when
the thermosetting resin composition is 100 weight parts. By such a
preferred embodiment, excellent flexibility and processing property
can be provided.
[0014] It is preferable in the sheet for the thermally conductive
substrate of the present invention that the main component of the
thermosetting resin that is solid at room temperature is one or
more components selected from the group consisting of bisphenol A
epoxy resin, bisphenol F epoxy resin and liquid phenol resin. By
this preferred embodiment, the "B stage" resin has a long shelf
life and the hardened resin has excellent electrical insulating
property and mechanical strength.
[0015] It is preferable in the sheet for the thermally conductive
substrate of the present invention that the main component of the
thermosetting resin composition is at least one resin selected from
the group consisting of epoxy resin, phenol resin and cyanate
resin.
[0016] It is preferable in the sheet for the thermally conductive
substrate of the present invention that the thermosetting resin
composition comprises brominated multifunctional epoxy resin as a
main component, bisphenol A novolak resin as a hardener, and
imidazole as a hardening accelerator. By such a preferred
embodiment, the substrate can be made excellent in flame retardant
property, electric insulating property and mechanical strength.
[0017] It is preferable in the sheet for the thermally conductive
substrate of the present invention that the brominated
multifunctional epoxy resin be in the range of 60 to 80 weight
parts; bisphenol A novolak resin as a hardener be in the range of
18 to 39.9 weight parts, and imidazole as a hardening accelerator
be in the range of 0.1 to 2 weight parts.
[0018] It is preferable in the sheet for the thermally conductive
substrate of the present invention that the inorganic filler is at
least one kind of filler selected from the group consisting of
Al.sub.2O.sub.3, MgO, BN and AlN, because these fillers are
excellent in thermal conductivity.
[0019] It is preferable in the sheet for the thermally conductive
substrate of the present invention that at least one additives is
selected from the group consisting of coupling agent, dispersing
agent, coloring agent and tack free agent is further added to the
sheet for a thermally conductive substrate.
[0020] Next, the thermally conductive substrate of the present
invention is characterized in that when the thermosetting resin
component of the thermally conductive substrate sheet is hardened,
the coefficient of thermal expansion is in the range of 8 to 20
ppm/.degree. C. and the thermal conductivity is in the range of 1
to 10 W/mK. In the thermally conductive substrate, thermal
deformation or the like is not generated and the coefficient of
thermal expansion approximates that of a semiconductor.
[0021] It is preferable in the sheet for the thermally conductive
substrate of the present invention that the flexural strength of
the thermally conductive substrate is not less than 10
Kgf/mm.sup.2. If the flexural strength is within the above
mentioned range, practical mechanical strength can be obtained. The
flexural strength herein is measured according to JIS R-1601 (the
testing method of bending strength of fine ceramics) in the
following manner: test sample is cut in a predetermined size; the
test sample is placed on two supporting points which are located at
certain distance; load is applied to the middle point of the test
sample between two supporting points; the maximum bending stress
when the test sample breaks is measured and this value is defined
as flexural strength. This value is also called the three-point
bending strength.
[0022] The dimensions of the test sample are as follows:
[0023] Whole Length (Lr): 36 mm
[0024] Width (w): 4.0.+-.0.1 mm
[0025] Thickness (t): 3.0.+-.0.1 mm
[0026] The bending strength is calculated by the following
equation:
.sigma.=3PL/2wt.sup.2
[0027] wherein .sigma. denotes the three-point bending strength
(kgf/mm.sup.2). P denotes the maximum load when the test piece is
broken, L denotes the distance between lower supporting points
(mm), w denotes the width of the test piece (mm) and t denotes the
thickness of the test piece (mm).
[0028] It is preferable in the sheet for the thermally conductive
substrate of the present invention that the flexural strength is in
the range of 10 to 20 Kgf/mm.sup.2.
[0029] It is preferable in the sheet for the thermally conductive
substrate of the present invention that a lead frame is further
integrated to the thermally conductive substrate, and the thermally
conductive substrate is filled to the surface of the lead frame. By
such a preferred embodiment, electronic parts can easily be
attached to the lead frame and thermal resistance for connecting
thermal radiation can be inhibited. Moreover, soldering terminals
for connecting a removable electrode are not required. Instead, the
lead frame can be connected directly to an outside signal source,
which may be an electrode for taking current. Thus, reliability by
such a preferred embodiment is excellent.
[0030] It is preferable in the sheet for the thermally conductive
substrate of the present invention that a metal substrate for
thermal radiation is further formed on the face opposite to the
face to which the lead frame is adhered to the thermally conductive
substrate. By such a preferred embodiment, thermal resistance can
be further decreased and the mechanical strength is improved.
[0031] It is preferable in the sheet for the thermally conductive
substrate of the present invention that a printed circuit board
having two or more wiring layers be integrated into a part of the
face of the thermally conductive substrate to which the lead frame
is adhered, the thermally conductive substrate be filled to the
surface of the lead frame, and the printed circuit board comprises
two or more wiring layers. By such a preferred embodiment, the
control circuit for overcurrent protection or temperature
compensation can be integrated into the substrate. Thus,
miniaturization and high density of the apparatus can be
realized.
[0032] It is preferable in the sheet for the thermally conductive
substrate of the present invention that the thermally conductive
substrate has a through hole. The through hole is filled with
conductive resin composition or is plated with copper, and a
metallic foil wiring pattern is formed and integrated on both sides
of the substrate. By such a preferred embodiment, double-sided
wiring substrate which is excellent in thermal radiation can be
obtained.
[0033] It is preferable in the sheet for the thermally conductive
substrate of the present invention that a plurality of the
thermally conductive substrates are layered and each thermally
conductive substrate has a through hole. The through hole is filled
with conductive resin composition and an internal wiring pattern is
composed of conductive resin composition. In addition, a metallic
foil wiring pattern is formed and integrated on both sides of the
substrate. By such a preferred embodiment, conductivity between
layers of the thermally conductive substrate is excellent and
internal wiring pattern can be formed. Furthermore, excellent
thermal conductivity can be provided.
[0034] It is preferable in the sheet for the thermally conductive
substrate of the present invention that the metallic foil is a
copper foil having a thickness of 12 to 200 .mu.m and having faces
at least one surface of which is a rough surface.
[0035] It is preferable in the sheet for the thermally conductive
substrate of the present invention that the conductive resin
composition comprises 70 to 95 weight parts of at least one
metallic powder selected from the group consisting of silver,
copper and nickel: and 5 to 30 weight parts of thermosetting resin
and hardener.
[0036] It is preferable in the sheet for the thermally conductive
substrate of the present invention that the inorganic filler has an
average particle diameter of 0.1 to 100 .mu.m.
[0037] The first method of manufacturing the sheet for the
thermally conductive substrate of the present invention comprises
the steps of: forming a slurry mixture comprising 70 to 95 weight
parts of an inorganic filler, 4.9 to 28 weight parts of a
thermosetting resin composition and 0.1 to 2 weight parts of a
solvent having a boiling point of not less than 150.degree. C. and
solvent having a boiling point not more than 100.degree. C.;
forming the slurry mixture into a film having a desired thickness;
and drying the solvent having a boiling point of not more than
100.degree. C. of the film slurry.
[0038] The second method of manufacturing the sheet for the
thermally conductive substrate of the present invention comprises
the steps of: forming a slurry mixture comprising 70 to 95 weight
parts of inorganic filler, 5 to 30 weight parts of thermosetting
resin mixture comprising a solid of thermosetting resin that is
solid at room temperature and a liquid thermosetting resin that is
liquid at room temperature and solvent having a boiling point not
more than 100.degree. C.; forming the slurry mixture into a film
having a desired thickness; and drying only the solvent having a
boiling point of not more than lOOOC of the film slurry.
[0039] It is preferable in the second manufacturing method that the
thermosetting resin mixture in the sheet for thermally conductive
substrate made according to the second method, comprises:
[0040] 1) 0 to 45 weight parts of resin that is solid at room
temperature,
[0041] 2) 5 to 50 weight parts of resin that is liquid at room
temperature,
[0042] 3) 4.9 to 45 weight parts of hardener, and
[0043] 4) 0.1 to 5 weight parts of hardening accelerator when the
total weight of the solid thermosetting resin and the liquid
thermosetting resin 100 is weight parts.
[0044] It is further preferable in the second manufacturing method
that the main component of the solid thermosetting resin is one or
more components selected from the group consisting of bisphenol A
epoxy resin, bisphenol F epoxy resin and liquid phenol resin.
[0045] It is preferable in the first and second manufacturing
methods that the thermosetting resin mixture comprises a brominated
multifunctional epoxy resin as a main component, a bisphenol A
novolak resin as a hardener, and an imidazole as a hardening
accelerator.
[0046] It is preferable in the first and second manufacturing
methods that the sheet for a thermally conductive substrate
comprises a brominated multifunctional epoxy resin in the range of
60 to 80 weight parts; a bisphenol A novolak resin as a hardener in
the range of 18 to 39.9 weight parts, and an imidazole as a
hardening accelerator in the range of 0.1 to 2 weight parts.
[0047] It is preferable in the first manufacturing method that the
solvent having a boiling point of not less than 150.degree. C. is
at least one solvent selected from the group consisting of ethyl
carbitol, butyl carbitol and butyl carbitol acetate.
[0048] It is preferable in the first and second manufacturing
methods that the solvent having a boiling point of not more than
100.degree. C. is one solvent selected from the group consisting of
methyl ethyl ketone, isopropanol and toluene.
[0049] It is preferable in the first and second manufacturing
methods that an additive selected from the group consisting of
coupling agent, dispersing agent, coloring agent and tack free
agent is further added to the sheet for a thermally conductive
substrate.
[0050] It is preferable in the first and second manufacturing
methods that the film forming method is at least one method
selected from the group consisting of doctor blade method, coater
method, and injection molding method.
[0051] The third method for manufacturing the thermally conductive
substrate of the present invention comprises the steps of: piling
up a lead frame on a face of the sheet for the thermally conductive
substrate manufactured by the first manufacturing method; molding
the sheet at a temperature below the hardening temperature of the
thermosetting resin composition and at a pressure in the range of
10 to 200 Kg/cm.sup.2; filling the sheet and integrating to the
surface of the lead frame; and hardening the thermosetting resin by
thermal pressing at the pressure in the range of 0 to 200
Kg/cm.sup.2.
[0052] It is preferable in the third manufacturing method that a
metal substrate for thermal radiation is further formed on the face
opposite to the face to which the lead frame is adhered to the
thermally conductive substrate.
[0053] Moreover, the third method for manufacturing the thermally
conductive substrate of the present invention comprises the steps
of: placing the lead frame and a printed circuit board having two
or more wiring layers on the sheet for the thermally conductive
substrate manufactured by the method according to claim 24 in a way
in which the lead frame and the printed circuit board are not
overlapped; molding the sheet at the temperature below the
hardening temperature of the thermosetting resin composition and at
the pressure in the range of 10 to 200 Kg/cm.sup.2; filling the
sheet and integrating to the surface of the lead frame and the
printed circuit board having two or more wiring layers; and
hardening the thermosetting resin by thermal pressing at the
pressure of 0 to 200 Kg/cm.sup.2.
[0054] Moreover, the third method for manufacturing the thermally
conductive substrate of the present invention comprises a series of
steps of: processing through holes on the sheet for the thermally
conductive substrate manufactured by the method according to claim
24; filling a conductive resin composition into the through holes;
piling up the metallic foil on both sides of the sheet into which
the conductive resin composition is filled in the through holes;
hardening the tbermosetting resin of the sheet by thermal pressing
at the pressure of 10 to 200 Kg/cm.sup.2; and forming wiring
pattern by processing the metallic foil.
[0055] Moreover, the method for manufacturing the thermally
conductive substrate of the present invention comprises the steps
of: piling up a metallic foil on the both sides of the sheet for
the thermally conductive substrate manufactured by the method
according to claim 24; hardening the thermosetting resin of the
sheet of thermally conductive substrate by thermal pressing at the
pressure of 10 to 200 Kg/cm.sup.2; processing through holes on the
hardened the thermally conductive sheet; conducting a copper
plating on the entire surface of the sheet on which through holes
are processed; and forming a wiring pattern by processing the
metallic foil and the copper plating layer.
[0056] Moreover, the third method for manufacturing the thermally
conductive substrate of the present invention comprises the steps
of: preparing a desired number of thermally conductive substrates
by the first manufacturing method; processing through holes at
desired locations on each of the sheets; filling a conductive resin
composition into the through holes; forming a wiring pattern on one
surface of the filled sheet by using the conductive resin
composition; piling up each of the sheet having the wiring pattern
in a way in which the surface having the wiring pattern is adjusted
to face upward and the sheet on which only the conductive resin
composition is filled to the through hole is adjusted to be the top
face to form a pile; piling up metallic foil on both sides of the
pile; hardening the thermosetting resin of the sheet for the
thermally conductive substrate by thermal pressing at the pressure
of 10 to 200 Kg/cm.sup.2; and forming a wiring pattern by
processing the metallic foil.
[0057] It is in the third manufacturing method that the through
holes are processed by the method selected from the group
consisting of laser beam process, drilling process and punching
process.
[0058] It is in the third manufacturing method that the metallic
foil is a copper foil having a thickness of 12 to 200 .mu.m and
having faces at least one surface of which is a rough surface.
[0059] It is in the third manufacturing method that the conductive
resin composition comprises 70 to 95 weight parts of at least one
metallic powder selected from the group consisting of silver,
copper and nickel; and 5 to 30 weight parts of thermosetting resin
and hardener.
[0060] It is in this third manufacturing method that the
temperature for the thermal pressing is in the range of 170 to
260.degree. C.
[0061] As mentioned above, according to the present invention, high
thermal radiation printed circuit wiring board for mounting
electronic power devices can be made of the thermally conductive
substrate by shaping and hardening the thermally conductive sheet
into a desired shape. Shaping is possible due to the flexibility of
the thermally conductive substrate sheet, hardening makes the
thermally conductive substrate rigid.
[0062] Moreover, according to the present invention, thermally
conductive substrate can be manufactured efficiently and
reasonably.
[0063] The first embodiment of the present invention basically
relates to a thermally conductive sheet having flexibility, where
an inorganic filler is added into a thermosetting resin in the
not-hardened state at high density; the coefficient of thermal
expansion in the plane direction is approximately the same as that
of Si semiconductor; and high thermal conductivity is provided. In
the thermally conductive sheet of the present invention, a high
boiling point solvent is added into the thermosetting resin
composition, or a thermosetting resin mixture containing a solid
resin that is solid at room temperature and a liquid thermosetting
resin that is liquid at room temperature, and films are formed by
using a low boiling point solvent for mixing with inorganic filler.
Consequently, in the thermally conductive sheet of the present
invention, inorganic filler can be added at a high filler loading.
Furthermore, the flexibility of the thermosetting resin of the
thermally conductive sheet is manufactured in the not-hardened
state, and, thus, molding the thermally conductive sheet into a
desired shape at a low temperature and at a low pressure is
possible. In addition, the thermally conductive substrate can be
made rigid by hardening the thermosetting resin by thermal
pressing. Also, a thermally conductive substrate on which a
semiconductor can be simply and directly mounted can be obtained by
the use of this thermally conductive sheet which is flexible.
[0064] The second embodiment of the present invention relates to a
thermally conductive substrate on which a semiconductor having
thermal radiation property can directly be mounted by using the
thermally conductive sheet; piling up a lead frame; and hardening
the thermally conductive sheet by means of thermal pressing to
integrate with the lead frame.
[0065] Moreover, the third embodiment of the present invention
relates to a doubled-sided thermally conductive substrate having
high thermal conductivity, which permits electrical conductivity on
both sides by forming through holes on the thermally conductive
sheet, filling the thorough holes with the conductive resin
composition and forming metallic foil patterns on both sides of the
sheet.
[0066] Moreover, the fourth embodiment of the present invention
relates to a high thermally conductive double-sided substrate which
permits electric conductivity by copper plating to the through
holes of the third embodiment.
[0067] Moreover, the fifth embodiment of the present invention
relates to a thermally conductive substrate (a multi-layered
substrate) having a multi-layered circuit structure in which a
plurality of the thermally conductive sheets are used, the through
holes to which conductive resin composition is filled are formed,
wiring pattern is formed on one side of the thermally conductive
sheet, and a plurality of the thermally conductive sheets are piled
up.
BRIEF DESCRIPTION OF DRAWINGS
[0068] FIG. 1 is a cross sectional view showing a structure of the
thermally conductive sheet of one embodiment of the present
invention.
[0069] FIGS. 2A to 2E are cross sectional views showing each step
of a manufacturing process of the thermally conductive substrate
which is manufactured by using the thermally conductive sheet of
one embodiment of the present invention.
[0070] FIG. 3 is a cross sectional view of the thermally conductive
substrate on which the thermal radiation metal substrate is further
formed on the face opposite to face the lead frame is adhered to
the thermally conductive substrate manufactured by the process
according to FIG. 2.
[0071] FIGS. 4A to 4F are cross sectional views showing each step
of a manufacturing process of the thermally conductive substrate
which is manufactured by using the thermally conductive sheet of
one embodiment of the present invention.
[0072] FIG. 5 is a cross sectional view showing a process for
manufacturing the thermally conductive multi-layered wiring
substrate of one embodiment of the present invention.
[0073] FIGS. 6A to 6J are cross sectional views showing each step
of a manufacturing process of the thermally conductive
multi-layered wiring substrate of one embodiment of the present
invention.
[0074] FIGS. 7A and 7B are cross sectional views showing each step
of a manufacturing process of the thermally conductive substrate of
another embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0075] Hereinafter, the thermally conductive substrate
(single-sided wiring substrate, double-sided wiring substrate,
multi-layered wiring substrate) for mounting bare chip of one
embodiment of the present invention will be explained by referring
to figures.
[0076] FIG. 1 is a cross sectional view showing a structure of the
thermally conductive sheet of one embodiment of the present
invention. In FIG. 1, a thermally conductive sheet 100 is formed on
a tack free film 101. The forming method includes: preparing the
slurry mixture which comprises at least one inorganic filler,
thermosetting resin composition, a solvent having a boiling point
of not less than 150.degree. C. and a solvent having a boiling
point of not more than 100.degree. C.; and forming the mixture into
a film on the tack free film 101. The film forming method can be,
for example, a doctor blade method, a coater method and an
injection molding method can be employed. A thermally conductive
sheet having flexibility can be obtained by drying only the solvent
having a boiling point of not more than 100.degree. C. of the film
slurry.
[0077] Moreover, similarly, a thermally conductive sheet having
flexibility can be obtained by the process comprising the steps of:
preparing the slurry mixture which comprises at least one inorganic
filler, a thermosetting resin composition that is solid at room
temperature, and a solvent having a boiling point of not more than
100.degree. C.; forming the slurry mixture into a film on the tack
free film 101, similar to the above; and drying the solvent.
[0078] The examples of the thermosetting resin include, epoxy
resin, phenol resin and cyanate resin. Moreover, the examples of
the inorganic filler include Al.sub.2O.sub.3, MgO, BN, and AlN. The
examples of the solvent having a boiling point of not less than
150.degree. C. include ethyl carbitol, butyl carbitol and butyl
carbitol acetate.
[0079] Moreover, the examples of the thermosetting resin that is
liquid at room temperature include epoxy resin such as bisphenol A
epoxy resin, bisphenol F epoxy resin and liquid state phenol
resin.
[0080] In addition, the examples of the solvent having a boiling
point of not more than 100.degree. C. include methyl ethyl ketone,
isopropanol and toluene. Moreover, if necessary, coupling agent,
dispersing agent, coloring agent and tack free agent can be added
as an additive into the thermally conductive sheet composition.
[0081] Moreover, as mentioned above, the half hardened or partially
hardened sheet for the thermally conductive substrate having a
moderated viscosity (10.sup.2 to 10.sup.5 Pa.multidot.s) can be
obtained by adding the solvent having a boiling point of not less
than 150.degree. C. or adding the thermosetting resin that is
liquid at room temperature, and drying the solvent having a boiling
point of not more than 100.degree. C. If the viscosity is not more
than 10.sup.2 Pa.multidot.s, the adhesion of the sheet is so strong
that it is difficult to be peeled apart from the tack free film and
furthermore changing the shapes after the process is large and the
operation efficiency is bad. It is preferable that the viscosity is
in the range of 10.sup.3 to 10.sup.4 Pa.multidot.s in the view of
the operation efficiency and processing property.
[0082] Since high filler loading (ie., high filler content) in the
thermally conductive substrate using this thermally conductive
sheet is possible in the present invention, the coefficient of
thermal expansion of the substrate can be made to be approximately
the same as that of a semiconductor, and furthermore the substrate
can be made to have excellent thermal radiation.
[0083] FIGS. 2A to 2E are cross sectional views showing each step
of a manufacturing process of the thermally conductive substrate
manufactured by using the thermally conductive sheet 100. In FIG.
2A, numeral 200 denotes the thermally conductive sheet manufactured
by the above method; 201 of FIG. 2B denotes a lead frame forming a
wiring. The lead frame 201 can be obtained by punching a copper
plate into a desired shape, or can be formed by an etching method.
A processed lead frame whose surface is plated with nickel prevent
oxidation of copper is generally used.
[0084] FIG. 2C shows a structure in which the lead frame 201 and
the thermally conductive sheet 200 are piled up.
[0085] FIG. 2D shows a structure in which the lead frame and
thermally conductive sheet are thermally pressed. Then the
thermally conductive sheet is filled to the surface of the lead
frame by using the flexibility of the thermally conductive sheet.
Finally, the thermosetting resin in the thermally conductive sheet
is hardened. Then, FIG. 2E shows the hardened thermally conductive
substrate in which the portion except the necessary portion of the
lead frame of the thermally conductive substrate is cut. In FIG.
2E, the hardened thermally conductive substrate is bent
perpendicularly so as to form a removable electrode. Thus, as
described above, a thermally conductive substrate is manufactured.
Subsequently, steps of mounting parts by soldering or filling
insulating resin are carried out, but they are not important herein
and omitted.
[0086] FIG. 3 shows a structure in which the thermal radiation
metal substrate 302 is further formed on the face opposite to the
portion where the lead frame is adhered to the thermally conductive
substrate manufactured by the steps illustrated in FIG. 2.
[0087] FIGS. 4A to 4F show the method for forming a thermally
conductive substrate having a double-sided wiring, which is
different from the above mentioned method. FIG. 4A shows the
thermally conductive sheet 400 formed on the tack free film 401. In
FIG. 4B, the through holes 402 is formed from the side of the tack
free film 401 of the thermally conductive sheet 400. The formation
of the through holes can be conducted by a laser processing method
using carbon dioxide, excimer or the like, or by a metal molding
process, or furthermore, by drilling. Punching by using laser beam
is preferred, because punching holes at a fine pitch is possible
and scrapings are not generated. In FIG. 4C, the conductive resin
composition 403 is filled into the through hole 402. As a
conductive resin composition, for example, a conductive paste
formed by mixing copper powder, epoxy resin and hardener of epoxy
resin can be used. In FIG. 4D, the metallic foils 404 are further
piled up on both sides of the thermally conductive sheet. FIG. 4D
is thermally pressed in this state, and the thermally conductive
sheet is hardened as shown in FIG. 4E. Finally, the metallic foil
applied onto both sides are processed as shown in FIG. 4F, and
thereby the wiring pattern 405 can be obtained. Thus, the thermally
conductive substrate having wiring patterns on both sides of the
thermally conductive sheet can be obtained. At this time, the lead
frame can be used instead of the metallic foil. In this case, the
last step, namely, the step for forming wiring pattern can be
omitted.
[0088] FIG. 5 is a cross sectional view of the thermally conductive
substrate, where the method of electrically connecting both sides
of the thermally conductive substrate manufactured by the process
of FIG. 4 is conducted not by the use of conductive resin
composition but by processing through holes after hardening by
thermal pressing, followed by connecting the inside layers by the
copper plating method. Numeral 501 denotes a copper plating layer
formed on the inside surface of the through hole; 502 denotes a
wiring pattern; and 500 denotes the thermally conductive substrate
wherein the thermally conductive sheet is hardened.
[0089] FIG. 6 is a cross sectional view showing each step of a
manufacturing process of a thermally conductive multi-layered
wiring substrate of one embodiment of the present invention. FIGS.
6A to 6C are the same as the thermally conductive sheet shown in
FIG. 4 where through holes are processed on the thermally
conductive sheet and a conductive resin composition is filled into
the through holes. FIGS. 6D, 6F and 6G show thermally conductive
sheets into which the conductive resin composition 603 is filled
and the conductive resin composition 603 is further used on one
side thereof to produce wiring pattern 604. The method for forming
the wiring pattern can be a screen printing method or a copper
plate offset printing method or the like. In FIG. 6E, the wiring
pattern by the conductive resin composition is not formed.
[0090] FIG. 6H is a pile where the thermally conductive sheets
shown in FIGS. 6E to 6G are piled up as shown in the figure, and a
metallic foil 605 is further piled up on the both sides of the
pile. FIG. 61 shows a structure in which each thermally conductive
sheet is laminated, hardened and adhered by thermal pressing. FIG.
6J shows a structure in which the wiring pattern of the top layer
606 is finally formed. The formation of the wiring pattern herein
is carried out by an etching method. The etching method is wet
etching, where ferric chloride is used as the etching reagent.
Thus, a high density thermally conductive substrate having a
multi-layered wiring structure can be obtained.
[0091] Moreover, herein, in manufacturing the printed circuit
board, there are steps of applying soldering resist, printing
letters or marks and punching holes for inserting parts. For these
steps, however, any conventional technique can be employed, and
they are not important herein and therefore omitted.
[0092] FIGS. 7A and 7B are cross sectional views showing each step
of a manufacturing process of the thermally conductive substrate
manufactured by using the thermally conductive sheet 700. In FIG.
7A, numeral 700 denotes the thermally conductive sheet manufactured
by the above method; 701 denotes a lead frame for forming wiring.
The lead frame 701 can be obtained by punching a copper plate into
a desired shape, or can be formed by an etching method. A processed
lead frame whose surface is plated with nickel preventing oxidation
of copper is generally used. Numeral 702 denotes the printed wiring
circuit having two or more wiring layers and it has a via 704 for
electrically connecting between the wiring pattern 703 and the
layers.
[0093] FIG. 7B shows a structure in which the lead frame 701,
thermally conductive sheet 700 and the printed wiring circuit 702
having two layers or more are thermally pressed; then the thermally
conductive sheet is filled to the surface of the lead frame by
using the flexibility of the thermally conductive sheet; and
furthermore, the thermosetting resin in the thermally conductive
sheet is hardened. Then, as in FIG. 2E, the hardened thermally
conductive substrate in which the portion except the necessary
portion of the lead frame of the thermally conductive substrate is
cut, the hardened thermally conductive substrate is bent
perpendicularly so as to form a removable electrode. Thus, a
thermally conductive substrate is manufactured. Subsequently, steps
of mounting parts by soldering or filling insulating resin are
carried out, but they are not important herein and omitted.
[0094] Hereinafter, the present invention will be explained by
referring to Examples.
EXAMPLE 1
[0095] In the formation of the thermally conductive sheet of the
present invention; inorganic filler, thermosetting resin and
solvent were mixed and alumina balls were further added into the
above mixture so as to obtain a sufficient dispersion. The
compositions of the thermally conductive sheet of this Example are
shown in Table 1.
1TABLE 1 Thermosetting Solvent having a Sheet resin boiling point
of after Experi- Inorganic (including not more than dried ment
Filler hardener) 150.degree. C. Other additives Viscosity No. Name
Vol. (wt %) Name Vol. (wt %) Name Vol. (wt %) *1 *2 *3 (Pa
.multidot. s) 1a Al.sub.2O.sub.3 60 Epoxy 36 Butyl 4 -- -- -- 1.5
.times. 10.sup.2 resin calbitol 1b Al.sub.2O.sub.3 70 Epoxy 28
acetate 2 -- -- -- 3.3 .times. 10.sup.3 resin (BCA) 1c
Al.sub.2O.sub.3 80 Epoxy 18 2 -- -- -- 26 .times. 10.sup.4 resin 1d
Al.sub.2O.sub.3 90 Epoxy 9.5 0.5 -- -- -- 81 .times. 10.sup.4 resin
1e Al.sub.2O.sub.3 95 Epoxy 4.9 0.1 -- -- -- 1.3 .times. 10.sup.5
Resin *1: coloring agent *2: coupling agent *3: dispersing
agent
[0096] Table 1 shows an evaluation of the performance of the
thermally conductive sheet when the content of Al.sub.2O.sub.3 as
an inorganic filler is changed. As Al.sub.2O.sub.3, "AL-33" having
a particle diameter of 12 .mu.m on the average, the product of
Sumitomo Chemical Company Limited was used; and as an epoxy resin,
the epoxy resin comprising the following composition was used: 1)
thermosetting resin main agent: 65 weight parts of brominated
multifunctional epoxy resin (5049-B-70, the product of Yuka-shell
epoxy Co., Ltd.); 2) hardener: 34.4 weight parts of bisphenol A
novolak resin (152, the product of Yuka-shell epoxy Co., Ltd.); and
3) hardening acceleratoer: 0.6 weight parts of imidazol (EMI-12,
the product of Yuka-shell epoxy Co., Ltd.). This resin composition
was in a solid state and it was softened to a paste-like
consistence by adding methyl ethyl ketone. The content in the state
of solid was 70%.
[0097] First, the resin compositions in Table 1 were weighed. Then,
methyl ethyl ketone solvent, having a boiling point of not more
than 100.degree. C. for adjusting the viscosity, was added to the
compositions until the viscosity of the slurry became about 20
Pa.multidot.s. Subsequently, the alumina balls were added and mixed
thereof in a pot with a rotating at a speed of 500 rpm for 48
hours. At this time, the low boiling point solvent was used so as
to adjust the viscosity of the alumina ball filled slurry.
Maintaining a low slurry-like viscosity by this slurry is important
for adding an inorganic filler in a high concentration in the
slurry. However, the low boiling point solvent was volatilized in
the following drying step. Since no low boiling point solvent
remained in the thermally conductive sheet composition, it is not
included in Table 1. Next, a polyethylene terephthalate sheet
having a thickness of 75 .mu.m was prepared as the tack free
surface and the above mentioned slurry was spread out into a film
by the doctor blade method with a gap of approximately 1.4 mm.
Then, methyl ethyl ketone in the above mentioned film was dried by
allowing the film to stand at 100.degree. C. for an hour. Thereby,
as shown in Table 1, the flexible thermally conductive sheet (the
thickness was 750 .mu.m ) having a moderate viscosity was
obtained.
[0098] From the thermally conductive sheet manufactured like this,
the tack free film of polyethylene terephthalate film was peeled
apart. Then, the thermally conductive sheet was again covered with
a thermal resistance tack free film (PPS: polyphenylene sulfite
having a thickness of 75 .mu.m), and was hardened at the
temperature of 200.degree. C. and at the pressure of 50
Kg/cm.sup.2. The PPS tack free film was peeled apart and the
thermally conductive sheet was processed into a predetermined shape
and size. The thermal conductivity, coefficient of thermal
expansion, break down voltage and flexural strength were measured.
The results are shown in Table 2.
2 TABLE 2 Evaluation of thermally conductive substrate Thermal
Thermal Break Down Flexural Experiment Conductivity Expansion
Voltage Strength No. (W/mK) (ppm/.degree. C.) (kV/mm) (Kg/mm.sup.2)
1a 1.1 28 15 9.5 1b 1.2 24 14 12.3 1c 1.9 18 15 15.5 1d 3.5 10 12
18.8 1e 4.1 8 9 13.1
[0099] The thermal conductivity was defined by calculating the
temperature transmitted from one surface to another surface of the
sample that was cut into 10 mm in size, when the sample was heated
by bringing it into contact with a heater. Similarly, the break
down voltage by AC voltage shown in Table 2 was defined by
measuring the break down voltage in the direction of the thickness
of the thermally conductive substrate and calculating the value per
a unit thickness. The break down voltage is affected by the
adhesion between the thermosetting resin and the inorganic filler
in the thermally conductive substrate. In other words, if the
wettability of the inorganic filler and the thermosetting resin was
bad, micro gaps were generated between them. As a result, the
strength of the substrate and break down voltage are deteriorated.
In general, the break down voltage of a resin alone is
approximately 15 KV/mm. If the break down voltage is not less than
10 KV/mm, it is judged that the adhesion between the thermosetting
resin and the inorganic filler is excellent.
[0100] From the results in Tables 1 and 2, the thermally conductive
substrate obtained by the thermally conductive sheet manufactured
by the above mentioned method had about 20 times as much thermal
conductivity as the conventional glass epoxy substrate, and not
less than 2 times as high a performance as the thermally conductive
sheet manufactured by the conventional injection molding method. In
addition, as to the coefficient of thermal expansion, when the
thermally conductive sheet contained not less than 90 wt. % of
Al.sub.2O.sub.3, the coefficient of thermal expansion was similar
to that of a silicon semiconductor. Moreover, the flexural strength
of the substrate was not less than 15 Kg/mm.sup.2, exhibiting
sufficient strength as substrate. Therefore, the thermally
conductive substrate of the present invention is promising as a
substrate for a flip chip on which a semiconductor is directly
mounted.
[0101] Then, the performance was evaluated when the type of
inorganic filler was changed. The compositions are shown in Table 3
and the evaluation results are shown in Table 4.
3TABLE 3 Thermosetting Solvent having a Sheet resin boiling point
of After Experi- Inorganic (including not more than Dried ment
Filler hardener) 150.degree. C. Other additives Viscosity No. Name
Vol. (wt %) Name Vol. (wt %) Name Vol. (wt %) *1 *2 *3 (Pa
.multidot. s) 1f Al.sub.2O.sub.3 91 Epoxy 8 Butyl 0 5 0.3 0.2. --
61 .times. 10.sup.4 resin calbitol 1g AlN 85 Epoxy 14 acetate 0.5
0.3 0.2 -- 16 .times. 10.sup.4 resin (BCA) 1h AlN 90 Epoxy 9 0.5
0.3 -- 02 58 .times. 10.sup.4 resin 1I BN 80 Epoxy 19 0.5 0.3 0.2
-- 71 .times. 10.sup.3 resin 1j MgO 87 Epoxy 12 0.3 0.3 0.2 -- 64
.times. 10.sup.4 resin *1: coloring agent (wt. %) *2: coupling
agent (wt. %) *3: dispersing agent (wt. %)
[0102]
4 TABLE 4 Evaluation of Thermal Conductive Substrate Thermal
Thermal Break Down Flexural Experiment Conductivity Expansion
Voltage Strength No. (W/mK) (ppm/.degree. C.) (kV/mm) (Kg/mm.sup.2)
1f 3.7 9 11 18.5 1g 4.0 11 14 15.3 1h 7.4 7.5 12 13.6 1I 3.5 12 15
10.9 1j 4.2 19 10 12.0
[0103] As is apparent from Tables 3 and 4, if a powder other than
Al.sub.2O.sub.3, for example, AIN, MgO, BN (approximately 7 to 12
.mu.m) was used as the inorganic filler, the performance peculiar
to the inorganic filler was exhibited. In other words, if AlN
having excellent thermal conductivity was used, then the thermal
conductivity similar to that of the ceramic substrate was obtained
(Example 1h). Moreover, in a case where BN was added, then high
thermal conductivity and low thermal expansion property was
obtained as shown in Example 1i. At this time, the additives
content was determined in a way in which a suitable state could be
obtained in accordance with the density and dispersion of inorganic
fillers. More inorganic fillers can be added by adding dispersing
agents such as AlN. Moreover, the thermally conductive substrate
having a sufficient thermal radiation property could be obtained by
coloring the thermally conductive sheet. Moreover, as mentioned
above, the addition of silane coupling agent for improving the
adhesion between the organic filler and the thermosetting resin
also improves the break down voltage characteristics of the
thermally conductive sheet.
[0104] In Table 5, the performance of the thermally conductive
sheet was evaluated in a case where Al.sub.2O.sub.3 was used as the
inorganic filler and resin that is liquid at room temperature was
added for providing flexibility. As Al.sub.2O.sub.3, "AL-33" (the
product of Sumitomo Chemical Company Limited) having an average
particle diameter of 12 .mu.m, was used; and an epoxy resin was
obtained by substituting a part of NVR-1010 containing a hardener
(the product of Japan REC Co., Ltd.) by liquid resin shown in Table
5.
5TABLE 5 Thermosetting Thermosetting resin that is resin that is
Sheet Experi- Inorganic Solid at room liquid at room after ment
Filler Temperature Temperature Hardener Other Additives dried No.
Name Vol. (wt %) Name Vol. (wt %) Name Vol. (wt %) Name Vol. (wt %)
Name Vol. (wt %) (Pa .multidot. s) 1k Al.sub.2O.sub.3 89.5 Epoxy 9
bis F 1 Sl-100 0.2 Raven 0.3 31 .times. 10.sup.5 resin 1060 1l
Al.sub.2O.sub.3 89.5 Epoxy 8 bis F 2 Sl-100 0.2 Raven 0 3 13
.times. 10.sup.4 resin 1060 1m Al.sub.2O.sub.3 89.5 Epoxy 6 bis F 4
Sl-100 0.2 Raven 0.3 44 .times. 10.sup.3 resin 1060 1n
Al.sub.2O.sub.3 89.5 Epoxy 4 bis F 6 Sl-100 0.2 Raven 0.3 2.1
.times. 10.sup.2 resin 1060 1o Al.sub.2O.sub.3 89.5 Epoxy 6 bis A 4
Sl-100 0.2 Raven 0.3 6.7 .times. 10.sup.4 resin 1060 1p
Al.sub.2O.sub.3 89.5 Epoxy 6 phenol 4 Sl-100 0.2 Raven 0.3 39
.times. 10.sup.3 resin 1060 Bis F: bisphenol F epoxy resin (806,
the product of Yuka-Shell Epoxy) Bis A: bisphenol A epoxy resin
Phenol: liquid state phenol resin (110, the product of Cemedyne
Co., Ltd.) Hardener Sl-110: San-aid (the product of Sanshin Kagaku
Co., Ltd.) Coloring agent: carbon black (Raven 1060, the product of
Colombia Carbon Japan Co., Ltd.)
[0105] First, the compositions in Table 5 were weighed. Then,
methyl ethyl ketone solvent, having a boiling point of not more
than 100.degree. C. for adjusting the viscosity, was added to the
compositions until the viscosity of the slurry became about 20
Pa.multidot.s. Subsequently, the alumina balls were added and mixed
thereof in a pot with a mixing device rotating at a speed of 500
rpm for 48 hours. At this time, the low boiling point solvent was
used to adjust the viscosity of the alumina balls filled slurry.
Maintaining a low slurry-like viscosity by the slurry is important
for adding an inorganic filler in a high concentration in the
slurry. However, the low boiling point solvent was volatilized in
the following drying step. Since no low boiling point solvent
remained in the thermally conductive sheet composition, it Is not
included in Table 1. Next, a polyethylene terephthalate sheet
having the thickness of 75 .mu.m was prepared as the tack free
surface and the above mentioned slurry was spread out into a film
by the doctor blade method with a gap of approximately 1.4 mm.
Then, methyl ethyl ketone in the above mentioned film was dried by
allowing to stand at 100.degree. C. for an hour. Thereby, as shown
in Table 5, the flexible thermally conductive sheet (the thickness
was 750 .mu.m ) having a moderate viscosity was obtained by adding
a resin that is liquid at room temperature.
[0106] From the thermally conductive sheet manufactured like this,
the tack free film of polyethylene terephthalate film was peeled
apart. Then, the thermally conductive sheet was again covered with
a thermal resistance tack free film (PPS: polyphenylene sulfite
having a thickness of 75 .mu.m), and was hardened at the
temperature of 200.degree. C. and at the pressure of 50
Kg/cm.sup.2. The PPS tack free film was peeled apart and the
thermally conductive sheet was processed into a predetermined shape
and size. The thermal conductivity, coefficient of thermal
expansion, break down voltage and flexural strength were measured.
The results are shown in Table 6.
6 TABLE 6 Evaluation of Thermally conductive Substrate Thermal
Thermal Break Down Flexural Experiment Conductivity Expansion
Voltage Strength No. (W/mK) (ppm/.degree. C.) (kV/mm) (Kg/mm.sup.2)
1k 3.6 14 12 11.3 1l 3.7 13 14 13.5 1m 3.9 13 14 15.5 1n 4.1 15 15
17.8 1o 3.6 14 15 14.3 1p 3.9 13 15 18.9
[0107] As is apparent from Table 6, flexibility could be provided
to the thermally conductive sheet by adding the resin that was
liquid at room temperature. Moreover, the performance peculiar to
inorganic filler was exhibited. As compared with the method of the
above mentioned Example where a high boiling point solvent was
added, the break down voltage by void and the flexural strength
were excellent, because no solvent existed in the sheet at the time
of molding the thermally conductive sheet.
EXAMPLE 2
[0108] In this Example, a thermally conductive substrate in which
the thermally conductive sheet was manufactured by the same method
as in Example 1 and integrated with a lead frame will be explained.
The compositions of the thermally conductive sheet used in this
Example will be described hereinafter.
[0109] (1) Inorganic filler: 90 weight % of Al.sub.2O.sub.3,
"AS-40(.RTM." (the product of SHOWA DENKO K.K.) having a spherical
shape and an average particle size of 12 .mu.m.
[0110] (2) Thermosetting resin: 9 weight % of cyanate ester resin,
"AroCy M30.RTM." (the product of Asahi-Ciba CO., Ltd.)
[0111] (3) Solvent having a boiling point of not less than
150.degree. C.: 0.5 weight % of butyl carbitol. (the first grade of
chemical reagent of Kanto Chemical CO, Inc.).
[0112] (4) Other additives: 0.3 weight % of "Carbon Black" (the
product of Toyo-carbon CO., Ltd.), and 0.2 wt. % of dispersing
agent, "PLYSURF F-208.RTM." (the product of DAI-ICHI SEIYAKU KOGYO
CO., LTD.).
[0113] A thermally conductive sheet (a thickness was 770 .mu.m)
comprising the above mentioned compositions was used. As the lead
frame, a copper plate having a thickness of 500 .mu.m which was
processed by the etching method and further applied with nickel
plating was piled up and thermally pressed at the temperature of
110.degree. C. and pressed at the pressure of 60 Kg/cm.sup.2. By
such a process, the thermally conductive sheet flowed into gaps of
the lead frame and was filled to the surface of the lead frame to
form a structure as shown in FIG. 2D. Then, the thermally
conductive sheet with which the lead frame was integrated was
heated by a drier at 175.degree. C. for one hour, and thermosetting
resin of the thermally conductive sheet was hardened. Such process
could be conducted for a short time by only conducting the molding
at low temperature, and the hardening could be conducted as a whole
after molding, so that mass treatment in a short time was realized
as an entire process. Moreover, as shown in FIG. 2E, the outer
circumference of the lead frame was cut and the bending of the
terminal was conducted, to thus completely form the thermally
conductive substrate. Moreover, in the above, the molding process
and the hardening process were separately conducted. However, a
series of process from thermal molding with pressing to hardening
could be continuously conducted.
[0114] When the thermal conductivity of the thermally conductive
substrate obtained as above was evaluated, the value was 3.7 W/mK.
Consequently, about 2 times as high a performance as that of a
conventional injection molding method or metal substrate could be
realized. Moreover, for the evaluation of reliability, a reflow
test was conducted at the maximum temperature of 260.degree. C. for
10 seconds. At this time, there were no abnormalities at the
interface between the substrate and lead frame, thus indicating a
strong adhesion at the interference.
EXAMPLE 3
[0115] In this Example, a thermally conductive substrate will be
explained, where the thermally conductive sheet was manufactured by
the same method as in Example 1 and both sides of the sheet had
metallic foil wiring layers and conductive resin composition was
filled between the layers to electrically connect the layers. The
compositions of the thermally conductive sheet used in this Example
will be described hereinafter.
[0116] (1) Inorganic filler: 90 weight % of Al.sub.2O.sub.3,
"AS-40.RTM." (the product of SHOWA DENKO K.K.) having a spherical
shape and an average particle size of 12 .mu.m.
[0117] (2) Thermosetting resin: 9 weight % of "NRV-1010.RTM." (the
product of Japan REC CO., Ltd.), a mixture comprising 60 weight
parts of brominated multifunctional epoxy resin as a main agent,
39.5 weight parts of bisphenol A nobolak resin as a hardener, and
0.5 weight parts of imidazol as a hardening accelerator.
[0118] (3) Solvent having a boiling point of not less than
150.degree. C.: 0.5 weight % of butyl carbitol (the first grade
chemical reagent of Kanto Chemical Co, Inc.).
[0119] (4) Other additives: 0.3 weight % of "Carbon Black" (the
product of Toyo-carbon CO., Ltd., and 0.2 wt. % of coupling agent,
"Plen-act KR-55.RTM." (the product of AJINOMOTO CO., INC).
[0120] A thermally conductive sheet having the tack free film
manufactured from the above mentioned compositions and was cut into
a predetermined size with through holes having a diameter of 0.15
mm punched in it by the use of carbon dioxide laser. The through
holes were equally spaced at a pitch of 0.2 to 2 mm from the
surface of the tack free film (FIG. 4B).
[0121] A conductive resin composition for filling via hole 403,
containing 85 wt. % of spherical shaped copper metal powder, 3 wt.
% of bisphenol A epoxy resin (Epikote 828, the product of
Yuka-shell epoxy Co., Ltd.) as the resin composition, 9 wt. % of
glycidyl ester system epoxy resin (YD-171, the product of Tohto
Kasei Co., Ltd.), and 3 wt. % of amine adducts hardener (MY-24, the
product of AJINOMOTO CO.,INC) were kneaded with three rolls, and
filled in the through holes by the screen printing method (FIG.
4C). After the polyethylene terephthalate film 401 was removed from
the thermally conductive sheet to which the paste was filled, a
copper foil having a thickness of 35 .mu.m and a rough surface on
one surface was adhered in a way in which the rough surface facing
the side of the thermally conductive sheet. Subsequently, the
thermally conductive sheet was thermally pressed at the pressing
temperature of 180.degree. C. and at the pressure of 50 kg/cm.sup.2
for 60 minutes to form a double-sided thermally conductive
substrate (FIG. 4E).
[0122] By such a process, epoxy resin of the thermally conductive
sheet was hardened and a strong adhesion to the rough surface of
the copper foil was obtained. At the same time, epoxy resin in the
conductive resin composition 403 was also hardened and mechanically
and electrically connected with both sides of the copper foil
through the inner via hole connection.
[0123] The copper foil of this double-sided copper plated board was
etched by means of an etching technique and a double sided wiring
substrate, having a circuit on which an electrode pattern and a
wiring pattern with a diameter of 0.2 mm were formed on the inner
via holes, was obtained. When the thermal conductivity and the
coefficient of thermal expansion of the thermally conductive
substrate manufactured by this method were measured, the thermal
conductivity was 4.1 W/mK and the coefficient of thermal expansion
for the temperature ranges from room temperature to 150.degree. C.
was 10 ppm/.degree. C., thus, exhibiting excellent properties. The
flip chip mounting of a semiconductor was conducted by using this
thermally conductive substrate. The method includes: forming Au
bump on the electrode of the semiconductor device by the
conventional wire bonding method; applying adhesives containing
Ag--Pd as the conductive materials on the top of this bump: bonding
to the electrode pattern that was formed on the double-sided
thermally conductive substrate by the flip chip method in which the
surface of the semiconductor device was faced downward; hardening;
and further mounting with molding resin. On the double-sided
thermally conductive substrate the semiconductor manufactured as
mentioned above was mounted, a reflow test was conducted 20 times
at a maximum temperature of 260.degree. C. for 10 seconds. At this
time, the change in the electrical resistance value including that
of connection between the substrate and semiconductor was very
small. That is, the initial connecting resistance was 35
m.OMEGA./bump and the connecting resistance after the test was 40
m.OMEGA./bump.
[0124] In comparison, in a conventional glass epoxy substrate on
which the through holes were provided at 2 mm intervals, the
resistance at the bonding portion between the semiconductor and the
substrate was increased, because the coefficient of thermal
expansion of semiconductor was different from that of the
substrate, so that the reflow test ended at ten times. On the other
hand, the substrate of the present invention has a coefficient of
thermal expansion in the plane direction of the substrate that is
similar to that of a semiconductor. Thus, the change in the
resistance value as a function of the numbers of reflow tests was
small.
EXAMPLE 4
[0125] In this Example, a thermally conductive substrate, wherein
the thermally conductive sheet was manufactured by the same method
as in Example 1, both sides of the sheet have a metallic foil
wiring layers and through hole copper plating was filled between
the layers to electrically connect the layers, will be explained.
The compositions of the thermally conductive sheet used in this
Example will be described hereinafter.
[0126] (1) Inorganic filler: 87 weight % of Al.sub.2O.sub.3,
"AM-28.RTM." (the product of SHOWA DENKO K.K.) having a spherical
shape and an average particle size of 12 .mu.m.
[0127] (2) Thermosetting resin: 11 weight % of phenol resin,
"Phenolite VH4150.RTM." (the product of DAINIPPPON INK AND
CHEMICALS, INC.)
[0128] (3) Solvent having a boiling point of not less than
150.degree. C.: 1.5 weight % of ethyl carbitol (the first grade
chemical reagent of Kanto Chemical Co, Inc.).
[0129] (4) Other additives: 0.3 weight % of "Carbon Black" (the
product of Toyo-carbon CO., Ltd.), and 0.2 wt. % of coupling agent,
"Plen-act, KR-55.RTM." (the product of AJINOMOTO CO., INC).
[0130] After the tack free film was peeled off from the thermally
conductive sheet which was manufactured by using the above
mentioned compositions, this thermally conductive sheet was cut
into a predetermined size. A copper foil having a thickness of 35
.mu.m and a rough surface on one side was adhered to the thermally
conductive sheet in a way in which the rough surface was faced to
the side of the thermally conductive sheet. Then this structure was
thermally pressed for 60 minutes at 180.degree. C. and at the
pressure of 50 kg/cm.sup.2 to form a double-sided thermally
conductive substrate.
[0131] By such a process, phenol resin in the thermally conductive
sheet was hardened to form the strong adhesion between the rough
surface of the copper foil and the thermally conductive sheet.
Processing through holes, having a diameter of 0.3 mm and by using
the drill was conducted on the thermally conductive substrate on
which the copper foil was adhered. Moreover, a 20 .mu.m thick
copper plating was applied to the entire surface including the
through holes. The copper foil of this double-sided copper plated
thermally conductive substrate was etched by an etching technique,
and thereby a double sided substrate, on which a wiring pattern can
be formed, was obtained (FIG. 5). The thermal conductivity and the
coefficient of thermal expansion of the thermally conductive
substrate manufactured by this method were measured and the thermal
conductivity and the coefficient of thermal expansion in the
temperature ranges from room temperature to 150.degree. C. were
formed to be 2.8 W/mK and 18 ppm/.degree. C., and thus, exhibiting
excellent properties.
EXAMPLE 5
[0132] Here, an example of the multi-layered wiring thermally
conductive substrate will be explained. A plurality of the
thermally conductive sheets manufactured by the same method as in
Example 1 were used. Wiring layers were provided to the plurality
of the layers of the thermally conductive sheets and they were
electrically connected to the thermally conductive sheets by using
a conductive resin composition. The composition of the thermally
conductive sheet used in this Example will be described
hereinafter.
[0133] (1) Inorganic filler: 92 weight % of Al.sub.2O.sub.3,
"AM-28.RTM." (the product of SHOWA DENKO K.K.) having a spherical
shape and an average particle size of 12 .mu.m.
[0134] (2) Thermosetting resin: 7.3 weight % of cyanate ester
resin. "BT2170.RTM." (the product of the Mitsubishi Gas Chemical
Company, Inc.)
[0135] (3) Solvent having a boiling point of not less than
150.degree. C.: 0.2 weight % of ethyl carbitol (the first grade
chemical reagent of Kanto Chemical CO, Inc.).
[0136] (4) Other additives: 0.3 weight % of "Carbon Black" (the
product of Toyo-carbon CO., Ltd.) and 0.2 wt. % of coupling agent
"Plen-act, KR-55.RTM.," (the product of AJINOMOTO CO., INC).
[0137] A thermally conductive sheet 600 comprising the above
mentioned compositions and having a tack free film polyethylene
terephthalate 601 was used. From the side of the polyethylene
terephthalate film, which is on one side of this thermally
conductive sheet, through holes 602 having a diameter of 0.15 mm
were formed at an equal spaced pitch of 0.2 to 2 mm by the use of a
carbon dioxide laser (FIG. 6). A conductive resin composition 603
containing 85 wt. % of copper metal spherical shaped powder, 3 wt.
% of bisphenol A epoxy resin (Epikote 828, the product of
Yuka-shell epoxy Co., Ltd.) as the resin composition, 9 wt. % of
glycidyl ester system epoxy resin (YD-171, the product of Tohto
Kasei Co., Ltd.) and 3 wt. % of amine adducts hardener (MY-24, the
product of AJINOMOTO CO.,INC) as a hardener was kneaded by three
rolls and filled in the through hole 602 by the screen printing
method.
[0138] Moreover, the tack free film 601 was peeled apart. A
conductive resin composition for forming wiring pattern containing
80 wt. % of the needle-like Ag powder, 10 wt. % of bisphenol A
epoxy resin (Epikote 828, the product of Yuka-shell epoxy Co.,
Ltd.) as the resin composition, 2 wt. % of amine adducts hardener
(MY-24, the product of AJINOMOTO CO.,INC) as the hardener, and 8
wt. % of turpentine oil as a solvent, was kneaded by three rolls
and filled to the portion where the tack free film 601 was peeled
apart by the screen printing method (FIG. 6D). Two other thermally
conductive sheets on which wiring patterns were formed were
prepared by the similar process (FIG. 6F and 6G). In addition, by
the same method, a thermally conductive sheet, where the conductive
resin composition 603 was filled in the through holes 602 (FIG.
6E), was prepared and piled up in a way in which the thermally
conductive sheet was made to be at the top by adjusting places as
shown in FIG. 6H. Onto the outer most layer, a copper foil of 18
.mu.m thickness and having a rough surface on one side. The
laminate of this thermally conductive sheet was thermally pressed
for 60 minutes at a temperature of 180.degree. C. and a pressure of
50 Kg/cm.sup.2 to form a multi-layered thermally conductive
substrate.
[0139] The copper foil of the multi-layered thermally conductive
substrate was etched by an etching technique to form a wiring
pattern. Since this multi-layered thermally conductive substrate
used copper foil for the outer most layer portion, mounting of
parts by means of soldering was possible. Moreover, on an inner
layer, a wiring pattern was formed by the screen printing method. A
line having a width of about 50 .mu.m and inner via holes could be
formed by a conductive resin composition. Thus, a high density
wiring was possible, which makes this multi-layered thermally
conductive substrate very promising as a substrate for mounting
high density electrical circuits. When the thermal conductivity and
the coefficient of thermal expansion of the thermally conductive
substrate manufactured by this method were measured, the thermal
conductivity was 4.5 W/mK and the coefficient of thermal expansion
in the temperature range from room temperature to 150.degree. C.
was 8 ppm/.degree. C., thus, showing good results.
[0140] Then, similar to the above, by using the flip chip mounting
of a semiconductor, the thermally conductive substrate was
evaluated as a multi-chip module. The method includes: forming Au
bump on the electrode of the semiconductor device by the
conventional wire bonding method; applying adhesives containing
Ag--Pd as the conductive material on the top of this bump; bonding
to the electrode pattern formed on the thermally conductive
substrate by a flip chip method in which the surface of the
semiconductor device was faced downward; hardening; and mounting
with molding resin. On the thermally conductive substrate
semiconductor was mounted, and a reflow test was conducted 20 times
at a maximum temperature of 260.degree. C. for 10 seconds. At this
time, the change in the electrical resistance value including that
of the bonding between the substrate and semiconductor was
recognized to be very stably small. That is, the initial connecting
resistance of 34 m.OMEGA./bump was only changed to 37 m.OMEGA./bump
after the test.
[0141] In addition, when the certain current was flowed to the
mounted semiconductor chip through the substrate of the present
invention and 1 W of heat was continuously generated, the change of
the electrical resistance value including that of the bonding
between substrate and semiconductor was measured. In the substrate
of the present invention, the change in the resistance value was
insignificant in respective of the number of inner via holes.
[0142] Moreover, in the above mentioned Examples 1 to 5, copper and
silver particles were used as the conductive filler in the
conductive resin composition. However, in the present invention,
the conductive particles are not limited to copper particles and
other metal particles can be used. In particular, when nickel is
used, a high electric conductivity in the conductive portion can be
maintained.
[0143] As mentioned above, the thermally conductive sheet of the
present invention can be used for a thermally conductive substrate,
where an inorganic filler can be added at a high filler content
into a thermosetting resin which is in the not-hardened state; the
coefficient of thermal expansion in the plane direction is
approximately the same as that of a semiconductor; and the high
thermal conductivity can be provided. In the thermally conductive
sheet of the present invention, a high boiling point solvent can be
added or a thermosetting resin that is liquid at room temperature
can be used. In the thermally conductive sheet of the present
invention, an inorganic filler can be added at a high fiber content
while flexibility of the thermosetting resin in the thermally
conductive sheet is maintained in the not-hardened state, and
molding the thermally conductive sheet into a desired shape at low
temperature and low pressure is possible. In addition, a substrate
can be made rigid by hardening the thermosetting resin by a thermal
pressing. The thermally conductive substrate on which a
semiconductor can be simply and directly mounted can be obtained by
the use of this flexible, thermally conductive sheet. Furthermore,
in a thermally conductive sheet in which the above mentioned
thermally conductive resin was mixed with a thermosetting resin
that is liquid at room temperature there existed no solvent in the
sheet since the drying of the solvent of not more than 100.degree.
C. had already been completed. Therefore, when this sheet is heated
and hardened, voids are not generated. Consequently, its thermal
conductivity is excellent and insulating property is also
excellent.
[0144] The thermally conductive substrate of the present invention
can realize a thermally conductive substrate on which a
semiconductor having thermal radiation property can directly be
mounted by using the thermally conductive sheets by piling up a
lead frame, and hardening the thermally conductive sheet by means
of thermal pressing to integrate with the lead frame.
[0145] Moreover, the thermally conductive substrate of the present
invention can realize a doubled-sided thermally conductive
substrate having a high thermal conductivity. This structure
permits electrical conductivity on both sides by forming through
holes in the thermally conductive sheet, and filling the thorough
holes with a conductive resin composition. Then, metallic foil
patterns can be formed on both sides of the sheet.
[0146] Moreover, the thermally conductive substrate of the present
invention can realize a high thermally conductive double-sided
substrate which permits electric conductivity by copper plating to
the through holes of the third embodiment.
[0147] Moreover, the thermally conductive substrate of the present
invention can realize a thermally conductive substrate which is a
multi-layered substrate having a multi-layered circuit structure in
which a plurality of the thermally conductive sheets are used,
through holes to which conductive resin composition is filled are
formed. a wiring pattern is formed on one side of the thermally
conductive sheet and a plurality of the thermally conductive sheets
are piled up.
[0148] As mentioned above, since the thermally conductive substrate
(the substrate having a single-sided wiring structure, double-sided
wiring structure, and multi-layered wiring structure) using the
thermally conductive sheet of the present invention can be filled
with an inorganic filler at a high filler content, it has high
thermal conductivity that cannot be obtained in the case where the
usual printed circuit board is used. Moreover, since the thermally
conductive sheet has flexibility and can be molded and processed
into any shape, the substrate can be manufactured by a simple
process. This case of manufacturing is extremely effective from an
industrial viewpoint. Furthermore, the hardened substrate is rigid
and mechanically strong, and it has the thermal conductivity and
the coefficient of thermal expansion equal to that of a
semiconductor. Therefore, the thermally conductive substrate of the
present invention is a promising material for using as a power
circuit substrate, which will be increasingly used in the future,
or as a substrate for mounting a digital high speed signal
processing LSI in which there occurs a loss of high power. In
addition, it is effective as a multi chip module (M&M) or chip
size package (SP) for mounting flip chip where the semiconductors
are directly mounted.
[0149] Finally, it is understood that the invention may be embodied
in other specific forms without departing from the spirit or
essential characteristics thereof. The embodiments disclosed in
this application are to be considered in all respects as
illustrative and not restrictive, so that the scope of the
invention being indicated by the appended claims rather than by the
foregoing description, and all changes which come within the
meaning and range of equivalency of the claims are intended to be
embraced therein.
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