U.S. patent number RE38,959 [Application Number 10/141,286] was granted by the patent office on 2006-01-31 for glasses for display panels and photovoltaic devices.
This patent grant is currently assigned to Corning Incorporated. Invention is credited to Jeffrey T. Kohli.
United States Patent |
RE38,959 |
Kohli |
January 31, 2006 |
Glasses for display panels and photovoltaic devices
Abstract
An aluminosilicate glass having a composition consisting
essentially of, as calculated in weight percent on an oxide basis,
of 58-70% SiO.sub.2, 12-22% Al.sub.2O.sub.3, 3-15% B.sub.2O.sub.3,
2-12% CaO, 0-3% SrO, 0-3% BaO, 0-8% MgO, 10-25% MCSB (i.e.,
MgO+CaO+SrO+BaO), and SrO and BaO in combination being less than
3%.
Inventors: |
Kohli; Jeffrey T. (Corning,
NY) |
Assignee: |
Corning Incorporated (Corning,
NY)
|
Family
ID: |
21871356 |
Appl.
No.: |
10/141,286 |
Filed: |
May 8, 2002 |
Related U.S. Patent Documents
|
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
60033603 |
Dec 17, 1996 |
|
|
|
Reissue of: |
08977413 |
Nov 24, 1997 |
06060168 |
May 9, 2000 |
|
|
Current U.S.
Class: |
428/428; 501/66;
313/523; 501/70; 501/32; 501/69 |
Current CPC
Class: |
C03C
3/091 (20130101) |
Current International
Class: |
B32B
9/00 (20060101); C03C 3/087 (20060101) |
Field of
Search: |
;501/65,66,69,70,32
;428/426 ;313/523 |
References Cited
[Referenced By]
U.S. Patent Documents
|
|
|
2231811 |
February 1941 |
Littleton et al. |
2961328 |
November 1960 |
Babcock et al. |
4255198 |
March 1981 |
Danielson et al. |
4394453 |
July 1983 |
Dumbaugh |
4409337 |
October 1983 |
Dumbaugh, Jr. |
4634683 |
January 1987 |
Dumbaugh, Jr. et al. |
4634684 |
January 1987 |
Dumbaugh, Jr. et al. |
4666868 |
May 1987 |
Dumbaugh, Jr. et al. |
4666869 |
May 1987 |
Dumbaugh, Jr. et al. |
5116787 |
May 1992 |
Dumbaugh, Jr. et al. |
5116788 |
May 1992 |
Dumbaugh |
5116789 |
May 1992 |
Dumbaugh, Jr. et al. |
5244847 |
September 1993 |
Kushitani et al. |
5326730 |
July 1994 |
Dumbaugh, Jr. et al. |
5374595 |
December 1994 |
Dumbaugh, Jr. et al. |
5489558 |
February 1996 |
Moffatt et al. |
5508237 |
April 1996 |
Moffatt et al. |
5741746 |
April 1998 |
Kohli et al. |
5770535 |
June 1998 |
Brix et al. |
5811361 |
September 1998 |
Miwa |
5851939 |
December 1998 |
Miwa |
6169047 |
January 2001 |
Nishizawa et al. |
6319867 |
November 2001 |
Chacon et al. |
|
Foreign Patent Documents
|
|
|
|
|
|
|
0 576 362 |
|
Jun 1993 |
|
EP |
|
0 559 389 |
|
Sep 1993 |
|
EP |
|
0 672 629 |
|
Feb 1995 |
|
EP |
|
0714862 |
|
Jun 1996 |
|
EP |
|
2 675 795 |
|
Apr 1992 |
|
FR |
|
479173 |
|
Jan 1938 |
|
GB |
|
60-215547 |
|
Oct 1985 |
|
JP |
|
61-132536 |
|
Jun 1986 |
|
JP |
|
361281041 |
|
Dec 1986 |
|
JP |
|
64-083538 |
|
Jun 1989 |
|
JP |
|
402133334 |
|
May 1990 |
|
JP |
|
4-160030 |
|
Jun 1992 |
|
JP |
|
7-277763 |
|
Oct 1995 |
|
JP |
|
408295530 |
|
Nov 1996 |
|
JP |
|
9-048632 |
|
Feb 1997 |
|
JP |
|
9-156953 |
|
Jun 1997 |
|
JP |
|
WO 97/11919 |
|
Apr 1997 |
|
WO |
|
WO 97/11920 |
|
Apr 1997 |
|
WO |
|
Other References
Patent Abstracts of Japan; vol. 013, No. 290, Jul. 5, 1989, JP
01-083538 (Nippon Sheet Glass), Mar. 29, 1989. cited by other .
Patent Abstracts of Japan, vol. 097, No. 006, Jun. 30, 1997, JP
09-048632 (Nippon Electric Glass) Feb. 18, 1997. cited by other
.
Patent Abstracts of Japan, vol. 097, No. 010, Oct. 31, 1997, JP
09-156953 (Nippon Electric Glass) Jun. 17, 1997. cited by
other.
|
Primary Examiner: Stein; Stephen
Attorney, Agent or Firm: Klee; Maurice M. Beall; Thomas
R.
Parent Case Text
This application claims the benefit of U.S. provisional application
Ser. No. 60/033,603, filed Dec. 17, 1996.
Claims
What is claimed is:
1. A substrate for a flat panel display or photovoltaic device
wherein said substrate is comprised of a flat, transparent glass
exhibiting a linear coefficient of thermal expansion (CTE) over the
temperature range 0-300.degree. C. between
30-40.times.10.sup.-7/.degree. C. and a strain point over
.[.600.degree. C..]. .Iadd.650.degree. C..Iaddend., said glass
consisting essentially of an aluminosilicate having a composition
as calculated in weight percent on an oxide basis, of 58-70%
SiO.sub.2, 12-22% Al.sub.2O.sub.3, .[.3.]. .Iadd.5.Iaddend.-15%
B.sub.2O.sub.3, .[.2.]. .Iadd.5.Iaddend.-12% CaO, 0-3% SrO, 0-3%
BaO, 0-8% MgO, .[.and.]. SrO and BaO in combination being less than
3%.Iadd., said glass containing in addition to CaO, at least one of
MgO, SrO, and BaO.Iaddend..
2. A substrate .[.glass.]. in accordance with claim 1 .[.which.].
.Iadd.wherein the glass .Iaddend.is manufactured by the float
process, said glass having a liquidus viscosity greater than about
50 .[.MPas.]. .Iadd.Pas .Iaddend.(500 poises).
3. A substrate according to claim 2, wherein said glass has a CTE
of 32-38.times.10.sup.-7/.degree. C. .[.and a strain point over
650.degree. C..].
4. A substrate according to claim 3, wherein said glass has a
strain point over 675.degree. C.
5. A substrate according to claim 3, wherein the combined SrO and
BaO content of said glass is less than about 1 weight percent.
6. A substrate according to claim 3, wherein said glass is
essentially free of SrO and BaO.
7. A flat panel display comprising a substrate in accordance with
claim 1.
8. A substrate according to claim 1, wherein said glass consists
essentially of a composition, as calculated in weight percent on an
oxide basis, of 58-67%, SiO.sub.2, 15-20% Al.sub.2O.sub.3, 5-13%
B.sub.2O.sub.3, 5-12% CaO, 0-3% SrO, 0-3% BaO, 0-8% MgO, and SrO
and BaO in combination is less than 3 wt %.
9. A substrate according to claim 3, wherein said glass consists
essentially of a composition, as calculated in weight percent on an
oxide basis, of 58-67% SiO.sub.2, 15-20% Al.sub.2O.sub.3, 5-13%
B.sub.2O.sub.3, 5-12% CaO, 0-3% SrO, 0-3% BaO, 1-8% MgO, and SrO
and BaO in combination is less than 3 wt %.
10. A substrate according to claim 9, wherein said glass has a
strain point over 675.degree. C.
11. A substrate according to claim 9, wherein the combined SrO and
BaO content of said glass is less than about 1 weight percent.
12. A substrate according to claim 9, wherein the glass has a
weight loss less than 5.0 mg/cm.sup.2 when immersed in 5% HCl at
95.degree. C. for one hour.
13. A substrate .[.according to claim 1, wherein.]. .Iadd.for a
flat panel display or photovoltaic device wherein said substrate is
comprised of a flat, transparent glass exhibiting a linear
coefficient of thermal expansion (CTE) over the temperature range
0-300.degree. C. between 30-40.times.10.sup.-7/.degree. C. and a
strain point over 600.degree. C., .Iaddend.said glass consists
essentially of .Iadd.an aluminosilicate having .Iaddend.a
composition, as calculated in weight percent on an oxide basis, of
58-64% SiO.sub.2, 16-19% Al.sub.2O.sub.3, greater than 6 and less
than 13% B.sub.2O.sub.3, 5-11% CaO, 0-3% SrO, 0-3% BaO, 1-8% MgO,
and SrO and BaO in combination being less than 3%.
14. A glass exhibiting a linear coefficient of thermal expansion
(CTE) over the temperature range 0-300.degree. C. between
30-40.times.10.sup.-7/.degree. C. and a strain point over
.[.600.degree. C..]. .Iadd.650.degree. C..Iaddend., said glass
comprising an aluminosilicate having a composition as calculated in
weight percent on an oxide basis, consisting essentially of 58-70%
SiO.sub.2, 12-22% Al.sub.2O.sub.3, .[.3.]. .Iadd.5.Iaddend.-15%
B.sub.2O.sub.3, .[.2.]. .Iadd.5.Iaddend.-12% CaO, 0-3% SrO, 0-3%
BaO, 0-8% MgO, and SrO and BaO in combination being less than
3%.Iadd., said glass containing in addition to CaO, at least one of
MgO, SrO, and BaO.Iaddend..
15. A glass in accordance with claim 14 which is manufactured by
the float process, said glass having a liquidus viscosity greater
than about 50 .[.MPas.]. .Iadd.Pas .Iaddend.(500 poises).
16. A glass according to claim 14, wherein said glass has a CTE of
32-38.times.10.sup.-7/.degree. C. .[.and a strain point over
650.degree. C..].
17. A glass according to claim 16, wherein said glass has a strain
point over 675.degree. C.
18. A photovoltaic device comprising a substrate in accordance with
claim 1.
19. A .[.substrate.]. .Iadd.glass .Iaddend.according to claim 14,
wherein said glass consists essentially of a composition, as
calculated in weight percent on an oxide basis, of 58-67%
SiO.sub.2, 15-20% Al.sub.2O.sub.3, 5-13% B.sub.2O.sub.3, 5-12% CaO,
0-3% SrO, 0-3% BaO, 1-8% MgO, and SrO and BaO in combination is
less than 3 wt %.
20. A substrate according to claim 1, wherein MgO+CaO+SrO+BaO is
.[.10-25.]. .Iadd.greater than or equal to 10 and less than 23
.Iaddend.weight percent.
21. A substrate according to claim 1, wherein MgO+CaO+SrO+BaO is
.[.8.6-18.2.]. .Iadd.8.6-14.8 .Iaddend.weight percent.
.Iadd.22. A substrate for a flat panel display or photovoltaic
device wherein said substrate is comprised of a flat, transparent
glass exhibiting a linear coefficient of thermal expansion (CTE)
over the temperature range 0-300.degree. C. between
30-40.times.10.sup.-7/.degree. C. and a strain point of 600.degree.
C., said glass consisting essentially of an aluminosilicate having
a composition as calculated in weight percent on an oxide basis, of
58-70% SiO.sub.2, 12-22% Al.sub.2O.sub.3, 6.5-15% B.sub.2O.sub.3,
6-12% CaO, 0-1.9% SrO, 0-3% BaO, 0-8% MgO, SrO and BaO in
combination being less than 3%, said glass containing in addition
to CaO, at least one of MgO, SrO, and BaO..Iaddend.
.Iadd.23. A glass exhibiting a linear coefficient of thermal
expansion (CTE) over the temperature range 0-300.degree. C. between
30-40.times.10.sup.-7/.degree. C. and a strain point over
600.degree. C., said glass comprising an aluminosilicate having a
composition as calculated in weight percent on an oxide basis,
consisting essentially of 58-70% SiO.sub.2, 12-22% Al.sub.2O.sub.3,
6.5-15% B.sub.2O.sub.3, 6-12% CaO, 0-1.9% SrO, 0-3% BaO, 0-8% MgO,
and SrO and BaO in combination being less than 3%, said glass
containing in addition to CaO, at least one of MgO, SrO, and
BaO..Iaddend.
.Iadd.24. A substrate for a flat panel display or photovoltaic
device wherein said substrate is comprised of a flat, transparent
glass exhibiting a density of less than 2.50 g/cm.sup.3, a linear
coefficient of thermal expansion (CTE) over the temperature range
0-300.degree. C. between 30-40.times.10.sup.-7/.degree. C. and a
strain point over 600.degree. C., said glass consisting essentially
of an aluminosilicate having a composition as calculated in weight
percent on an oxide basis, of 58-70% SiO.sub.2, 12-22%
Al.sub.2O.sub.3, 7.1-15% B.sub.2O.sub.3, 6-12% CaO, 0-1.9% SrO,
0-3% BaO, 0-8% MgO, SrO and BaO in combination being less than 3%,
said glass containing in addition to CaO, at least one of MgO, SrO,
and BaO..Iaddend.
.Iadd.25. A glass exhibiting a density of less than 2.50
g/cm.sup.3, a linear coefficient of thermal expansion (CTE) over
the temperature range 0-300.degree. C. between
30-40.times.10.sup.-7/.degree. C. and a strain point over
600.degree. C., said glass comprising an aluminosilicate having a
composition as calculated in weight percent on an oxide basis,
consisting essentially of 58-70% SiO.sub.2, 12-22% Al.sub.2O.sub.3,
7.1-15% B.sub.2O.sub.3, 6-12% CaO, 0-1.9% SrO, 0-3% BaO, 0-8% MgO,
and SrO and BaO in combination being less than 3%, said glass
containing in addition to CaO, at least one of MgO, SrO, and
BaO..Iaddend.
.Iadd.26. A substrate for a flat panel display or photovoltaic
device wherein said substrate is comprised of a flat, transparent
glass exhibiting a density of less than 2.50 g/cm.sup.3, a linear
coefficient of thermal expansion (CTE) over the temperature range
0-300.degree. C. between 30-40.times.10.sup.-7/.degree. C. and a
strain point over 600.degree. C., said glass consisting essentially
of an aluminosilicate having a composition as calculated in weight
percent on an oxide basis, of 60.5-70% SiO.sub.2, 12-22%
Al.sub.2O.sub.3, 7.1-15% B.sub.2O.sub.3, 6.1-12% CaO, 0-1.9% SrO,
0-3% BaO, 0-6% MgO, SrO and BaO in combination being less than 3%,
said glass containing in addition to CaO, at least one of MgO, SrO,
and BaO..Iaddend.
.Iadd.27. A glass exhibiting a density of less than 2.50
g/cm.sup.3, a linear coefficient of thermal expansion (CTE) over
the temperature range 0-300.degree. C. between
30-40.times.10.sup.-7/.degree. C. and a strain point over
600.degree. C., said glass comprising an aluminosilicate having a
composition as calculated in weight percent on an oxide basis,
consisting essentially of 60.5-70% SiO.sub.2, 12-22%
Al.sub.2O.sub.3, 7.1-15% B.sub.2O.sub.3, 6.1-12% CaO, 0-1.9% SrO,
0-3% BaO, 0-6% MgO, and SrO and BaO in combination being less than
3%, said glass containing in addition to CaO, at least one of MgO,
SrO, and BaO..Iaddend.
.Iadd.28. A substrate for a flat panel display or photovoltaic
device wherein said substrate is comprised of a flat, transparent
glass exhibiting a density of less than 2.50 g/cm.sup.3, a linear
coefficient of thermal expansion (CTE) over the temperature range
0-300.degree. C. between 30-40.times.10.sup.-7/.degree. C. and a
strain point over 600.degree. C., said glass consisting essentially
of an aluminosilicate having a composition as calculated in weight
percent on an oxide basis, of 58-70% SiO.sub.2, 15-18.9%
Al.sub.2O.sub.3, 7.1-15% B.sub.2O.sub.3, 6-12% CaO, 0-1.9% SrO,
0-3% BaO, 0-8% MgO, SrO and BaO in combination being less than
3%..Iaddend.
.Iadd.29. A glass exhibiting a density of less than 2.50
g/cm.sup.3, a linear coefficient of thermal expansion (CTE) over
the temperature range 0-300.degree. C. between
30-40.times.10.sup.-7/.degree. C. and a strain point over
600.degree. C., said glass comprising an aluminosilicate having a
composition as calculated in weight percent on an oxide basis,
consisting essentially of 58-70% SiO.sub.2, 15-18.9%
Al.sub.2O.sub.3, 7.1-15% B.sub.2O.sub.3, 6-12% CaO, 0-1.9% SrO,
0-3% BaO, 0-8% MgO, and SrO and BaO in combination being less than
3%..Iaddend.
.Iadd.30. A substrate for a flat panel display or photovoltaic
device wherein said substrate is comprised of a flat, transparent
glass exhibiting a density of less than 2.50 g/cm.sup.3, a linear
coefficient of thermal expansion (CTE) over the temperature range
0-300.degree. C. between 30-40.times.10.sup.-7/.degree. C. and a
strain point over 600.degree. C., said glass consisting essentially
of an aluminosilicate having a composition as calculated in weight
percent on an oxide basis, of 60.5-70% SiO.sub.2, 15-18.9%
Al.sub.2O.sub.3, 7.1-15% B.sub.2O.sub.3, 6.1-12% CaO, 0-1.9% SrO,
0-3% BaO, 0-6% MgO, SrO and BaO in combination being less than
3%..Iaddend.
.Iadd.31. A glass exhibiting a density of less than 2.50
g/cm.sup.3, a linear coefficient of thermal expansion (CTE) over
the temperature range 0-300.degree. C. between
30-40.times.10.sup.-7/.degree. C. and a strain point over
600.degree. C., said glass comprising an aluminosilicate having a
composition as calculated in weight percent on an oxide basis,
consisting essentially of 60.5-70% SiO.sub.2, 15-18.9%
Al.sub.2O.sub.3, 7.1-15% B.sub.2O.sub.3, 6.1-12% CaO, 0-1.9% SrO,
0-3% BaO, 0-6% MgO, and SrO and BaO in combination being less than
3%..Iaddend.
.Iadd.32. A substrate for a flat panel display or photovoltaic
device wherein said substrate is comprised of a flat, transparent
glass exhibiting a linear coefficient of thermal expansion (CTE)
over the temperature range 0-300.degree. C. between
30-40.times.10.sup.-7/.degree. C. and a strain point over
600.degree. C., said glass consisting essentially of an
aluminosilicate having a composition as calculated in weight
percent on an oxide basis, of 58-70% SiO.sub.2, 15-18.9%
Al.sub.2O.sub.3, 6.5-15% B.sub.2O.sub.3, 6-12% CaO, 0-1.9% SrO,
0-3% BaO, 0-8% MgO, SrO and BaO in combination being less than
3%..Iaddend.
.Iadd.33. A glass exhibiting a linear coefficient of thermal
expansion (CTE) over the temperature range 0-300.degree. C. between
30-40.times.10.sup.-7/.degree. C. and a strain point over
600.degree. C., said glass comprising an aluminosilicate having a
composition as calculated in weight percent on an oxide basis,
consisting essentially of 58-70% SiO.sub.2, 15-18.9%
Al.sub.2O.sub.3, 6.5-15% B.sub.2O.sub.3, 6-12% CaO, 0-1.9% SrO,
0-3% BaO, 0-8% MgO, and SrO and BaO in combination being less than
3%..Iaddend.
.Iadd.34. A substrate for a flat panel display or photovoltaic
device wherein said substrate is comprised of a flat, transparent
glass exhibiting a linear coefficient of thermal expansion (CTE)
over the temperature range 25-300.degree. C. between
30-41.5.times.10.sup.-7/.degree. C. and a strain point over
650.degree. C., said glass consisting essentially of an
aluminosilicate having a composition as calculated in weight
percent on an oxide basis, of 58-70% SiO.sub.2, 12-22%
Al.sub.2O.sub.3, 3.8-15% B.sub.2O.sub.3, 6-12% CaO, 0-1.9% SrO,
0-3% BaO, 0-8% MgO, SrO and BaO in combination being less than 3%,
said glass containing in addition to CaO, at least one of MgO, SrO,
and BaO..Iaddend.
.Iadd.35. A glass exhibiting a linear coefficient of thermal
expansion (CTE) over the temperature range 25-300.degree. C.
between 30-41.5.times.10.sup.-7/.degree. C. and a strain point over
650.degree. C., said glass comprising an aluminosilicate having a
composition as calculated in weight percent on an oxide basis,
consisting essentially of 58-70% SiO.sub.2, 12-22% Al.sub.2O.sub.3,
3.8-15% B.sub.2O.sub.3, 6-12% CaO, 0-1.9% SrO, 0-3% BaO, 0-8% MgO,
and SrO and BaO in combination being less than 3%, said glass
containing in addition to CaO, at least one of MgO, SrO, and
BaO..Iaddend.
.Iadd.36. A substrate for a flat panel display or photovoltaic
device wherein said substrate is comprised of a flat, transparent
glass exhibiting a linear coefficient of thermal expansion (CTE)
over the temperature range 25-300.degree. C. between
30-41.5.times.10.sup.-7/.degree. C. and a strain point over
650.degree. C., said glass consisting essentially of an
aluminosilicate having a composition as calculated in weight
percent on an oxide basis, of 58-70% SiO.sub.2, 15-18.9%
Al.sub.2O.sub.3, 3.8-15% B.sub.2O.sub.3, 6-12% CaO, 0-1.9% SrO,
0-3% BaO, 0-8% MgO, SrO and BaO in combination being less than
3%..Iaddend.
.Iadd.37. A glass exhibiting a linear coefficient of thermal
expansion (CTE) over the temperature range 25-300.degree. C.
between 30-41.5.times.10.sup.-7/.degree. C. and a strain point over
650.degree. C., said glass comprising an aluminosilicate having a
composition as calculated in weight percent on an oxide basis,
consisting essentially of 58-70% SiO.sub.2, 15-18.9
Al.sub.2O.sub.3, 3.8-15% B.sub.2O.sub.3, 6-12% CaO, 0-1.9% SrO,
0-3% BaO, 0-8% MgO, and SrO and BaO in combination being less than
3%..Iaddend.
.Iadd.38. A substrate according to claim 1 or 13, wherein the glass
has a density of less than 2.50 g/cm.sup.3..Iaddend.
.Iadd.39. A glass according to claim 14, wherein the glass has a
density of less than 2.50 g/cm.sup.3..Iaddend.
.Iadd.40. A substrate according to claim 1 or 13, wherein the glass
has a liquidus temperature below about 1250.degree. C..Iaddend.
.Iadd.41. A glass according to claim 14, wherein the glass has a
liquidus temperature below about 1250.degree. C..Iaddend.
.Iadd.42. A substrate according to claim 13, 22, 24, 26, 28, 30,
32, 48, 50, 52, or 54 wherein the glass has a strain point over
650.degree. C..Iaddend.
.Iadd.43. A glass according to claim 23, 25, 27, 29, 31, 33, 49,
51, 53, or 55 wherein the glass has a strain point over 650.degree.
C..Iaddend.
.Iadd.44. A substrate in accordance with claim 1, 13, 22, 24, 26,
28, 30, 32, 34, 36, 48, 50, 52, or 54 wherein the glass is
manufactured by the float process..Iaddend.
.Iadd.45. A glass in accordance with claim 14, 23, 25, 27, 29, 31,
33, 35, 37, 49, 51, 53, or 55 which is manufactured by the float
process..Iaddend.
.Iadd.46. A flat panel display comprising a substrate in accordance
with claim 13, 22, 24, 26, 28, 30, 32, 34, 36, 48, 50, 52, or
54..Iaddend.
.Iadd.47. A photovoltaic device comprising a substrate in
accordance with claim 13, 22, 24, 26, 28, 30, 32, 34, 36, 48, 50,
52, or 54..Iaddend.
.Iadd.48. A substrate for a flat panel display or photovoltaic
device wherein sad substrate is comprised of a flat, transparent
glass exhibiting a density of less than 2.50 g/cm.sup.3, a linear
coefficient of thermal expansion (CTE) over the temperature range
0-300.degree. C. between 30-40.times.10.sup.-7/.degree. C. and a
strain point over 600.degree. C., said glass consisting essentially
of an aluminosilicate having a composition as calculated in weight
percent on an oxide basis, of 58-70% SiO.sub.2, 15-18.9%
Al.sub.2O.sub.3, 7.1-15% B.sub.2O.sub.3, 6-12% CaO, 0-1.9% SrO,
0-3% BaO, 0-8% MgO..Iaddend.
.Iadd.49. A glass exhibiting a density of less than 2.50
g/cm.sup.3, a linear coefficient of thermal expansion (CTE) over
the temperature range 0-300.degree. C. between
30-40.times.10.sup.-7/.degree. C. and a strain point over
600.degree. C., said glass comprising an aluminosilicate having a
composition as calculated in weight percent on an oxide basis,
consisting essentially of 58-70% SiO.sub.2, 15-18.9%
Al.sub.2O.sub.3, 7.1-15% B.sub.2O.sub.3, 6-12% CaO, 0-1.9% SrO,
0-3% BaO, 0-8% MgO..Iaddend.
.Iadd.50. A substrate for a flat panel display or photovoltaic
device wherein said substrate is comprised of a flat, transparent
glass exhibiting a density of less than 2.50 g/cm.sup.3, a linear
coefficient of thermal expansion (CTE) over the temperature range
0-300.degree. C. between 30-40.times.10.sup.-7/.degree. C. and a
strain point over 600.degree. C., said glass consisting essentially
of an aluminosilicate having a composition as calculated in weight
percent on an oxide basis, of 60.5-70% SiO.sub.2, 15-18.9%
Al.sub.2O.sub.3, 7.1-15% B.sub.2O.sub.3, 6.1-12% CaO, 0-1.9% SrO,
0-3% BaO, 0-6% MgO..Iaddend.
.Iadd.51. A glass exhibiting a density of less than 2.50
g/cm.sup.3, a linear coefficient of thermal expansion (CTE) over
the temperature range 0-300.degree. C. between
30-40.times.10.sup.-7/.degree. C. and a strain point over
600.degree. C., said glass comprising an aluminosilicate having a
composition as calculated in weight percent on an oxide basis,
consisting essentially of 60.5-70% SiO.sub.2, 15-18.9%
Al.sub.2O.sub.3, 7.1-15% B.sub.2O.sub.3, 6.1-12% CaO, 0-1.9% SrO,
0-3% BaO, 0-6% MgO..Iaddend.
.Iadd.52. A substrate for a flat panel display or photovoltaic
device wherein said substrate is comprised of a flat, transparent
glass exhibiting a density of less than 2.50 g/cm.sup.3, a linear
coefficient of thermal expansion (CTE) over the temperature range
0-300.degree. C. between 30-40.times.10.sup.-7/.degree. C. and a
strain point over 600.degree. C., said glass comprising an
aluminosilicate having a composition as calculated in weight
percent on an oxide basis that comprises 58-70% SiO.sub.2, 15-18.9%
Al.sub.2O.sub.3, 7.1-15% B.sub.2O.sub.3, 6-12% CaO, 0-1.9% SrO,
0-3% BaO, 0-8% MgO..Iaddend.
.Iadd.53. A glass exhibiting a density of less than 2.50
g/cm.sup.3, a linear coefficient of thermal expansion (CTE) over
the temperature range 0-300.degree. C. between
30-40.times.10.sup.-7/.degree. C. and a strain point over
600.degree. C., said glass comprising an aluminosilicate having a
composition as calculated in weight percent on an oxide basis that
comprises 58-70% SiO.sub.2, 15-18.9% Al.sub.2O.sub.3, 7.1-15%
B.sub.2O.sub.3, 6-12% CaO, 0-1.9% SrO, 0-3% BaO, 0-8%
MgO..Iaddend.
.Iadd.54. A substrate for a flat panel display or photovoltaic
device wherein said substrate is comprised of a flat, transparent
glass exhibiting a density of less than 2.50 g/cm.sup.3, a linear
coefficient of thermal expansion (CTE) over the temperature range
0-300.degree. C. between 30-40.times.10.sup.-7/.degree. C. and a
strain point over 600.degree. C., said glass comprising an
aluminosilicate having a composition as calculated in weight
percent on an oxide basis that comprises 60.5-70% SiO.sub.2,
15-18.9% Al.sub.2O.sub.3, 7.1-15% B.sub.2O.sub.3, 6.1-12% CaO,
0-1.9% SrO, 0-3% BaO, 0-6% MgO..Iaddend.
.Iadd.55. A glass exhibiting a density of less than 2.50
g/cm.sup.3, a linear coefficient of thermal expansion (CTE) over
the temperature range 0-300.degree. C. between
30-40.times.10.sup.-7/.degree. C. and a strain point over
600.degree. C., said glass comprising an aluminosilicate having a
composition as calculated in weight percent on an oxide basis that
comprises 60.5-70% SiO.sub.2, 15-18.9% Al.sub.2O.sub.3, 7.1-15%
B.sub.2O.sub.3, 6.1-12% CaO, 0-1.9% SrO, 0-3% BaO, 0-6%
MgO..Iaddend.
.Iadd.56. A substrate in accordance with claim 1, 13, 22, 24, 26,
28, 30, 32, 34, 36, 48, 50, 52, or 54 wherein the glass is
essentially free of intentionally added alkali metal
oxide..Iaddend.
.Iadd.57. A glass in accordance with claim 14, 23, 25, 27, 29, 31,
33, 35, 37, 49, 51, 53, or 55 wherein the glass is essentially free
of intentionally added alkali metal oxide..Iaddend.
Description
FIELD OF THE INVENTION
The invention relates to a family of aluminosilicate glass
compositions exhibiting physical and chemical properties suitable
for flat panel display.
BACKGROUND OF THE INVENTION
Liquid crystal displays (LCDs) are passive flat panel displays
which depend upon external sources of light for illumination. They
are manufactured as segmented displays or in one of two basic
configurations. The substrate needs (other than being transparent
and capable of withstanding the chemical conditions to which it is
exposed during display processing) of the two matrix types vary.
The first type is intrinsic matrix addressed, relying upon the
threshold properties of the liquid crystal material. The second is
extrinsic matrix or active matrix (AM) addressed, in which an array
of diodes, metal-insulator-metal (MIM) devices, or thin film
transistors (TFTs) supplies an electronic switch to each pixel. In
both cases, two sheets of glass form the structure of the display.
The separation between the two sheets is the critical gap
dimension, of the order of 5-10 .mu.m.
Intrinsically addressed LCD's are fabricated using metal deposition
techniques, typically at temperatures .ltoreq.350.degree. C.,
followed by standard metal etching procedures. As a result, the
substrate requirements therefor are often the same as those for
segmented displays. Soda-lime-silica glass with a barrier layer has
proven to be adequate for most needs. A high performance version of
intrinsically addressed LCDs, the super twisted nematic (STN) type,
has an added requirement of extremely precise flatness for the
purpose of holding the gap dimensions uniform.
Extrinsically addressed LCD's can be further subdivided depending
upon the nature of the electrical switch located at each optical
element (subpixel). Two of the most popular types of extrinsically
(or active matrix, AMLCD) addressed LCD's are those based on either
amorphous (a-Si) or poly-crystalline (poly-Si) silicon thin film
transistors (TFT's).
U.S. Pat. No. 4,824,808 (Dumbaugh, Jr.) lists four desirable
properties for a glass to exhibit in order to fully satisfy the
needs of a substrate for extrinsically addressed LCD's:
First, that the glass be essentially free of intentionally added
alkali metal oxide to avoid the possibility of alkali metal
contamination of the TFT;
Second, that the glass be sufficiently chemically durable to
withstand the reagents used during the manufacture of the TFT;
Third, that the expansion mismatch between the glass and the
silicon present in the TFT array be maintained at a relatively low
level even as processing temperatures for the substrates increase;
and
Fourth, that the glass be capable of being produced in high quality
thin sheet form at low cost; that is, it must not require extensive
grinding and polishing to secure the necessary surface finish.
Recent improvements in the resolution of extrinsically addressed
LCD's have led to the desirability of .[.a.]. further glass
properties, namely, a high glass strain point, a low density, and a
high modulus. Strain point is used as an indication of the thermal
shrinkage of the glass. As can be appreciated, the lower the strain
point, the greater is this thermal shrinkage. Low thermal shrinkage
is desirable for precise alignment during successive
photolithographic and other patterning steps during the TFT
processing. Consequently, glasses having higher strain points are
generally preferred for extrinsically addressed LCD's, particularly
those which employ poly-Si TFT technology. Thus, there has been
considerable research to develop glasses demonstrating high strain
points so that thermal shrinkage is minimized during device
processing. Corning Code 1737 glass, which has the highest strain
point (666.degree. C.) in the AMLCD substrate industry, is rapidly
becoming an industry standard. Concurrent with their high strain
points, these glasses often have high melting temperatures, e.g. on
the order of 1550-1650.degree. C. Low densities and high modulii
are desired to minimize sag during thermal processing and to allow
for thinner and lighter displays.
Another technology termed "chip-on-glass" (COG) has further
emphasized the need for the substrate glass to closely match
silicon in thermal expansion. Thus, the initial LCD devices did not
have their driver chips mounted on the substrate glass. Instead,
the silicon chips were mounted remotely and were connected to the
LCD substrate circuitry with compliant or flexible wiring. As LCD
device technology improved and as the devices became larger and
required finer resolutions, these flexible mountings became
unacceptable, both because of cost and of uncertain reliability.
This situation led to Tape Automatic Bonding (TAB) of the silicon
chips. In that process the silicon chips and electrical connections
to the chips were mounted on a carrier tape, that subassembly was
mounted directly on the LCD substrate, and thereafter the
connection to the LCD circuitry was completed. TAB decreased cost
while improving reliability and increasing the permitted density of
the conductors to a pitch of approximately 200 .mu.m--all
significant factors. COG, however, provides further improvement
over TAB with respect to those three factors. Hence, as the size
and quality requirements of LCD devices increase, COG is demanded
for those devices dependent upon the use of integrated circuit
silicon chips. For that reason, the substrate glass preferably
demonstrate a linear coefficient of thermal expansion closely
matching that of silicon; i.e., a linear coefficient of thermal
expansion (0.degree.-300.degree. C.) between about
32-39.times.10.sup.-7/.degree. C.
It would therefore be desirable to provide a glass substrate having
a CTE in the 30-40.degree..times.10.sup.-7/.degree. C. range and a
strain point greater than 650.degree. C., more preferably greater
than 675.degree. C. A density less than 2.50 g/cm.sup.3 and a
Young's modulus of greater than 11.0 Mpsi would also be desirable.
It would also be desirable for the glass to be capable of being
manufactured using the float process.
SUMMARY OF THE INVENTION
The present invention is directed to boro-aluminosilicate glasses
having a coefficient of thermal expansion (CTE) between
30-39.times.10.sup.-7/.degree. C. over the temperature range of
25.degree.-300.degree. C. and have a composition consisting
essentially of as calculated in weight percent on an oxide basis,
58-70 SiO.sub.2, 12-22 Al.sub.2O.sub.3, 3-15 B.sub.2O.sub.3, 0-8
MgO, 2-12 CaO, 0-3 SrO, 0-3 BaO, and SrO+BaO in combination is less
than 3. The glasses also preferably employ a combination of MgO,
CaO, SrO+BaO (MCSB) between about 10-25 weight percent. Other
oxides may include, for example, the transition metals,
particularly those in period 4 (such as ZnO and TiO.sub.2), as well
as Y.sub.2O.sub.3, La.sub.2O.sub.3, ZrO.sub.2, and P.sub.2O.sub.3,
and those ingredients employed for fining (e.g. CaSO.sub.4,
As.sub.2O.sub.3, Sb.sub.2O.sub.3, halides, and so forth). These
other oxides listed above should preferably not exceed 5 wt % in
total. Na.sub.2O and K.sub.2O content each is preferably kept less
than 1 weight percent and more preferably the glasses of the
present invention are essentially alkali-free.
More preferably the glass consists essentially of 58-67 SiO.sub.2,
15-20 Al.sub.2O.sub.3, 5-13 B.sub.2O.sub.3, 0-8 MgO, 5-12 CaO, 0-3
SrO, 0-3BaO, and SrO and BaO in combination being less than 3.
Most preferably the glass consists essentially of 58-64 SiO.sub.2,
16-19 Al.sub.2O.sub.3, greater than 6 and less than 13
B.sub.2O.sub.3, 1-8 MgO, 5-11 CaO, 0-3 BaO, and SrO and BaO in
combination being less than 3.
The glasses of the present invention exhibit a coefficient of
thermal expansion (CTE) in the range of 30-39 (more preferably
31-38, and most preferably 32-38).times.10.sup.-7/.degree. C., from
25-300.degree. C. and a high strain point (at least 650.degree. C.,
preferably greater than 675.degree. C., in order to eliminate or
minimize the need for a pre-compaction annealing step. Low density
(preferably less than 2.5 g/cm.sup.3, most preferably less than 2.4
g/cm.sup.3) and high Young's modulus is desirable to minimize
display weight and panel sag and at the same time maximize hardness
in order to improve resistance to scratching and edge defects.
The glass compositions covered in the present invention disclosure
are believed to be well suited to flat glass manufacture via the
float process in that they generally: 1) do not necessarily include
certain oxides or elements in amounts which are known to be
detrimental to the float bath, such as As, Sb, Pb, Bi, Ti; 2) are
easily melted (having 200 poise isokom temperatures less than
1600.degree. C., more preferably below 1550.degree. C.); and 3)
exhibit liquidus viscosities greater than 10.sup.3 poise. Moreover,
the preferred compositions contain little or no SrO or BaO oxides
in order to achieve low density, high Young's modulus, high strain
point, and low melting temperature. For this reason, each of the
SrO and BaO content is preferably less than 3, more preferably less
than 1 (and less than 2 weight percent in combination), and most
preferably is essentially zero.
DESCRIPTION OF THE INVENTION
The present invention is concerned with improved glasses for use as
flat panel display substrates. In particular, the glasses meet the
various property requirements of such substrates. It is believed
that glasses of the present invention are capable of being formed
using the float glass manufacturing process. To provide flexibility
in the melting process, and particularly to enable the production
of the glasses via the float process, it is desirable that the
glass have several characteristics related to melting properties.
For example, a melting temperature (i.e., temperature at which the
viscosity is about 20 Pas (200 poises)) less than or equal to about
1550.degree. C., and more preferably less than or equal to about
1500.degree. C. More importantly, in order to manufacture the glass
via the float glass manufacturing process, it is desirable for the
glass to exhibit a viscosity at the liquidus temperature which is
greater than 50 .[.MPas.]. .Iadd.Pas .Iaddend.(500 poises), more
preferably greater than 100 .[.MPas.]. .Iadd.Pas .Iaddend.(1000
poises), and most preferably greater than about 250 .[.MPas.].
.Iadd.Pas .Iaddend.(2500 poises). In addition, it is desirable that
the glass be capable of exhibiting a Liquidus Temperature below
about 1250.degree. C., most preferably below about 1200.degree.
C.
The preferred glasses in accordance with the present invention have
a CTE in the range of 30-39.times.10.sup.-7/.degree. C., more
preferably 31-38.times.10.sup.-7/.degree. C., and most preferably
32-38.times.10.sup.-7/.degree. C. The desire for such a CTE is
primarily driven by the desire to match the CTE of silicon
transistor chips. The glasses of the present invention preferably
have a strain point greater than 650.degree. C., more preferably
greater than 675.degree. C. A high strain point is desired to help
prevent panel distortion due to compaction/shrinkage during
subsequent thermal processing. In the most preferred embodiments,
the glasses exhibit a combination of desirable CTE's and strain
point. For example, the most preferred glasses exhibit a CTE
between 31-38.times.10.sup.-7/.degree. C., in combination with a
strain point greater than about 675.degree. C.
Chemical durability generally improves as the ratio of glass
formers plus intermediates to glass modifiers increases. It is
desirable that glasses for present purposes have a weight loss less
than about 5.0 mg/cm.sup.2, more preferably less than 2.0
mg/cm.sup.2 and most preferably less than 1.0 mg/cm.sup.2 after
exposure to the 5% HCl solution at 95.degree. C. for 20 minutes.
Glasses having compositions within the following oxide ranges in
weight percent are generally characterized by wt. loss values less
than 5.0 mg/cm.sup.2:
TABLE-US-00001 SiO.sub.2 58-70 Al.sub.2O.sub.3 12-22 CaO 2-12 SrO
0-3 BaO 0-3 MgO 1-8 B.sub.2O.sub.3 3-15 MgO + CaO + SrO + BaO 10-25
SrO + BaO 0-3
The present glasses employ 58-70% by weight SiO.sub.2 as the
primary glass former. Increasing SiO.sub.2 content generally
improves durability, but raises the melting point. The glasses also
comprise 12-22 wt % Al.sub.2O.sub.3. As the Al.sub.2O.sub.3 content
increases, glass durability increases, but CTE decreases and the
melting point increases. Boric oxide (B.sub.2O.sub.3) decreases
melting temperature, but is generally detrimental to HCl
durability, and strain point. B.sub.2O.sub.3 content is between 3
and 15 percent by weight. Generally speaking MgO and/or CaO can
replace B.sub.2O.sub.3 to maintain a low CTE, density, Young's
modulus and flux the melt. B.sub.2O.sub.3 tends to decrease the
liquidus temperature and increase the viscosity at the liquidus.
However, relatively high levels of B.sub.2O.sub.3 are detrimental
to HCl durability. The role of MgO and CaO is to limit alkali
mobility and flux the melt at relatively high temperatures, while
at the same time enabling a high strain point and low density. MgO
is limited to 8, more preferably is 1-8, and most preferably is 2-6
weight percent. SrO and BaO in combination are preferably less than
3% more preferably less than 2%, and most preferably are
essentially avoided to minimize the formation of BaSO.sub.4,
SrSO.sub.4, as well as to lower the density, increase the strain
point, and increase the modulus of the glass.
The invention is further illustrated by the following examples,
which are meant to be illustrative, and not in any way limiting, to
the claimed invention. TABLE I sets forth exemplary glass
compositions in weight percent, as calculated on an oxide basis
from the glass batches. These example glasses were prepared by
melting 1000-5000 gram batches of each glass composition at a
temperature and time to result in a relatively homogeneous glass
composition, e.g. at a temperature of about 1550-1600.degree. C.
for a period of about 6 to 16 hours in platinum crucibles. Also set
forth are relevant glass properties for each glass composition,
determined on the glasses in accordance with techniques
conventional in the glass art. Thus, the linear coefficient of
thermal expansion (CTE) over the temperature range
25.degree.-300.degree. C. expressed in terms of
.times.10.sup.-7/.degree. C., and the softening point (Soft.Pt.),
annealing point (Anneal.Pt.), and strain point expressed in terms
of .degree. C. Softening point was measured using the parallel
plate method, and annealing point and strain point were both
measured using beam bending viscometry.
The internal liquidus temperatures (Liq.Temp.) of the glasses were
measured using the standard liquidus method, which involves placing
crushed glass particles in a platinum boat, placing the boat in a
furnace having a region of gradient temperatures, heating the boat
in an appropriate temperature region for 24 hours, and determining
by means of microscopic examination the highest temperature at
which crystals appear in the interior of the glass. The 200 poise
temperature (in .degree. C.) (defined as the temperature at which
the glass melt demonstrates a viscosity of 200 poises [20 Pa.s])
was calculated employing the Fulcher equation as fit to the high
temperature viscosity data. Also listed is Young's modulus, shear
modulus and specific modulus (Young's modulus/density), as well as
Knoop hardness, which was measured using a 100 gram load.
TABLE-US-00002 TABLE I wt % 1 2 3 4 5 A SiO.sub.2 60.2 60.7 60.5
62.0 61.0 57.8 Al.sub.2O.sub.3 17.8 18.0 17.9 17.0 18.0 16.5
B.sub.2O.sub.3 3.8 6.5 7.1 7.1 7.1 8.5 MgO 7.6 6.1 4.3 5.8 5.8 .75
CaO 10.6 8.7 10.2 8.1 8.1 4.15 SrO 0.0 0.0 0.0 0.0 0.0 1.9 BaO 0.0
0.0 0.0 0.0 0.0 9.4 Liquidus (.degree. C.) 1220 1240 1210 1240 1200
1090 Temperature Soft Pt (.degree. C.) 947 937 940 945 942 975
Anneal Pt (.degree. C.) 739 723 728 730 730 721 Strain Pt (.degree.
C.) 692 677 681 686 683 666 CTE (.times.10.sup.-7/.degree. C.) 41.5
39.5 39.0 37.3 36.5 37.8 Density (g/cm.sup.3) 2.575 2.501 2.459
2.459 2.466 2.544 Young's Modulus (Mpsi) 12.0 10.2 Shear Modulus
(Mpsi) 4.8 4.1 Specific Modulus 4.9 4.0 (Mpsi cm.sup.3/g) Knoop
Hardness (100 g) 505 460 200 Poise Temp (.degree. C.) 1515 1625 wt
% 6 7 8 9 10 SiO.sub.2 61.3 62.4 63.5 62.7 62.1 Al.sub.2O.sub.3
18.1 18.0 18.9 18.7 18.5 B.sub.2O.sub.3 7.2 7.1 8.4 8.3 8.2 MgO 7.4
5.2 3.0 2.2 2.2 CaO 6.0 7.3 6.2 6.2 6.1 SrO 0.0 0.0 0.0 1.9 0.0 BaO
0.0 0.0 0.0 0.0 2.8 Liquidus (.degree. C.) 1240 1240 >1260 1250
>1250 Temperature Soft Pt (.degree. C.) 943 958 984 985 986
Anneal Pt (.degree. C.) 736 738 754 751 748 Strain Pt (.degree. C.)
691 691 704 700 697 CTE (.times.10.sup.-7/.degree. C.) 35.8 34.3
31.0 32.7 31.0 Density (g/cm.sup.3) 2.458 2.442 2.397 2.416 2.431
wt % 11 12 13 14 15 16 SiO.sub.2 62.8 61.9 62.7 62.4 62.5 61.5
Al.sub.2O.sub.3 16.5 16.2 16.4 16.3 17.2 17.1 B.sub.2O.sub.3 11.2
11.1 12.3 12.2 11.7 12.8 MgO 0.0 0.0 0.0 0.6 0.0 0.0 CaO 9.5 8.5
8.6 6.9 8.6 8.6 SrO 0.0 0.0 0.0 1.6 0.0 0.0 BaO 0.0 2.3 0.0 0.0 0.0
0.0 Liquidus (.degree. C.) 1160 1145 1110 1135 1170 1185
Temperature Soft Pt (.degree. C.) 959 960 961 959 962 952 Anneal Pt
(.degree. C.) 730 724 718 711 722 714 Strain Pt (.degree. C.) 679
671 668 651 670 663 CTE (.times.10.sup.-7/.degree. C.) 34.7 34.4
34.3 32.8 33.6 34.5 Density (g/cm.sup.3) 2.389 2.419 2.370 2.381
2.377 2.371
A glass having a composition and properties as shown in Example 5
is currently regarded as representing the best mode of the
invention, that is, as providing the best combination of properties
for the purposes of the invention at this time. Comparative Example
A set forth in Table I represents the compositions and properties
of Corning Incorporated's code 1737 glass, currently one of the
most popular substrates for LCD applications. Compared to code 1737
glass, Example 5 has a higher strain point (683.degree. C. vs.
666.degree. C. for 1737), lower density (2.45 vs. 2.54 g/cm.sup.3),
lower softening point (942 vs. 975.degree. C.), higher Young's
modulus (12 vs. 10.2 Mpsi), and higher Knoop hardness (505 vs. 460
with 100 g load), yet has a 200 poise temperature of about
1516.degree. C. (vs. 1625 for code 1737 glass), thereby potentially
enabling formation of this glass at significantly lower
temperatures.
Although the invention has been described in detail for the purpose
of illustration, it is understood that such detail is solely for
that purpose and variations can be made therein by those skilled in
the art without departing from the spirit and scope of the
invention which is defined by the following claims. For example,
while the glass is described herein primarily as a flat panel
display substrate, it may also be used in photovoltaic device
applications.
* * * * *