Low-temperature sealing glass frit composition

MAIMOTOMONTANT UIT DIE HI HINDI HII
US009950948B2
(12) United States Patent (10) Patent No.: US 9 ,950,948 B2

Naito et al. (45) Date of Patent: * Apr. 24 , 2018
(54 ) LEAD -FREE LOW -MELTING GLASS (2013 .01); CO3C 8 /08 (2013.01); C03C 8 / 14
COMPOSITION , LOW - TEMPERATURE ( 2013 .01) ; C03C 8 / 16 ( 2013 .01) ; C03C 8 / 18
SEALING GLASS FRIT , ( 2013.01) ; C09D 5 /24 ( 2013 .01) ; HOIB 1/ 14
LOW - TEMPERATURE SEALING GLASS (2013 .01 ); HOIL 31/02168 ( 2013 .01) ; HOIL
PASTE , CONDUCTIVE MATERIAL , AND 31/022425 ( 2013 .01 ) ; HOIL 31/ 068 ( 2013 .01 ) ;
CONDUCTIVE GLASS PASTE CONTAINING HOIL 41/053 (2013 .01 ); HOIL 51/5246
GLASS COMPOSITION , AND (2013 .01 ); HOIL 2224 / 16225 ( 2013 .01) ; HOIL
GLASS -SEALED COMPONENT AND 2924 / 16152 (2013 .01 ); HOBH 3 /02 ( 2013 .01 ) ;
ELECTRIC /ELECTRONIC COMPONENT HO3H 9 / 1014 ( 2013 .01); HO3H 9 / 19
PREPARED USING THE SAME (2013 . 01 ); H05K 1/ 092 ( 2013 .01); H05K
2203/ 1126 ( 2013 .01)
(71) Applicant: HITACHI CHEMICAL COMPANY, (58 ) Field of Classification Search
LTD ., Tokyo (JP ) CPC .... CO3C 8 /00 ; CO3C 8 /02 ; CO3C 8 /08 ; CO3C
8 / 14 ; CO3C 8 / 16 ; CO3C 8 / 18 ; CO3C 8 /24 ;
(72 ) Inventors: Takashi Naito, Tokyo ( JP ); Shinichi CO3C 3 /122; CO3C 3 /21 ; HO1L 31 /068 ;
Tachizono, Tokyo (JP ); Kei HO1L 31/02168 ; HO1L 31/ 022425 ; HOLL
Yoshimura , Tokyo ( JP ); Yuji Hashiba , 51/5246 ; HO1L 41/053 ; HO1L
Tokyo (JP ); Takuya Aoyagi, Tokyo 2224 / 16225 ; HO1L 2924 / 16152; CO9D
( JP ); Taigo Onodera , Tokyo ( JP ); 5 /24 ; HO1B 1/ 14 ; CO3B 23 / 203; HO3H
Tatsuya Miyake , Tokyo (JP ) 9/ 19 ; HO3H 3 /002; HO3H 9 / 1014 ; HO3H
(73 ) Assignee : HITACHI CHEMICAL COMPANY, 9/10 ; HO5K 1/09; HO5K 1/115; HO5K
LTD ., Tokyo (JP ) 2203 /1126
See application file for complete search history.
Subject to any disclaimer, the term of this
( * ) Notice : patent is extended or adjusted under 35 (56 ) References Cited
U . S .C . 154 (b ) by 0 days .
This patent is subject to a terminal dis U .S. PATENT DOCUMENTS
claimer . 3,798 , 114 A 3 /1974 Chvatal
3 ,853 ,568 A 12/ 1974 Chvatal
(21) Appl. No.: 15 /598 ,674 (Continued )
(22 ) Filed : May 18 , 2017 FOREIGN PATENT DOCUMENTS
JP 2013 - 032255 A 2 /2013
(65) Prior Publication Data
US 2017 /0253522 A1 Sep. 7 , 2017 Primary Examiner — Elizabeth A . Bolden
(74 ) Attorney , Agent, or Firm — Volpe and Koenig, P.C .
Related U .S . Application Data
(63 ) Continuation of application No. 14 /834 ,386 , filed on (57 ) ABSTRACT
Aug . 24, 2015, now Pat. No. 9,670 ,090 .
(30) Foreign Application Priority Data An Ag20 - V205 — TeO2 lead-free low -melting glass com
position that is prevented or restrained from crystallization
Aug . 29, 2014 ( JP ) ................................. 2014 - 175642 by heating so as to soften and flow more satisfactorily at a
low temperature contains a principal component which
(51) Int. CI. includes a vanadium oxide, a tellurium oxide and a silver
CO3C 8 /24 ( 2006 .01)
oxide ; a secondary component which includes at least one
HOIL 51/52 ( 2006 .01)
HOIL 41/053 ( 2006 .01 ) selected from the group consisting of BaO , WO3 and P2O5 ;
HOIL 31/ 068 ( 2012 .01) and an additional component which includes at least one
HOIL 31/0224 ( 2006 .01 ) selected from the group consisting of oxides of elements in
HOIL 31/0216 ( 2014 .01) Group 13 of periodic table . A total component of the
HOIB 1/ 14 (2006 .01)
CO9D 5 / 24 (2006 .01) principal component is 85 mole percent or more in termsof
CO3C 8 / 18 ( 2006 .01) V205, T 02 and Ag, 0 . Contents of Teo , and Ag,0 each is
CO3C 8 / 16 ( 2006 .01) 1 to 2 times as much as a content of V205. A content of the
(Continued ) secondary component is 0 to 13 mole percent. A content of
(52) U .S . CI. the additional component is 0 .1 to 3.0 mole percent.
CPC .............. C03C 8 / 24 ( 2013.01 ); C03B 23 / 203
( 2013.01); CO3C 3 / 122 ( 2013 .01); CO3C 3/ 14
( 2013.01); C03C 3/21 (2013.01); C03C 8/02 20 Claims, 23 Drawing Sheets
US 9, 950,948 B2
Page 2
(51) Int. CI.

?03C 8 / 4 ( 2006. 01 )
?03C 808 (2006 .01 )
?03C 802 ( 2006.01)
?03C 321 ( 2006 . 01 )
?03C 3 / 4 (2006. 01 )
?03C 3 / 2 ( 2006. 01 )
?03B 23203 ( 2006. 01 )
H05K / 09 ( 2006. 01 )
???? 9 /10 ( 2006. 01)
Ho3H 3 / 02 ( 2006 . 01)
???? 9 /19 ( 2006. 01 )
( 56) References Cited
U .S. PATENT DOCUMENTS
4 ,945, 071 A 7 /1990 Friesen
9 , 670 ,090 ?2 * 6/ 2017 Naito ..... ?03C 8 / 24
2014 / 0145122 ?1 5 /2014 Sawai et al .
* cited by examiner
U . S . Patent Apr . 24 , 2018 Sheet 1 of 23 US 9,950,948 B2
FIG . 1
GLASS- SPECIFIC DTA CURVE
Wht My www it www # www th th * * * *
?EXOTHERM
EXOTHERMIC
CRYSTALLIZATION PEAK
LHOFAIMBEORAUTNEDCBRYSTALYIZ ON
w
- - - -
EfNDrOToHEmRM w
Tg Mg Ts Tary
TEMPERATURE (°C ) wowote
( T : GLASS TRANSITION POINT, Mq: YIELD POINT, Ts: SOFTENING POINT,
Tarv : CRYSTALLIZATION ONSET TEMPERATURE )
FIG . 2
(a ) 2 (2 ' )
1 (1 ' )
- 3 (3 )
A 2 (2 )
1 (1 )
ON
4 (4 ') .
- 2 (2 )
- 1 ( 11 ' )
- 1 ( 1 ') 5 (5' )
4 (4 ' )
U . S . Patent Apr. 24 ,2018 Sheet 3 of 23 US 9, 950,948 B2
FIG . 3
10 - 1
10 -2 - - - - - - - - - - - - - - - - - - - - - ??? ? ? ? ? - - - -
2
-
-
-
-
-
-
+- - - -
C(R12/mm2)EOSNITACNTE Cu /Cu
10 -4 1 - 4 - - - - - - - -
-
-
- - - - - - - - - -
10-5 --- - AI/ALLA

10 -6
AQ
murning
Ag / Ag
I*
10 - 7
0 20 40 60 80 100
100
SILVER CONTENT (VOLUME PERCENT )
LIIIIIII
100 80 60 40 20
VTA --130 CONTENT (VOLUME PERCENT)
FIG . 4
10 - 1
-
- - -
- -
-
- -
- -
10 -2 EM TERE
-
-
-
- -
- -
- -
Cu /cu -
-
-
-
how -
-
- -
(12/mm2)RCEOSNITANCTE ***XXE*IXWIIIII - -
- -
- -
- -
-
-
-
-
-
-
- -
-
-
- -
-
- -
-
- -
-
- - -
- -
-
- -
- - - -
- - - - -
- - - -
- - *
- Al/ AI -
*
10-5 therecommended - - - - -
I
- - - - - - - - - - - - - - -
-
- - - - - - - - - - - - - - -
* * * ** * ** *
10 -6
. .
- - - - - - - - - -
-
-
Ag / Ag
-- - - - - - - - - - - - - - - - - - -- - - - - - - - - - - - - - - -
-
-
- - - - - - - - - - - - - - -
- -
- -
- -
- -
- -
- -
- - -
- -
10 -7
õ - -
-
1
0 20 40 60 100
COPPER CONTENT (VOLUME PERCENT)
. ed p
100 80 60 40 20
VTA -130 CONTENT (VOLUME PERCENT)
FIG . 5
10 - 1 -
- -
- - -
A -
- -
-
-
-
-
-
10 -2 -
- - - -
-
-
- - - - - - -
- -
- - -
- -
- -
- -
- -
-
- -
- -
- -
- - - - - - - - - - - - -
-
- - - - * - Y
-
CUCU
(2/mm²)RCEOSNITANCTE -
-
-
-
-
-
-
-
-
-
10 - 5 -
- - - - - - -
Al/ AI SIIRIK -
11 . 11. DIT
* ** * * *1 . . -
Ag/ Ag
10 -6 - - - - - - - - - - - - - - -- - - - - - - -- - - - - - - - -- - - - - - - - - - - - - - - - - - - - - - - - - - - -
-
-
- - - - # #
- -
+ -
+ -
-
-
10 - 7 L -
0 20 40 60 80 100
ALUMINUM CONTENT (VOLUME PERCENT)
LLLLLLLL
100
100 80 60
VTA - 130 CONTENT (VOLUME PERCENT)
40 20 70
U . S . Patent A pr. 24 , 2018 Sheet 6 of 23 US 9,950,948 B2
FIG. 6
10 -1 -
10- 2
?
- - - - ? - • • -
? ? ? ? ? ? ? ? ? ? ? ? ??
-
1 - - - • ? ? - - - -
)
mm2
RCEOSINSTANCTE
/
s2
( ?? ? ?
10- 4
\\ cuCu//cucu AAl// ?A/
------ -- ? - ? ? ? - - - - - ?
-
?
• •? • - - - d = ? ? ? ? ?- -
- - - - - -
• -
• -
- -
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?
-
- - - - - - - - - - - - - - ? - ? - ? ? ? ? ? ? ?
??????????????????????
Ag/ Ag
10- 6 | - - - -- -. -
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?
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•
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Hai
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020406080100
TIN CONTENT ( VOLUME PERCENT )
L , ? ? ? | | | | | … ... . .. . ?????
100806040200
VTA- 130 couTENT (VOLUME PERCENT)
FIG . 7
7 8 9 10 11 12 13
Meer
MAS
Mihaita?1tz MARATHON arbe

an
* TERIAL ****
FIG . 8
10 - 1
g
O : Al2O3 SUBSTRATE
A : BOROSILICATE GLASS SUBSTRATE
10-2 - - - - - - - - -
-
- - - - -- -- -
D : SILICON SUBSTRATE - - --- -
V : FERRITE SUBSTRATE
- -
-
-
-
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O : POLYIMIDE SUBSTRATE
-
? * * **
-
- - - - - u . .
(cm)RINETS COTNAECT
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10 - 5 -
-
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-
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-
-
- -
-
-
- -
- -
10 - 7 -
-
50 60
SILVER CONTENT ( VOLUME PERCENT)
50 40
VTA - 141 CONTENT (VOLUME PERCENT )
30 20 10 ??
U . S . Patent Apr. 24 , 2018 Sheet 9 of 23 US 9,950,948 B2
FIG . 9A
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22
atent Apr. 24 , 2018 Sheet 10 of 23 US 9 ,950 , 948 B2
FIG . 10A
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FIG . 10B
14
atent Apr. 24 , 2018 Sheet 11 of 23 US 9 ,950 , 948 B2
FIG . 11A
FIG . 11B
22
IZITZZZZZZZZZZZZZZZZZZ ZZZZZZZZZZZZZZILLIAZILLIIIIIII
U . S . Patent Apr . 24 , 2018 Sheet 12 of 23 US 9 , 950,948 B2
FIG . 12
EVACUATION
19 18 , 20 19 14
KITZELULIT TIZITZZZTITITIZITETIT 7777TTTTTTTIIIIIIIIIIIIITETIT
17 15
SEALING
UNDER VACUUM
19 1914
malo
7777 77777777777777
17 5 22
777777777777RNIH
20
U . S . Patent Apr . 24 , 2018 Sheet 13 of 23 US 9 ,950 , 948 B2
FIG . 13
SEALING TEMPERATURE
( VTA - 146 : 280°C )
HOLDING
FOR 30 MIN .
ADJACENT TO SOFTENING POINT
( VTA - 146 : 250°C )
TEMPRAU HOLDING
FOR 30 MIN .
IN AIR WITH EVACUATION
TIME mot
U . S . Patent Apr . 24, 2018 Sheet 14 of 23 US 9 , 950,948 B2
FIG . 14A
/ 23 25
FIG . 14B
wwwwww
: m
#
D
U . S . Patent Apr. 24 , 2018 Sheet 15 of 23 US 9 ,950 ,948 B2
FIG . 15A
- - - -
FIG . 15B
U . S . Patent Apr . 24 , 2018 Sheet 16 of 23 US 9 ,950 , 948 B2
FIG . 16A
FIG . 16B
U . S . Patent Apr. 24 , 2018 Sheet 17 of 23 US 9 , 950 , 948 B2
FIG . 17
26
FIG . 18A
27 28
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U . S . Patent Apr. 24 , 2018 Sheet 21 of 23 US 9 ,950 , 948 B2
AAceptd ceptd Aceptd Aceptd Aceptd Aceptd Rejcted

test
sCthaebmilcaty WAactiedrresitancetest Ac ept d Aceptd Aceptd Ac ept d Aceptd
Rejcted
ofReductioncrystaliz ontedncy + + 3 -
Amount ofheat )
UV
( 12 0 5
.
0 2
.
2
5
GYby|lCSrioysbftaelrsinzatdeogn
Tcry 260 260
eNoxothermpicCreystalikzton 288 280 261
(°C)tCheamrpctaeriustec tcopreaymsnilzeotaurn TS 215 220 219 218

216
182 217
180
20
.
FIG Mg 181 184 183 181
313332386Ac epted
PTgoint 167 167 168 166 166 162
cg-mlfofs,atVrhioeypnrobcmdfalstieznuwdoracetsigly
Vitrfcaion Aceptd Aceptd Aceptd Aceptd Aceptd ed
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3
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.
0
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3
.
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(
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None B203 Al2O3 Ga20: In203 TAVA-1cl0e2p5Ote3d
PB-100None
2e81rAVc82e0n5t
31
TeOz
p38
mole
(
1W03
3BaO
-
)
VTA-101 VTA-102 VTA
103 VTA-104
- 1e3r8c2e0n1t
84PbO
p3
mass
(
Al20a
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-
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100
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Example
CompartiveExample CompartiveExample
U . S . Patent Apr. 24 , 2018 Sheet 22 of 23 US 9 ,950 , 948 B2
FIG . 21
[Table 2 ]
Formulation (mole percent) of lead- free low -melting glass composition
w. . . . .. .. .... . . ... . .. . . . . .. ..
Glass Principal component Secondary component Additional component
www
number vor | Teo Aggo Baowo. | P205 | Alzoz Gazoz In2O3

VTA - 106 1 20.0 40 .0 40 .0 0 .0 Comparative Example
| VTA - 107 20 .0 40 .0 39 .9 . LEL011 0 .1
Tilon I
VTA - 108 | 20.0 40.0 39.9
VTA - 109 200 39 .7 40 .0 0 .3
VTA - 110 20 .0
| VTA - 111 | 20 .0
| VTA - 11220.0
40 .0
40 .0
40 .0
39 ,5
39 .5
39.0
-
-- online
0 .5
10
1 13
www
.
VTA 13 200 40 . 0 39 ,0 0,5 0,5
VIA - 114 20 . 0 400 36 . 0 20
VTA - 15 400 39 . 0
| VTA -- 116 | 20 .0
Www.wanawe
VTA117
VTA - 118
VTA - 119
ANALLAH
20 .0 | 39.0
20.0
20 .0
39.0 | 38.0 L - Lommel
39.0
39 .0
36 .0
36 .0
36 .0
5.0
5 .0
!I I 3.0
10
5 .0
-
Comparative Example
Comparative Example
Comparative Example
| VTA - 120 | 20 .0 | 37.0
| VTA - 123
TVTA 124
IVTA - 125
???????????????? ???? ?
VTA - 121 | 20 .0
. . . .. .. . . . . . . . . . . .. . . . . . . .
VTA - 122 30 .0
| VTA - 126 20 .0 38.0

| VTA - 27 | 20 .0 | 38 .5
| VTA - 128 20 .0 38.5
20 . 0
20 .0
20 . 0
1 .. .
40 .0
30 .0
389 .
39.9
380 .
.
33.0
30 . 0
30 .0
36 .0
30 .0
360
36 .0
36 .0
36 .0
5.0
5 .0
5 .0
5 .0
5 .0
50
5 .0
50
-
5 .0
5 .0
-
5 .0
0 .7
- 1
5.0 -
05
0.1
0 .3
0 .5
!PITU UIT Comparative Example
Comparative Example
Comparative Example
TU 38W2 18S
VTA - 129 200 . 39.5 30 .0 5 .0 5.0 - 0.5
1 VTA - 130 37 .5 35 .0 5 .0 20 0 .5
VTA - 131 20 .0 36 .5 33 .0 5 .0 5 .0 - 0 .5 -
| VTA - 132 20 .0 37.5 35 .0 5. 0 * * 12
TorTYTI
0. 0 .5
| VTA - 133 270 35.0 270 40 6 .5 0 ,5
| VTA - 134 1 19.0 | 37.5 33.0 4 .0 14.0 12.0 | 051
. WILL
| VTA – 135 20 .0 40 .0 26 .5 13.0 1 - - - 10. 5

VTA - 136 20 .0 35 .0 40 .0 2 .0 05
| VTA - 137 20 .0 36 ,5 1 30 .0 5 .0 5 .0 l 3. 0 T 10.5
VIA - 138 20. 0 36.5 3001
. 1 30 7. 0 l 3.0
| VTA - 139 | 200 | 38 .5 35 .5 5 .0 Lom - 110I
.
| VTA W 140 200 38 . 5 35 . 5 10
| VTA - 141200 36 . 0 32 . 0 6 . 0 15. 0
| VTA - 142200 . 38 .0 28 .0 5 .0 8.0 - 1.0 -
| VTA - 143 255 . 35 .0 25 .5 - 8.0 5.0 1.0
VIA - 144 20 . 0 40. 0 36 , 0 to 1,0 10
1 *1 1 0
??
| VTA - 145 20. 0 38. 5 35.5 5 .0 L - 05 0 .5
| VTA - 146 2 0 . 0 40 .0 29 .0 5 .0 5.0 - 0 .5 0 .5
VTA - 147 200 . 36 .0 33.0 5 .0 5.0 0.5 0 .5
VTA - 14820 ,0 36 ,0 33,0 5. 0 5.0 0.5 - 0 .5
VTA - 149 200 36 .0 23 .0 5 .0 5.0 - 0 .5 0 .5
VTA - 150 20 .0 38.0 35 .0 5 .0 2 .0
VTA - 151 200 . 37 .0 31. 0 5 .0 5.0 20
VTA - 152 17. 0 34. 0 340 .0 5 .0
VTA 53 200 . 37 , 0 35 . 0 5 .0 ?
METAI
VTA - 154 | 200 . 370300 5. 0 5 .0 - 3.0
VTA - 755 | 200 37.0 1 300 5 .0 5.0 on 3.0
VTA -- 156 | 200 . 37.0 30 .0 5 .0 15.0 - 1.0 1. 0 1.0
VTA - 157 20 .0 35 .0 | 35 .0 50 ? 5 .0 Comparative Example
VTA - 158
???????????????????????????????????
20 . 0 37 . 0 28 .0 50 50 8
1
5 .0 - Comparative Example
VTA - 159 20.0 37.0 www 28 .0 5 .0 TE 5.0
werom 5.0
WWW
- Comparative Example
VTA - 160 1 20.0 37.0 28 .0 5 .0 5 .0 - 2.0 2.0 1.0 T Comparative Example
FIG . 22
[ Table 3 ]
Vitrification, characteristic temperatures , crystallization tendency, and chemical stability of lead - free low -melting glass compositions
Characteristic temperatures (°C ) Amount Chemical stability
Glass of heat Reduction of
number Vitrification Softening Crystallization liberated by crystallization Water Acid
transition pan point onset temperature crystallization tendency resistance resistance
Point Tg Mg TS Tory (MV ) test test
VTA - 106 Accepted 153 168 196 260 150 Accepted Accepted Comparative Example
VTA - 107 Accepted 155 169 i 197 295 Accepted Accepted
VT4 - 108 Accepted 152 ?? 194 278 35 Accepted Accepted
NMVI
VTA - 109 Accepted 153 166 195 293 Accepted Accepted
VTA “ 110 Accepted 156 172 1 {? 299 Accepted Accepted
VT4 - 112 Accepted
VTA - 113 Accepted
VT4 – 114
VTA - 115 Accepted
Accepted
158
157
162
159
175
174
180
207
214
203
305
301
303
AA Accepted Accepted
Accepted Accepted
Accepted Accepted
Accepted Accepted
209
VTA - 116 Accepted 165 ] 188 224 310 Accepted Accepted
VTA - 119 Accepted
Alu Accepted Accepted Comparative Example

175 184 225 283
VTA - 120 Accepted 186 203 1 236 285 26 Accepted Accepted Comparative Example
VTA 121 Accepted 191 208 2 42 305 14 Accepted Accepted Comparative Example
VTA - 122 Accepted 224 247 284 337 Accepted Accepted Comparative Example
VTA - 1 24 Accepted 190 205 1 242 325 Accepted Accepted
VTA - 125 Accepted
VTA - 126 Accepted
VTA 127 Accepted
VTA - 128 Accepted
VTA - 129 Accepted
173
170
70 1186
172182
179
193
189
255
227
224
229
No axothermic poak
No exothermic peak
No exothermic peak
326
No exothermia peak
OQN Accepted Accepted
Accepted
Accepted
Accepted
Accepted
Accepted
Accepted
Accepted
Accepted
Accepted
Accepted
VTA - 130 Accepted 177 195 235 No exothennic peak
VTA - 131 Accepted 189 205 1 244 No exothermic peak Accepted Accepted
VTA - 132 Accepted 179 199 240 No exothemis peak Accepted Accepted
VTA - -193 Accepted 223 234 277 No exothermic peak Accepted Accepted
VTA - 134 Accepted 200 212 263 No exotherrnic peak Accepted Accepted
VTA - 135 Accepted 212 242 1 279 No exothermic peak Accepted Accepted
VTA - 137 | Accepted 221 245 280 No exothermic peak Accepted Accepted
ANO ucn
VTA - 139 | Accepted 171 191 230 No exothermic peak Accepted Accepted
VTA - 140 Accepted 74 237 No exothermic peak Accepted Accepted
VTA -
???? ???
141 Accepted 1 193 210 250 No exothermic peak Accepted Accepted
VTA -- 143 Accepted 228 241 1 280 No exothemio peak Accepted Accepted
VTA - 145 Accepted 70 195 232 No exothemic peak Accepted Accepted
VTA - 146 Accepted 197 213 253 No exothermic peak Accepted Accepted
VTA
php
- 147 Accepted 190 205 1 248 No exothennic peak Accepted Accepted
VTA - 148 Accepted 190 203 1 247 No exothenic peak Accepted Accepted
VTA -- - 149 Accepted 193 202 252 348 2 Accepted Accepted
VTA - 151 | Accepted 197 207 256 364 0 .7 Accepted Accepted
VTA - 152 Accepted
VTA - 153 Accepted
VTA - 154 Accepted
222
173
201
236
202
211
280
238
254
385
265
315
0 .5 *N NW Accepted
Accepted
Accepted
Accepted
Accepted
Accepted
VT4 - 155 Accepted 197 208 251 317 Accepted Accepted
VTA - 156 Accepted 200 209253 313 Accepted Accepted
VTA - 158 Accepted 207 221 to
265
her
295
itetit fiti
Accepted Accepted Comparative Example
US 9 , 950 , 948 B2
LEAD - FREE LOW -MELTING GLASS formation , the low -melting glass composition contained in
COMPOSITION , LOW - TEMPERATURE the conductive material or in the corresponding conductive
SEALING GLASS FRIT , glass paste softens , flows, and thereby allows the metal
LOW - TEMPERATURE SEALING GLASS particles to sinter or to be brought into intimate contact with
PASTE , CONDUCTIVE MATERIAL , AND 5 a substrate .
CONDUCTIVE GLASS PASTE CONTAINING The low -melting glass compositions to be contained in the
GLASS COMPOSITION , AND low - temperature sealing glass frit or the corresponding
GLASS - SEALED COMPONENT AND low -temperature sealing glass paste , as well as the conduc
ELECTRIC /ELECTRONIC COMPONENT tive material and the corresponding conductive glass paste
PREPARED USING THE SAME 10 have often employed Pb0 B ,0z low -melting glass com
positions containing a very large amount of lead oxide . The
CLAIM OF PRIORITY PbO — B20 , low -melting glass compositions have a low
softening point of 350° C . to 400° C ., can soften and flow
The present application is a continuation of U . S . appli- satisfactorily at 400° C . to 450° C ., and still have relatively
cation Ser. No. 14 / 834 , 386 filed on Aug . 24 , 2015 issued as 15 high chemical stability . The " softening point” refers to a
U .S . Pat. No. 9 ,670 ,090 B2 on Jun . 6 , 2017 and claims second endothermic peak temperature as determined by a
priority from Japanese Patent application serial No . 2014 - differential thermal analysis “ DTA ” .
175642, filed on Aug. 29 , 2014 , the contents of which are However,more safe materials have been demanded in the
both hereby incorporated by reference into this application . electrical and electronic equipment industry in accordance
20 with the recent global trend toward green procurement / green
BACKGROUND OF THE INVENTION design . Typically , the Directive on the restriction of the use
of certain hazardous substances in electrical and electronic
Field of the Invention equipment (RoHS directive ) took effective on 1 Jul. 2006 by
The present invention relates to lead - free low -melting the European Union . The RoHS directive restricts the use of
glass compositions . Specifically , the present invention 25 six hazardous materials, i.e ., lead , mercury , cadmium ,
relates to a lead - free low -melting glass composition that is hexavalent chromium , polybrominated biphenyls , and poly
prevented or restrained from crystallization and can thereby brominated diphenyl ether.
soften and flow satisfactorily at a lower temperature . The The PbO - B ,03 low -melting glass compositions contain
present invention also relates to a low -temperature sealing a large amount of lead that is restricted by the RoHS
glass frit, a low - temperature sealing glass paste , a conduc - 30 directive and are hardly applied to low - temperature sealing
tive material, and a conductive glass paste , each of which glass frits, corresponding low - temperature sealing glass
contains the lead -free low -melting glass composition ; and to pastes, conductive materials, and corresponding conductive
a glass -sealed component and an electrical/electronic com pastes. Thereby, the development of novel lead - free low
ponent prepared by using any of them . melting glass compositions has proceeded . In addition ,
Description of Related Art 35 strong demands have been made to develop lead - free low
In some articles, a low -temperature sealing glass frit melting glass compositions that soften and flow at a lower
including a low -melting glass composition and low -thermal temperature as compared with the PbOB ,03 low -melting
expansion ceramic particles is used typically for sealing glass compositions and still have good chemical stability .
and /or bonding . The articles are exemplified by vacuum These demands have been made so as to allow various
insulating double glass panels applied typically to window 40 glass -sealed components and electrical/ electronic compo
panes ; display panels such as plasma display panels, organic nents to less undergo thermal damage (to have higher
electroluminescent display panels, and fluorescent display functions) and to have better productivity (with reduced takt
tubes ; and electrical/ electronic components such as quartz time). Specifically , demands have been made to provide
resonators, IC ceramic packages, and semiconductor sen - lead - free low -melting glass compositions that soften and
sors. The low - temperature sealing glass frit is often applied 45 flow at a temperature of 350° C . or lower , preferably 300°
in the form of a low -temperature sealing glass paste . The C . or lower, and are applicable typically to sealing and /or
low -temperature sealing glass paste is applied typically by a bonding or to the formation of electrodes/ interconnections
screen process printing or dispensing , dried , and fired for use and conductive junctions.
in sealing and/ or bonding . Upon the sealing and/or bonding , Japanese Patent Application Laid -Open No . 2013 -32255
the low -melting glass composition contained in the low - 50 (Patent Literature 1) discloses a lead -free low -melting glass
temperature sealing glass frit or in the corresponding low - composition . The glass composition contains , in terms of
temperature sealing glass paste softens, flows, and thereby oxides, 10 to 60 mass percent ofAg20 , 5 to 65 mass percent
comes in intimate contact with a member to be sealed and/or of V , 05, and 15 to 50 mass percent of TeO2. The glass
to be bonded . composition contains Ag20 , V205, and Teo , in a total
Likewise , a conductive material including a low -melting 55 content of 75 mass percent to less than 100 mass percent,
glass composition and metal particles is used to form an with the remainder being at least one of P205, Bao , K20 ,
electrode and /or an interconnection in many electrical/elec - WO3, Fe2O3,MnO2, Sb2O3, and ZnO in a content of greater
tronic components such as solar cells, image display than 0 mass percent to 25 mass percent. The patent literature
devices , multilayer capacitors, quartz resonators, LEDs mentions that the Ag20 — V205 — Tell , lead - free low -melt
(light- emitting diodes ), and multilayered circuit boards . The 60 ing glass composition has a low softening point of 320° C .
conductive material is also used as a conductive bonding or lower, softens and flows at a lower temperature as
material for conduction . The conductive material is often compared with the conventional PbO _ B20 , low -melting
applied in the form of a conductive glass paste , as with the glass compositions, and still has good chemical stability ,
low - temperature sealing glass frit. The conductive glass where the softening point is determined from the second
paste is applied typically by a screen process printing or 65 endothermic peak temperature by the differential thermal
dispensing, dried , and fired to form an electrode, an inter - analysis (DTA ). In addition , Patent Literature 1 proposes a
connection, and/ or a conductive junction . Also upon the low - temperature sealing glass frit, a low -temperature sealing
US 9 ,950 ,948 B2
glass paste , a conductive material, and a conductive glass ent invention and Ag particles contained in a conductive
paste each containing the Ag20 _ V205 - Tell , lead -free material, where the contact resistance is determined in an
low -melting glass composition ; and an electrical/electronic A1/ A1 bonded article , a Ag/Ag bonded article , and a Cu/Cu
component prepared using any of them . bonded article each of which is assembled and bonded using
5 the conductive material;
SUMMARY OF THE INVENTION FIG . 4 is a graph illustrating how a contact resistance
varies depending on the contents of the lead -free low
The present invention provides , in an embodiment, a melting glass composition according to the embodiment of
lead -free low -melting glass composition containing a prin the present invention and Cu particles contained in a con
cipal component which includes a vanadium oxide , a tellu - 10 du
ductive material , where the contact resistance is determined
rium oxide and a silver oxide ; a secondary component which in an Al/Al bonded article , a Ag/ Ag bonded article , and a
includes at least one selected from the group consisting of Cu /Cu bonded article each of which is assembled and
BaO , WO , and P , 05 ; and an additional component which bonded using the conductive material ;
includes at least one selected from the group consisting of FIG . 5 is a graph illustrating how a contact resistance
oxides of elements in Group 13 of periodic table, in which 15 varies depending on the contents of the lead -free low
a total component of the principal component is 85 mole
melting
percent ormore in terms of V205, TeO2and Ag2O , contents the present glass composition according to the embodiment of
of Teo , and Ag , each is 1 to 2 times as much as a content invention and Al particles contained in a con
of V ,Os, and in which a content of the secondary component ductive material, where the contact resistance is determined
is 0 to 13 mole percent, and a content of the additional 20 in an Al/Al bonded article, a Ag Ag bonded article , and a
component is 0 . 1 to 3 .0 mole percent. Cu/Cu bonded article each of which is assembled and
The present invention allows a lead-free low -melting bonded using the conductive material ;
glass composition containing a vanadium oxide , a tellurium FIG . 6 is a graph illustrating how a contact resistance
oxide, and a silver oxide to have a smaller crystallization varies depending on the contents of the lead - free low
tendency and to be prevented or restrained from crystalli - 25 melting glass composition according to the embodiment of
zation upon heating - firing. This provides a lead -free low - the present invention and Sn particles contained in a con
melting glass composition that softens and flows more ductive material, where the contact resistance is determined
satisfactorily at a temperature of 350° C . or lower, and in an A1/ A1 bonded article , a Ag/ Ag bonded article , and a
preferably 300° C . or lower, still has excellent chemical Cu/Cu bonded article each of which is assembled and
stability , and meets the RoHS directive. 30 honded
bonded using
using the
the conductive material;
The lead - free low -melting glass composition according to FIG . 7 is a schematic perspective view of an intercon
the embodiment of the present invention , when combined nection pattern for interconnect resistance and peel test
with ceramic particles and/ or metal particles , can give a measurements of formed electrodes/ interconnections ;
low -temperature sealing glass frit , a low -temperature sealing
glass paste, a conductive material, and a conductive glass 35 FIG .varies
8 is a graph illustrating how an interconnect resis
paste each of which can enjoy advantageous effects of the tance depending on the contents of the lead- free
lead - free low -melting glass composition according to the low -melting glass composition according to the embodiment
embodiment of the present invention . of the present invention and Ag particles contained in a
The low - temperature sealing glass frit, low -temperature conductive material, where the interconnect resistance is
sealing glass paste , conductive material, and conductive 40 determined in an electrode / interconnection formed using the
paste each containing the lead - free low -melting glass com - conductive material;
position according to the embodiment of the present invenh . FIG . 9A is a schematic plan view of a vacuum - insulating
tion , when applied , can give a glass -sealed component and double glass panel prepared according to an embodiment of
an electrical/ electronic component that includes an elec - the present invention ;
trode /interconnection or a conductive junction . The glass - 45 FIG . 9B is a cross - sectional view taken along the line A - A
sealed component, the electrode/interconnection , and the of FIG . 9A ;
conductive junction are sealed , bonded , or formed at a firing FIG . 10A is a schematic plan view illustrating a step of a
temperature of 350° C . or lower, and preferably 300° C . or method for producing the vacuum - insulating double glass
lower. These components are obtained after consideration of panel of FIG . 9A ;
influence on the environmental burden . Specifically , use of 50 FIG . 10B is a cross-sectional view taken along the line
the lead - free low -melting glass composition according to the A - A of FIG . 10A ;
embodiment of the present invention allows the glass - sealed FIG . 11A is a schematic plan view illustrating another step
component and the electrical/ electronic component to less of the method for producing the vacuum -insulating double
undergo thermal damage (to have higher functions ), to have glass panel of FIG . 9A ;
better productivity (to require reduced takt time) and better 55 FIG . 11B is a cross -sectional view taken along the line
reliability (chemical stability at certain level), and to put less
burden on the environment. FIG . 12 is a schematic cross -sectional view illustrating
yet another step of the method for producing the vacuum
BRIEF DESCRIPTION OF THE DRAWINGS insulating double glass panel of FIG . 9A ;
60 FIG . 13 is a graph illustrating a sealing temperature
FIG . 1 is a glass -specific differential thermal analysis profile in the step of FIG . 12 of the method for producing the
(DTA ) curve on a typical glass formulation ; vacuum - insulating double glass panel;
FIG . 2 is a schematic diagram illustrating how to prepare FIG . 14A is a schematic plan view of an organic light
a bonded article for shear stress measurement; emitting diode (OLED ) display prepared according to an
FIG . 3 is a graph illustrating how a contact resistance 65 embodiment of the present invention ;
varies depending on the contents of a lead -free low -melting FIG . 14B is a cross -sectional view taken along the line
glass composition according to an embodiment of the pres- A - A of FIG . 14A ;
US 9, 950, 948 B2
FIG . 15A is a schematic plan view illustrating a step of a crystallization tendency, the glass composition disadvanta
method for producing the OLED display of FIGS . 14A and geously softens and flows unsatisfactorily at a low tempera
14B ; ture of 350° C . or lower, and preferably 300° C . or lower.
FIG . 15B is a cross -sectional view taken along the line Assume that the glass composition is mixed with low
A - A of FIG . 15A ; 5 thermal- expansion ceramic particles or metal particles or is
FIG . 16A is a schematic plan view illustrating another formed into a paste upon usage. In this case , the glass
step of the method for producing the OLED display of FIGS. composition more significantly undergoes crystallization .
14A and 14B ; This causes the glass composition to be hardly expanded
FIG . 16B is a cross-sectional view taken along the line into low -temperature sealing glass frits , low - temperature
A - A of FIG . 16A ; sealing glass pastes , conductive materials, and conductive
FIG . 17 is a schematic cross -sectional view illustrating pastes and to be hardly applied to glass-sealed components
yet another step of the method for producing the OLED
display of FIGS. 14A and 14B ; and electrical/ electronic components obtained using any of
FIG . 18A is a schematic plan view of a light-receiving them .
surface of a solar cell prepared according to an embodiment 15 restrainis anthe object
It of the present invention to prevent or
crystallization of a Ag20 _ V205- Tell , lead
of the present invention ;
FIG . 18B is a back view of the light-receiving surface of free low -melting glass composition and to thereby provide a
the solar cell of FIG . 18A ; lead -free low -melting glass composition that satisfactorily
FIG . 18C is a cross -sectional view taken along the line softens and flows at a temperature of 350° C . or lower, and
A - A of FIG . 18A ; 20 preferably 300° C . or lower. It is another object of the
FIG . 19A is a schematic cross -sectional view illustrating present invention to provide , based on the above , a lead - free
a step of a method for producing a quartz resonator package low -melting glass composition that has a smaller crystalli
according to an embodiment of the present invention ; zation tendency even when mixed with low -thermal- expan
FIG . 19B is a schematic cross - sectional view illustrating sion ceramic particles or metal particles , or formed into a
another step of the method for producing a quartz resonator 25 paste . It is yet another object of the present invention to
package according to the embodiment of the present inven - expand the lead - free low -melting glass composition so as to
tion ; provide a low - temperature sealing glass frit , a low - tempera
FIG . 19C is a schematic cross -sectional view illustrating ture sealing glass paste , a conductive material, and a con
yet another step of the method for producing a quartz ductive glass paste ; and a glass -sealed component and an
resonator package according to the embodiment of the 30 electrical/ electronic component obtained using any of them .
present invention ; The present invention provides a lead - free low -melting
FIG . 19D is a schematic cross -sectional view illustrating glass composition that contains a principal component, 0 to
still another step of the method for producing a quartz 13 mole percent of a secondary component, and 0 . 1 to 3 . 0
resonator package according to the embodiment of the mole percent, in terms of oxide , of an additional component.
present invention ; 35 The principal component includes a vanadium oxide, a
FIG . 19E is a schematic cross -sectional view illustrating tellurium oxide, and a silver oxide. The total content of the
another step of the method for producing a quartz resonator principal component is 85 mole percent ormore in terms of
package according to the embodiment of the present inven - V2O5, TeO2, and Ag2O . The contents of TeO2and Ag2O are
tion ; each 1 to 2 times as much as the content of V205. The
FIG . 19F is a schematic cross -sectional view illustrating 40 secondary component includes at least one selected from the
yet another step of the method for producing a quartz group consisting of BaO , WOz, and P , 05. The additional
resonator package according to the embodiment of the component includes at least one selected from oxides of
present invention ; and elements in Group 13 of the periodic table . As used herein
FIG . 19G is a schematic cross - sectional view of a quartz the term “ lead - free” also refers to and includes one contain
resonator package produced by the method illustrated in 45 ing the restricted materials in contents at the restricted levels
FIGS. 19A to 19F . or lower as restricted in the RoHS directive ( that took
FIG . 20 is Table 1 which shows data pertaining to effective on 1 Jul. 2006 ). The restricted level is 1000 ppm or
vitrification , characteristic temperature , crystallization ten - less for lead (Pb ).
dency and chemical stability of lead- free low -meting glass The glass composition preferably contains, as the addi
compositions. 50 tional component, at least one selected from the group
FIG . 21 is Table 2 which shows data pertaining to consisting of B203, Al2O3, Ga_ 03 and In203 in a content
formulation of lead -free low melting glass composition . (total content) in terms of oxide of 0 . 1 to 2 . 0 mole percent.
FIG . 22 is Table 3 which shows data pertaining to In particular, the glass composition may effectively contain
vitrification , characteristic temperature , crystallization ten - at least one selected from the group consisting of A1,03,
dency and chemical stability of lead -free low -meting glass 55 Ga203 and In203 as the additional component. The glass
compositions. composition more preferably contains the additional com
ponent in the content of 0 . 1 to 1 .0 mole percent.
DETAILED DESCRIPTION OF THE The lead - free low -melting glass composition according to
PREFERRED EMBODIMENTS the embodiment of the present invention may have a soft
60ening point of 280° C . or lower, where the softening point
The Ag, 0 — 1205 Tell , lead - free low -melting glass is determined by a differential thermal analysis (DTA ) as a
composition disclosed in Patent Literature 1 certainly has a second endothermic peak temperature . The glass composi
lower softening point as compared with the conventional tion may have a crystallization onset temperature higher
PbOB , 0 , low -melting glass compositions , but has a ten than the second endothermic peak temperature (softening
dency to crystallize and thereby softens and flows unsatis - 65 point ) by 60° C . or more , where the crystallization onset
factorily due to the crystallization tendency upon heating temperature is determined by the differential thermal analy
firing . Specifically , with insufficient consideration on the sis (DTA ).
US 9 ,950,948 B2
The present invention provides, in another embodiment, a The present invention provides, in still another embodi
low -temperature sealing glass frit containing 40 to 100 ment, a glass - sealed component including a seal portion
volume percent of the lead - free low -melting glass compo - containing a lead -free low -melting glass phase . The seal
sition and 0 to 60 volume percent of low - thermal-expansion portion contains 40 to 100 volume percent of the lead - free
ceramic particles. Herein , the low -temperature sealing glass 5 low -melting glass phase . The lead -free low -melting glass
frit contains the lead -free low -melting glass composition and phase may be derived from the lead - free low -melting glass
the low -thermal -expansion ceramic particles . Hence, the composition according to the embodiment of the present
content of the lead - free low -melting glass composition is invention . The glass - sealed component can be effectively
actually less than 100 volumepercent, and the content of the 10 panels and typically
expanded
display
into vacuum -insulating double glass
panels .
low - thermal-expansion ceramic particles is actually more The present invention provides, in another embodiment ,
than o volume percent. The same applies in the following an electrical/ electronic component including at least one unit
numerical
?? ranges . selected from electrodes , interconnections , and conductive
The low -thermal-expansion ceramic particles preferably junctions, where the at least one unit contains the lead -free
include at least one selected from the group consisting of 15 low -melting glass phase . The unit contains 5 to 100 volume
zirconium phosphate tungstate (Zr (WO ) ( PO4)2 ) r, quartz percent of the lead - free low -melting glass phase and 0 to 95
glass (SiO2), zirconium silicate (ZrS104), aluminum oxide volume percent of metal particles . The electrical/ electronic
( Al2O3) , mullite (3A1203.2SiO2), and niobium oxide component can be effectively expanded typically into solar
(Nb205). In particular, the low - thermal-expansion ceramic cells, image display devices, multilayer capacitors , quartz
particles are preferably particles of zirconium phosphate 20 resonators, LEDs (light-emitting diodes ), and multilayered
tungstate (Zr2 (W04) (PO4) 2) and /or particles of a compound circuit boards.
containing mainly zirconium phosphate tungstate (Zr2 The present invention will be illustrated in further detail
(WO2) (PO4)2). The glass frit effectively contains 30 to 50 with reference to certain embodiments thereof and the
volume percent of the low -thermal -expansion ceramic par - attached drawings . It should be noted , however, that the
ticles . 25 embodiments are never construed to limit the scope of the
The low - temperature sealing glass frit may be prepared present invention , and that various combinations , changes ,
from a low - temperature sealing glass paste that contains the modifications, and improvements are possible without devi
lead - free low -melting glass composition according to the a ting from the spirit and scope of the present invention .
embodiment of the present invention in the form of particles , (Glass Composition )
low - thermal-expansion ceramic particles, and a solvent. In 30 In general, a low -melting glass composition more satis
the low - temperature sealing glass paste , the low -thermal- factorily softens and flows at a low temperature with a
expansion ceramic particles preferably include at least one decreasing characteristic temperature (e.g., glass transition
selected from the group consisting of zirconium phosphate point, yield point, or softening point) . In contrast, the
tungstate (Zr2 (WO4) (PO4)2) , quartz glass (SiO2), zirconium low -melting glass composition has a higher crystallization
silicate (ZrSiO2), aluminum oxide (A1,0z), mullite 35 tendency , becomes more susceptible to crystallization upon
(3A1203.2SiO2), and niobium oxide (Nb205), and the sol- heating- firing , and , contrarily , softens and flows unsatisfac
vent preferably includes a -terpineol and /or diethylene gly - torily at a low temperature with an excessively low charac
col n -butyl ether acetate (e.g ., Butyl CARBITOL Acetate ). teristic temperature. In addition , a glass having a lower
In particular, the low - thermal- expansion ceramic particles characteristic temperature has inferior chemical stability
effectively include zirconium phosphate tungstate ( Zr , 40 such as water resistance and acid resistance . This glass also
(WO . ) (PO4)2 ) and /or a compound containing mainly zir- has a tendency to put a larger burden on the environment .
conium phosphate tungstate (Zr, (WO2) (POL), ), and the Typically, with an increasing content of hazardous PbO , the
solvent effectively includes a -terpineol. conventional PbO - B20 low -melting glass compositions
The present invention provides , in yet another embodi can have lower characteristic temperatures, but have a
ment, a conductive material containing 5 to 100 volume 45 higher crystallization tendency and lower chemical stability ,
percent of the lead - free low -melting glass composition , and and put larger burden on the environment.
0 to 95 volume percent of metal particles . The conductive The present inventors made intensive investigations on a
material preferably contains, as the metal particles, at least glass composition that is a low -melting glass composition
one selected from the group consisting of silver (Ag ), silver containing approximately no lead , but can soften and flow
alloys, copper (Cu ), copper alloys , aluminum (Al), alumi- 50 satisfactorily at a lower temperature as compared with the
num
?? alloys, tin (Sn ), and tin alloys. In particular , the conventional PbOB203 low -melting glass compositions,
conductive material preferably contains at least one of silver and still has good chemical stability . As a result, the present
( Ag) and aluminum (Al) as the metal particles . The content inventors have found that a novel low -melting glass com
of the metal particles is effectively 10 to 90 volume percent. position meets the requirements simultaneously. The present
The conductive material may be formed from a conduc - 55 invention has been made based on these findings .
tive glass paste that contains the lead - free low -melting glass As described above , the lead - free low -melting glass com
composition according to the embodiment of the present position according to the embodiment of the present inven
invention in the form of particles , and a solvent. The tion is a lead - free low -melting glass composition that con
conductive glass paste may further contain metal particles. tains a vanadium oxide , a tellurium oxide , and a silver oxide
The metal particles may include at least one selected from 60 as principal components . The total content of the principal
the group consisting of silver (Ag), silver alloys, copper components is 85 mole percent or more in terms of V 05,
( Cu ), copper alloys, aluminum ( Al), aluminum alloys, tin TeO2, and Ag20 . The contents of Tell , and Ag20 are each
(Sn ), and tin alloys . The solvent preferably includes a -ter 1 to 2 times as much as the content of V205. The glass
pineol and /or diethylene glycol n - butyl ether acetate . In an composition further contains 0 to 13 mole percent of a
effective embodiment, the metal particles may include silver 65 secondary component including at least one selected from
(Ag) and /or aluminum ( Al), and the solvent may include the group consisting of BaO , WO3, and P205. The glass
C -terpineol. composition still further contains 0 . 1 to 3 .0 mole percent of
US 9 ,950 ,948 B2
10
an additional component including at least one selected from higher than the range , the glass composition may cause a
oxides of elements in Group 13 of the periodic table . The metal silver precipitation upon glass production , may have
present inventors have found that the V205 — Te02 - Ag20 less effectively lowered characteristic temperatures, may
lead - free low -melting glass composition can have a lower undergo a significant crystallization upon heating- firing , or
crystallization tendency , when combined with a small 5 may have an inferior chemical stability . In addition , the glass
amount of at least one selected from oxides of elements in composition preferably further contains a secondary com
Group 13 of the periodic table . Specifically, the oxides of ponent including at least one of BaO , WO3, and P20 , in the
elements in Group 13 of the periodic table are exemplified content in terms of the oxides of greater than 0 to 13 mole
by B , 02, A1,02, Ga , Oz, In ,0z, and T1,02. The content of percent. This is preferred for the lead - free low -melting glass
the additional componentmay effectively fall the additional 10 composition according to the embodiment of the present
component in the content within the range of 0 . 1 to 3 .0 mole invention to form glass in a homogeneous vitreous state
percent. The additional component may little contribute to a (amorphous state ) and for the resulting glass to have a
lower crystallization tendency , if containing the additional smaller crystallization tendency. However, the glass com
component in the content less than 0 .1 mole percent. In position may have higher characteristic temperatures , if
contrast, the additional component may cause the glass 15 containing the secondary component in the content greater
composition to have a higher characteristic temperature such than 13 mole percent.
as softening point and / or to have a higher crystallization As having the above-mentioned configuration , the lead
tendency contrarily , if containing the additional component free low -melting glass composition according to the
in the content greater than 3 . 0 mole percent. T1 ,02, one of embodiment of the present invention can have a softening
the oxides of elements in Group 13 of the periodic table , is 20 point of 280° C . or lower, where the softening point is
not restricted by the RoHS directive, but is a toxic substance , determined by the differential thermal analysis (DTA ) as a
and its use should be avoided asmuch as possible even in a second endothermic peak temperature . In addition , the glass
small amount . For this reason , of the oxides of elements in composition can have a crystallization onset temperature
Group 13 of the periodic table , at least one of B ,02, A1, 02, higher than the second endothermic peak temperature ( soft
Ga, 03, and In2O3 is preferred . For a still lower crystalliza - 25 ening point ) by 60° C . or more , where the crystallization
tion tendency , the glass composition preferably contains the onset temperature is determined by the DTA . The lead - free
additional component in a content of 0 . 1 to 2 .0 mole percent. low -melting glass composition according to the embodiment
Among them , the glass composition more effectively con of the present invention preferably has a lower softening
tains at least one of A1, 03,Ga,03, and In ,03 so as to prevent point and , in contrast, a higher crystallization onset tem
or restrain crystallization . The content of the additional 30 perature . This allows the glass composition to soften and
component is more effectively 0 . 1 to 1 .0 mole percent. flow at a low temperature more satisfactorily . This is pre
Next, it will be illustrated how the vanadium oxide ferred so as to expand the glass composition into low
(V203), tellurium oxide ( Te02) and silver oxide (Ag20 ) temperature sealing glass frits , low -temperature sealing
which are the principal components act in the lead - free glass pastes , conductive materials, and conductive pastes
low -melting glass composition . 35 and to apply them to glass - sealed components and electrical/
Ag20 is added so as to allow the glass composition to electronic components . However, conventional low -melting
have lower characteristic temperatures such as glass transi- glass compositions may often suffer from a lower crystalli
tion point, yield point, and softening point and to have better z ation onset temperature , when designed to have a lower
chemical stability. V20 , is added so as to preventAg2O from softening point.
reduction and from precipitation as metal silver (Ag) upon 40 The characteristic temperatures in the present invention
glass production . Ag2O contained as a glass component may will be described below . The characteristic temperatures
fail to effectively offer characteristic temperatures at desired herein are measured by the differential thermal analysis
low levels unless it is present in the form of Ag * ion in the (DTA ). FIG . 1 is an exemplary DTA curve specific to glass
glass. The glass composition can offer lower characteristic on a typical glass formulation . Measurement of glass by the
temperatures with an increasing content of the silver oxide , 45 DTA is generally performed using glass particles having a
i. e., with an increasing amount of silver ions in the glass . particle diameter of about several tens ofmicrometers with
However, this requires a higher content of 1 , 0 , so as to high purity aluminum oxide ( a - A1,0z) particles as a refer
prevent or restrain the precipitation ofmetal silver (Ag). The ence standard . The measurement may be performed in the
glass can contain Ag * ion in a number of up to 2 per one V5+ air at a rate of temperature rise of 5° C . per minute . As
ion upon its production . Teo , acts as a vitrification compo - 50 illustrated in FIG . 1 , the onset temperature of a first endo
nent so as to cause vitrification upon glass production . The thermic peak is defined as the glass transition point T . ; the
glass composition fails to form glass, if containing no Te02. peak temperature of the first endothermic peak is defined as
The glass composition may have a higher crystallization the yield point ( deformation point) M . ; the second endo
tendency, if the glass composition containing Teo , in an thermic peak temperature is defined as the softening point
excessively low content. However, the Te * + ion can act 55 T .; and the onset temperature of the exothermic crystalliza
effectively when contained in a number up to 1 per one V5 + tion peak is defined as the crystallization onset temperature
ion . If the number is greater than 1, a compound between Te Tor . The characteristic temperatures are each generally
and Ag may precipitate . determined by the tangent method . The characteristic tem
In consideration of the above-described functions and peratures Tg, Mg, and T , are defined by the glass viscosity
actions of the vanadium oxide, tellurium oxide, and silver 60 and are temperatures respectively corresponding to viscosi
oxide, the lead - free low -melting glass composition accord - ties of 1013.3 poise , 1011.0 poise , and 107.65 poise . The
ing to the embodiment of the present invention effectively crystallization tendency may be determined by the crystal
has such a basic formulation that the total content of V ,05, lization onset temperature Ty, and the size of the exothermic
Teo , and Ag , in terms of the oxides is 85 mole percent or crystallization peak , i.e ., the amount of heat liberated by
more , and the contents of TeO2 and Ag20 are each 1 to 2 65 crystallization . It can be said that glass is less susceptible to
times as much as the content of V ,05. Disadvantageously , if crystallization when having a higher crystallization onset
the glass composition has a basic formulation lower than or temperature Tcru , i.e ., a larger difference between the soft
US 9 ,950 ,948 B2
ening point T , and the crystallization onset temperature Ter temperature higher than the softening point T , of the con
and having a smaller amount of heat liberated by crystalli tained lead - free low -melting glass composition by about 20°
zation . C . to about 60° C . The low -temperature sealing glass frit and
Assume that a low -melting glass composition is used to low -temperature sealing glass paste according to the
seal and /or bond various parts or components or to form 5 embodiments of the present invention each contain the
electrodes /interconnections and conductive junctions. In this lead -free low -melting glass composition having a lower
process , the low -melting glass composition is fired generally softening point and having a smaller crystallization ten
frequently at a preset temperature higher than the softening dency , can thereby soften and flow more satisfactorily at a
point T , by about 20° C . to about 60° C ., although the firing low temperature , and can be fired at a lower temperature .
temperature may vary depending typically on the type , 10 This reduces the burden on the environment and still allows
content, and particle diameter of the contained low -thermal the glass -sealed component to less undergo thermal damage
expansion ceramic particles or metal particles, and on the ( to have higher functions ) and to offer better productivity
firing conditions such as rate of temperature rise , atmo - (with reduced takt time). In addition , the lead - free low
sphere , and pressure. The low -melting glass composition has melting glass composition according to the embodiment of
to satisfactorily soften and flow at that firing temperature . It 15 the present invention has good chemical stability . This
is therefore very important to minimize the crystallization of allows the glass -sealed component to have reliability at
the low -melting glass composition at the firing temperature . certain level.
(Low - Temperature Sealing Glass Frit and Low - Tempera (Conductive Material and Conductive Glass Paste )
ture Sealing Glass Paste ) The conductive material according to an embodiment of
The low -temperature sealing glass frit according to an 20 the present invention contains 5 to 100 volume percent of the
embodiment of the present invention contains 40 to 100 lead - free low -melting glass composition according to the
volume percent of the lead - free low -melting glass compo - embodiment of the present invention , and 0 to 95 volume
sition according to the embodiment of the present invention , percent of metal particles . The conductive glass paste
and 0 to 60 volume percent of low - thermal-expansion according to the embodiment of the present invention con
ceramic particles. The low - temperature sealing glass paste 25 tains the lead - free low -melting glass composition according
according to an embodiment of the present invention con - to the embodiment of the present invention in the form of
tains the lead - free low -melting glass composition according particles, metal particles , and a solvent. The conductive
to the embodiment of the present invention in the form of material, if containing the lead - free low -melting glass com
particles , low -thermal- expansion ceramic particles, and a position according to the embodiment of the present inven
solvent. The glass frit may fail to achieve good sealing 30 tion in a content less than 5 volume percent, or if containing
and/ or bonding , if containing the lead -free low -melting glass the metal particles in a content greater than 95 volume
composition according to the embodiment of the present percent, may cause insufficient sintering between the metal
invention in the content less than 40 volume percent, or if particles or may offer insufficient bonding ( adhesion ) to a
containing the low - thermal-expansion ceramic particles in substrate .
the content greater than 60 volume percent. 35 Some metal particles offer good conductivity when mixed
Some low -thermal-expansion ceramic particles allow the with the lead - free low -melting glass composition according
lead - free low -melting glass composition according to the to the embodiment of the present invention . Such metal
embodiment of the present invention to less undergo crys - particles may include at least one selected from the group
tallization . The glass frit or glass paste may preferably consisting of silver (Ag), silver alloys , copper ( Cu), copper
contain , as such low -thermal-expansion ceramic particles , at 40 alloys, aluminum (Al), aluminum alloys , tin ( Sn ), and tin
least one selected from the group consisting of zirconium alloys. Of these metal particles , silver ( Ag ) and /or aluminum
phosphate tungstate (Zr2 (WO4) (PO4)2), quartz glass (SiO2), ( Al) particles are effective for allowing the conductive
zirconium silicate (ZrSiO4), aluminum oxide ( Al2O3), mul- material according to the embodiment of the present inven
lite (3A1203.2SiO2), and niobium oxide (Nb205). Among tion to have a lower electric resistance. The conductive
these low - thermal -expansion ceramic particles , zirconium 45 material may contain at least one of silver (Ag ) and alumi
phosphate tungstate ( Zr- (WO . ) (PO4)2 ) and/or a compound n um (Al) preferably in the content of 10 to 90 volume
containing mainly zirconium phosphate tungstate (Zr2 percent. The resulting lead - free low -melting glass compo
(WO4) (PO4)2 ) is effective to allow the low - temperature sition according to the embodiment of the present invention
sealing glass frit according to the embodiment of the present can accelerate the sintering of silver ( Ag) particles and can
invention to less undergo thermal expansion . The glass frit 50 remove a surface oxide film from aluminum ( Al) particles.
preferably contains at least one of the components in a Alpha - terpineol and diethylene glycol n -butyl ether acetate
content of 30 to 50 volumepercent. Some solvents allow the (e . g ., ButylCARBITOL Acetate ) are preferred as the solvent
lead -free low -melting glass composition according to the for the lead- free low -melting glass composition according to
embodiment of the present invention to less undergo crys - the embodiment of the present invention , of which a -terpi
tallization . Such solvents are exemplified by a - terpineol and 55 neol is particularly effective, as with the low - temperature
diethylene glycol n -butyl ether acetate , of which a -terpineol sealing glass paste according to the embodiment of the
is particularly effective . The low -temperature sealing glass present invention . The conductive glass paste may further
paste may further contain one or more additives such as contain one or more additives such as viscosity modifiers
viscosity modifier and wetting agents as needed so as to and wetting agents as needed so as to control the stability
control the stability and coatability . 60 and coatability .
Assume that the low -temperature sealing glass frit or Assume that the conductive material or conductive glass
low - temperature sealing glass paste according to the paste according to the embodiment of the present invention
embodiment of the present invention is used for sealing is used so as to form an electrode/ interconnection and /or a
and / or bonding to form a glass -sealed component. In this conductive junction in an electrical/ electronic component. In
case , the low -temperature sealing glass frit or low -tempera - 65 this case , the conductive material or conductive glass paste
ture sealing glass paste is arranged in or applied to a portion may be arranged in or applied to a predetermined portion
of an article to be sealed or to be bonded , and is fired at a typically of a substrate , and is fired at a temperature higher
US 9 ,950 ,948 B2
13 14
than the softening point Te of the contained lead -free low - examined . The lead - free low -melting glass composition
melting glass composition by about 20° C . to about 60° C . basically contains 21V205- 38Te02-37Ag20 - 3BaO - 1W03
Assume that the metal particles to be used include a metal (mole percent) as a formulation upon glass production . The
that is susceptible to oxidation . In this case , the firing is oxides of elements in Group 13 of the periodic table used
preferably performed in an inert gas atmosphere or in a 5 herein were B2O3, Al2O3, Ga2O3, In2O3, and T1203. The
vacuum atmosphere so as to prevent the metal particles from lead - free low -melting glass composition contained any one
oxidation . of these oxides in a content of 0 . 3 mole percent. The
The conductive material and conductive glass paste additional component was added while replacing part of
according to embodiments of the present invention contain WO3. Namely , the WOz content herein was set to 0 . 7 mole
the lead -free low -melting glass composition having a lower 10 percent.
softening point and a smaller crystallization tendency , can In this experimental example, six different lead - free low
thereby soften and flow more satisfactorily at a low tem melting glass compositions VTA - 100 to VTA - 105 including
perature , and can be fired at a lower temperature . Specifi- one having the basic formulation were prepared . The result
cally , the conductive material and conductive glass paste can ing lead - free low -melting glass compositions were exam
form the electrode /interconnection and/ or the conductive 15 ined and evaluated on vitrification , characteristic tempera
junction at a lower temperature , namely , can be fired at a tures in relation to crystallization tendency, and chemical
lower temperature . This reduces the burden on the environ - stability. VTA - 100 had the basic glass formulation of
ment and still allows the electrical/ electronic component to 211205- 38TeO2-37Ag20 -3BaO - 1WOz (mole percent ).
undergo less thermal damage ( to have higher functions ) and VTA - 101 to VTA - 105 are glass compositions containing
to offer better productivity (with reduced takt time). In 20 WO3 in the content of 0 .7 mole percent and respectively
addition , the lead - free low -melting glass composition containing B203, Al2O3, Ga ,03, In2O3, and T1,03 in the
according to the embodiment of the present invention has content of 0 .3 mole percent.
good chemical stability . This allows the electrical/electronic (Preparation of Lead -Free Low -Melting Glass Composi
component to have reliability at a certain level. tion )
(Glass -Sealed Component) 25. Lead -free low -melting glass compositions VTA - 100 to
The glass -sealed component according to an embodiment VTA - 105 as in Table 1 were prepared . The formulations
of the present invention is not limited , as long as including given in Table 1 are formulations upon glass production .
a portion sealed and /or bonded with any of the low -tem - Starting materials used herein were powders of V , 05
perature sealing glass frit and low -temperature sealing glass (Shinko Chemical Co ., Ltd .), TeO2 (Kojundo Chemical
paste according to the embodiments of the present invention . 30 Laboratory Co ., Ltd .), Ag , 0 ( Wako Pure Chemical Indus
Preferred examples of the glass -sealed component include tries, Ltd.), BaCO3 (Kojundo Chemical Laboratory Co .,
vacuum - insulating double glass panels applied typically to Ltd .), and WO3 (Kojundo Chemical Laboratory Co., Ltd .).
window panes ; as well as display panels such as plasma The oxides of elements in Group 13 of the periodic table
display panels , organic electroluminescent display panels , used herein were powders of B203, Al2O3, Ga203, In2O3,
and fluorescent display tubes. The glass frit and glass paste 35 and T1203 each supplied by Kojundo Chemical Laboratory
can also be expanded typically into bonding in electrical/ Co ., Ltd .
electronic components such as quartz resonators , IC ceramic Individual starting material powders were weighed , for
packages, and semiconductor sensors. mulated , and mixed to a total amount of about 200 g , and the
( Electrical/Electronic Component ) mixture was placed in a quartz glass crucible. The quartz
The electrical/electronic component according to an 40 glass crucible housing the starting material powdermixture
embodiment of the present invention is not limited , as long was placed in a glass melter, heated to a temperature of 700°
as including an electrode/interconnection and/or a conduc C . to 750° C . at a rate of temperature rise ofabout 10° C . per
tive junction formed using any of the conductive material minute , and held at the temperature for one hour with
and conductive glass paste according to embodiments of the stirring using an aluminum oxide rod so as to uniformize the
present invention . Preferred examples of the electrical/ elec - 45 formulation of the melt in the quartz glass crucible . The
tronic component include solar cells, image display devices, quartz glass crucible was retrieved from the glassmelter, the
multilayer capacitors , quartz resonators, LEDs, and multi melt was poured into a stainless steel mold previously
layered circuit boards. heated to about 120° C ., and thereby yielded the lead - free
low -melting glass compositions VTA - 100 to VTA - 105.
EXAMPLES 50 Next, each of the prepared lead -free low -melting glass
compositions was pulverized to a size of about 10 um .
The present invention will be illustrated in further detail ( Evaluation of Vitrification )
with reference to specific experimental examples below . It The prepared lead -free low -melting glass compositions
should be noted , however, that the experimental examples VTA - 100 to VTA - 105 were subjected to X -ray diffractom
are never construed to limit the scope of the present inven - 55 etry to determine whether crystallization occurred in each
tion ; and that various modifications and variations are pos glass composition in the form of powder and to evaluate the
sible without deviating from the spirit and scope of the vitrification . A sample suffering from no crystallization was
present invention . considered to be vitrified satisfactorily and evaluated as
" accepted ” . In contrast, a sample suffering from crystalliza
Experimental Example 1 60 tion was considered to fail to have a homogeneous amor
phous state as a result of vitrification and evaluated as
In this experimental example , a trace amount of any of " rejected ” .
oxides of elements in Group 13 of the periodic table was ( Evaluation of Characteristic Temperatures and Crystal
added as an additional component to a lead - free low -melting lization Tendency )
glass composition containing a vanadium oxide, a tellurium 65 The prepared lead- free low -melting glass compositions
oxide, and a silver oxide as principal components . In this VTA - 100 to VTA - 105 were subjected to differential thermal
process, how the addition affects the glass properties was analysis (DTA ) using a powder of each glass composition to
US 9, 950, 948 B2
15 16
evaluate or determine their characteristic temperatures and heat liberated by crystallization , and could less satisfactorily
crystallization tendency . The DTA was performed with a soften and flow upon heating- firing. It was difficult to
macrocell system , where about 500 mg of a sample glass expand the sample into the sealing and/or bonding and into
powder was placed in the macrocell, heated in the air from the formation of electrodes/interconnections and conductive
room temperature up to 400° C . at a rate of temperature rise 5 junctions. In contrast, the lead - free low -melting glass com
of 5° C . per minute to plot a DTA curve as illustrated in FIG . positions VTA - 101 to VTA - 105 (examples ) containing a
1. Based on the plotted DTA curve, the glass transition point trace amount of any of oxides of elements in Group 13 of the
Tg, yield point Mg, softening point Ts, and crystallization periodic table had a still lower crystallization tendency as
onset temperature T . , were determined . In addition , the size compared with the comparative example VTA - 100 . In addi
of the exothermic crystallization peak was measured to 10 tion , the examples VTA - 101 to VTA - 105 had little rise in the
determine the amount of heat liberated by crystallization . characteristic temperatures T ., M . and T and suffered from
How the crystallization tendency was effectively reduced
was evaluated in five grades based on the crystallization approximately no deterioration in chemical stability .
onset temperature Tem and the amount of heat liberated by is stance However, T1,0z contained in VTA - 105 is a toxic sub
crystallization . A sample offering no exothermic crystalli - 15 Stance ;, and its use should be avoided as much as possible
zation peak as compared with the VTA - 100 glass having the even in a trace amount. For this reason , of the oxides of
basic formulation was evaluated as extremely good and elements in Group 13 of the periodic table , B203, Al2O3,
rated “ 5 ” . A sample apparently offering both a higher Ga,03, and In2O3 are preferably used as in VTA -101 to
crystallization onset temperature T . and a smaller amount VTA - 104 . The data demonstrated as follows. Among them ,
of liberated heat was evaluated as very good and rated “ 4 ” , 20 particularly in VTA - 103 to VTA - 105 , the presence of A1,03,
and a sample apparently offering one of the two factors was Ga2O3 , and In2O3 is significantly effective for a lower
evaluated as good and rated “ 3 ” . In contrast, a sample crystallization tendency, of which A1, 0 , is most effective ,
apparently offering both a lower crystallization onset tem followed by Ga203 and In2O3 in this order.
perature Tom and a larger amount of liberated heat was These data and considerations demonstrated as follows.
evaluated as very faulty and rated “ 1” , and a sample appar - 25 Assume that lead - free low -melting glass compositions con
ently offering one of the two factors was evaluated as faulty tain a vanadium oxide ( V , 0 . ), a tellurium oxide ( Te0 , ), and
and rated “ 2” . Samples having a rating “ 3 ” or greater were a silver oxide (Ag2O ) as principal components. These lead
regarded as having an effectively reduced crystallization free low -melting glass compositions, when further contain
tendency . ing at least one of oxides of elements in Group 13 of the
(Evaluation of Chemical Stability )
The prepared lead - free low -melting glass compositions 30 have
periodi
periodic table as an additional component, can particularly
VTA - 100 to VTA - 105 were each subjected to a water in thea softening lower crystallization tendency without significant rise
point T , and without deterioration in chemi
resistance test and an acid resistance test to evaluate a cal stability . In consideration of influence on the environ
chemical stability . Glass test specimens were cullet having
a size of about 10 to about 20 mm before pulverization . In 35 mental burden , of the oxides of elements in Group 13 of the
the water resistance test , the cullet was immersed in pure periodic table , preferred to be contained are B203, Al2O3,
water at 50° C . for 48 hours . In the acid resistance test, the Ga203, and In203, of which Al2O3, Ga ,03, and In ,03
cullet was immersed in a 1 N aqueous nitric acid solution at significantly effectively contributed to a lower crystalliza
room temperature for 24 hours. The cullet specimens after tion tendency. Among them , A1,02 was most effective ,
the two tests were visually observed on appearance. A 40 followed by Ga2O3 and In2O3 in this order , for the lower
sample offering no change in appearance was evaluated as crystallization tendency.
“ accepted ” , whereas a sample offering a change in appear
ance was evaluated as " rejected ” . As a comparative Experimental Example 2
example , cullet of conventional lead - containing low -melting
glass composition PB - 100 was subjected to the tests as 45 In this experimental example, lead -free low -melting glass
above . The lead - containing low -melting glass composition
compositions containing a vanadium oxide ( V ,05), a tellu
PB -100 used as a comparative example had a formulation of rium oxide ( Te02), and a silver oxide (Ag20 ) as principal
84Pb0 - 13B203-2SiO2-1A1203 (mass percent), a glass tran - components and further containing any of oxides of ele
sition point T . of 313° C ., a yield point M , of 332° C ., and
ments in Group 13 of the periodic table were prepared. How
a softening point T . of 386° C . 50 the content of any of the oxides of elements in Group 13 of
Table 1 (FIG . 20 ) shows the evaluation results of the the periodic table affects the vitrification, characteristic
vitrification , characteristic temperatures in relation to crys - temperatures in relation to crystallization tendency , and
tallization tendency, and chemical stability of the lead - free chemical stability was investigated . The oxides of elements
low -melting glass compositions V ' l'A - 100 to VTA - 105 . in Group 13 of the periodic table used herein were A1,03,
Table 1 also shows the evaluation results of the conventional 55 Ga203, and In2O3, each ofwhich was contained in a content
lead - containing low -melting glass 20 composition PB - 100 . of 0 to 5 mole percent.
The lead -free low -melting glass composition VTA - 100 The investigated formulations (mole percent) of the lead
(comparative example ) having the basic formulation had free low -melting glass compositions are given in Table 2
significantly low characteristic temperatures T ,, Mg, and T . (FIG . 21 ). The lead - free low -melting glass compositions
and can soften and flow at a significantly low temperature as 60 were examined to evaluate the vitrification , characteristic
compared with the lead - containing low -melting glass com - temperatures in relation to crystallization tendency , and
position PB - 100 (comparative example ). The sample VTA - chemical stability , and the results are given in Table 3 ( FIG .
100 had very high chemical stability in spite of having low 22). The lead - free low -melting glass compositions were
characteristic temperatures . The sample , however, had a prepared and evaluated by the procedure of Experimental
crystallization tendency at a temperature around 260° C . The 65 Example 1. VTA - 106 and VTA - 118 to VTA - 122 in Tables 2
sample had a difference between the temperatures Tom and and 3 are lead -free low -melting glass compositions contain
T , of about 40° C ., but offered a relatively large amount of ing none of oxides of elements in Group 13 of the periodic
US 9 ,950,948 B2
17 18
table and were used as comparative examples. Other lead crystallization peak . This is because these samples contained
free low -melting glass compositions contained at least one at least one of BaO , WO , and P205 as a secondary compo
of A1203, Ga,03, and In2O3. nent, in addition to the additional component including at
The lead -free low -melting glass compositions VTA - 106 least one of A1, 02, Ga ,Oz and In Oz.
to VTA - 117 were V205 — Te02- Ag2O ternary composi - 5 The other samples VTA - 123 , VTA - 124 , VTA -128 , VTA
tions . Among them , VTA - 107 to VTA - 117 further contained , 136 , and VTA - 144 offered an exothermic crystallization
as an additional component , at least one of A1, 0 , and Ga, peak , but had a significantly lower crystallization tendency
in a content of 0 . 1 to 5 .0 mole percent, where A1203 and as compared with VTA - 118 to VTA - 122 containing none of
Ga ,O2 are oxides of elements in Group 13 of the periodic oxides of elements in Group 13 of the periodic table . The
table . VTA - 107 to VTA - 117 were compared with VTA - 106 10 data demonstrated that at least one of Al2O3, Ga 03 and
containing none of oxides of elements in Group 13 of the In ,Oz, when contained in a total content of 0 . 1 to 1 . 0 mole
periodic table . The comparison demonstrated that VTA - 107 percent, most effectively contributed to a lower crystalliza
to VTA - 116 containing at least one of A1203 and Ga202 in tion tendency . VTA - 157 to VTA - 160 containing at least one
a content of 0 . 1 to 3 .0 mole percent had a higher crystalli- of A1,03, Ga ,03, and In 0 , in a total content of 5 mole
zation onset temperature Tom , and a smaller amount of heat 15 percent could have a significantly smaller amount of heat
liberated by crystallization and could have a lower crystal- liberated by crystallization , but had a tendency to have an
lization tendency . In contrast, VTA - 117 containing 5 mole equal or somewhat lower crystallization onset temperature
percent of Al2O3 could have an amount of heat liberated by Tem as compared with VTA -118 to VTA - 122 . VTA - 123 to
crystallization as small as about one third that of VTA - 106 , VTA - 160 offered no deterioration in chemical stability as
but had a tendency to have a lower crystallization onset 20 compared with VTA - 118 to VTA - 122 .
temperature Tcr as compared with VTA - 106 . VTA - 107 to VTA - 123 to VTA - 160 had a tendency to have an increas
VTA - 117 had a softening point Tz at a target level, i.e ., equal ing softening point T , with an increasing total content of at
to or lower than 280° C ., although they had a tendency to least one of A1,0z, Ga , 0 , and In , Oz. VTA - 118 to VTA - 156
have a higher softening point T with an increasing content having a total content of at least one of Al2O3, Ga 0 and
of at least one of A1, 0 , and Ga , O , as compared with 25 In 02 of 0 .1 to 3 .0 mole percent could have a softening point
VTA - 106 . VTA - 107 to VTA - 117 offered no deterioration in T , at a target level, i.e., 280° C . or lower. However, VTA - 157
chemical stability as compared with VTA - 106 . The soften having a total content of at least one of A1, 0z, Ga Oz and
ing point T ., crystallization onset temperature Tom amount In O , of 5 .0 mole percent failed to reach the target. The
of heat liberated by crystallization , and chemical stability of softening point To, crystallization onset temperature Terug
VTA - 107 to VTA - 117 were synthetically evaluated . This 30 amount of heat liberated by crystallization , and chemical
demonstrated that at least one of Al, 0 , and Ga , 0 , is stability were synthetically evaluated . This demonstrated
effective when contained in a total content of 0 . 1 to 3 .0 mole that at least one of A1 ,02, Ga , 0 , and In , O , is most effective
percent. when contained in a total content of 0 .1 to 1.0 mole percent
The lead-free low -melting glass compositions VTA - 118 as in VTA - 123 to VTA - 148 .
to VTA - 160 contained a secondary component including at 35 These data and considerations demonstrated as follows.
least one selected from BaO , WOz, and P2O5 , in addition to Assume that lead - free low -melting glass compositions con
the principal components V205, TeO2, and Ag2O . Among tain a vanadium oxide (V205), a tellurium oxide ( Te02), and
them , VTA - 123 to VTA - 160 further contained an additional a silver oxide (Ag2O ) as principal components. These lead
component including at least one of oxides of elements in free low -melting glass compositions, when further contain
Group 13 of the periodic table selected from Al2O3, Ga,03, 40 ing at least one of oxides of elements in Group 13 of the
and In ,03 in a total content of 0 . 1 to 5 . 0 mole percent . The periodic table in a total content of 0 . 1 to 3 .0 mole percent,
lead - free low -melting glass compositions VTA - 118 to VTA - can effectively have a lower crystallization tendency . The
122 are comparative examples containing none of oxides of content of at least one of oxides of elements in Group 13 of
elements in Group 13 of the periodic table . These compara - the periodic table is more preferably 0 . 1 to 2 .0 mole percent,
tive examples had a smaller amount of heat liberated by 45 and is most effectively and preferably 0 . 1 to 1.0 mole
crystallization and offered a lower crystallization tendency percent when the softening point T , crystallization onset
as compared with the comparative example VTA - 106 , as the temperature Tom amount of heat liberated by crystallization ,
comparative examples containing at least one of BaO , WO , and chemical stability of the samples are synthetically
and P , O , as a secondary component. Based on the formu- evaluated . In addition, the glass compositions, when further
lations of the lead - free low -melting glass compositions 50 containing at least one selected from BaO , WOz, and P ,05
VTA - 118 to VTA - 122 , at least one of Al2O3, Ga203, and as a secondary component, can more effectively have a still
In , O , was added to the formulations. As a result, the lower crystallization tendency .
lead - free low -melting glass compositions had a higher crys - Lead - free low -melting glass compositions , when further
tallization onset temperature Tom and a smaller amount of containing at least one of oxides of elements in Group 13 of
heat liberated by crystallization when the lead - free low - 55 the periodic table , can have a lower crystallization tendency
melting glass compositions contain at least one of the regardless of their glass formulations, as long as containing
components in a total content of 0 . 1 to 3 . 0 mole percent as a vanadium oxide (V ,05), a tellurium oxide ( Te0 , ), and a
in VTA - 123 to VTA - 156 . And the lead -free low -melting silver oxide (Ag20 ) as principal components. However,
glass compositions could have a lower crystallization ten - there can be preferred content ranges ( formulation ranges )
dency. 60 on the principal components of V ,05, Te0 , and Ag , 0 and
Of VTA -123 to VTA - 156 , VTA - 123 to VTA - 152 had a on the secondary components of BaO , WO3, and P205, in
particularly effectively lowered crystallization tendency. order to expand the glass compositions into the sealing
These samples had a total content of Al2O3, Ga,03, and and /or bonding of glass -sealed components and electrical/
In 202 of 0 .1 to 2 .0 mole percent. In addition , VTA - 125 to electronic components and into the formation of electrodes/
VTA - 127 , VTA - 129 to VTA - 135 , VTA - 137 to VTA - 143 , 65 interconnections and conductive junctions. For the principal
and VTA - 145 to VTA -148 could have such a remarkably components , Tables 2 and 3 demonstrated that the total
lower crystallization tendency as to offer no exothermic content of V2O5, TeO2, and Ag20 are effectively 85 mole
US 9 ,950 ,948 B2
19 20
percentormore, and the contents of TeO2 and Ag2O are each (Preparation of Low - Temperature Sealing Glass Paste )
effectively 1 to 2 times as much as the content of V , 05. For A lead - free low -melting glass composition in the form of
the secondary component, Tables 2 and 3 also demonstrated particles, low -thermal-expansion ceramic particles, and a
that the glass
selected from
compositions
from Bao
effectively contain atofleast one solvent weresealingblended , mixed , and yielded a series of low
selected BaO ,wo
WOz, andand P2O5
P O iniñaa content
content of 1313 mole
mole 55 temperature glass pastes. The lead - free low -melting
percent or less . These can provide lead -free low -melting the form of particles havingwere
glass composition particles VTA - 126 and VTA - 131 in
a particle diameter of about 10
glass compositions having a softening point Ts of 280° C . or u m . The low -thermal-expansion ceramic particles were par
lower and having a crystallization onset temperature Tcry ticles of : zirconium phosphate tungstate (CF -01), zirconium
higher than the softening point T , by 60° C . ormore. 10 phosphate tungstate containing a trace amount of iron tung
state (CF -02) , quartz glass (CF - 03 ), zirconium silicate (CF
Experimental Example 3 04 ), aluminum oxide (CF -05 ), mullite (CF -06 ), and niobium
oxide (CF - 07), each of which had a particle diameter of
In this experimental example , low -temperature sealing
glass frits each containing a lead - free low -melting glass , Samples to be heated and fired in an inert gas or vacuum
composition according to an embodiment of the present 15 atmosphere contained
contained a -terpineol as the solvent and further
isobornylcyclohexanol as a viscosity modifier.
invention and low -thermal-expansion ceramic particles were Samples to be fired in the air contained
prepared . Using the frits, a pair ofmetal substrates, a pair of n -butyl ether acetate as the solvent and diethylene glycol
further contained
glass substrates, or a pair of ceramic substrates , each of the ethyl cellulose as a resin binder. The lead -free low -melting
same kind , was bonded , and how the pair of substrates was 20 glass composition particles and the low - thermal -expansion
bonded was evaluated with shear stress . The lead -free low ceramic particles were blended in eight different ratios (in
melting glass compositions used herein were two different volume percent ) of 100 : 0 , 90 : 10 , 80 :20 , 70 :30, 60 : 40 , 50 :50 ,
glass compositions VTA - 126 and VTA - 131 ( see Tables 2 40 : 60 , and 30 :70 to give corresponding low -temperature
and 3 ) in the form of particles. The low -thermal-expansion sealing glass pastes . The low -temperature sealing glass
ceramic particles used herein were seven different particles 25 pastes were prepared so as to have a solids content of about
of CF - 01 to CF -07 (see Table 4 ). 80 mass percent. The " solids content” refers to the total
Table 4 also shows the density and coefficient of thermal content of the lead - free low -melting glass composition par
expansion of the low -thermal- expansion ceramic particles . ticles and the low -thermal-expansion ceramic particles .
The lead -free low -melting glass compositions in Tables 2 ( Preparation of Evaluation Sample )
and 3 had a density of 5 .0 to 6 .0 g /cm3 and a coefficient of 30 FIG . 2 illustrates how to prepare each evaluation sample.
thermal expansion of 160x10 - 7 to 195x10 – 7 per degree Initially, a cylindrical substrate 1 including a bonding
centigrade at temperatures in the range of room temperature plane 2 and having a diameter of 5 mm and a thickness of
to 150° C . The metal substrates used herein were aluminum 5 mm was prepared (step (a )) .
(Al), silver (Ag), copper (Cu ), nickel (Ni), andiron (Fe) Next, the bonding plane 2 of the cylindrical substrate 1
substrates . The glass substrate was a soda -lime glass sub - 35 was coated with a low -temperature sealing glass paste 3 by
strate , and the ceramic substrate was an aluminum oxide dispensing ( step (b )).
( A1, 0z) substrate . Each evaluation sample was prepared in The resulting article was dried at 120° C . to 150° C . in the
the following manner. Initially , a low -temperature sealing air. This was placed in an electric furnace , heated up to 220°
glass paste containing a lead - free low -melting glass com - C . at a rate of temperature rise of 10° C . per minute in an
position in the form of particles , low - thermal- expansion 40 inert gas (nitrogen ) or in the air, held for 15 minutes, heated
ceramic particles , and a solvent was prepared . The paste was up to a temperature higher than the softening point Tz of the
applied to each substrate , dried , and preliminarily fired . The contained lead - free low -melting glass composition by about
pair of the substrates was then laminated , heated , and 50° C . at the same rate of temperature rise as above , held for
thereby bonded . 15 minutes , and thereby formed a low -temperature sealing
45 glass frit 4 on thebonding plane 2 of the cylindrical substrate
TABLE 4 1 ( step (c )). Specifically , the glass pastes containing the
lead - free low -melting glass compositions VTA - 126 and
Density and coefficient of thermal expansion VTA - 131 were heated respectively up to 270° C . and 295°
of tested low - thermal-expansion ceramic particles
Coefficient of 50 The resulting article was placed on a plate substrate 5
Low -thermal- expansion Density thermal expansion having a thickness of 3 to 5 mm and including a material of
No. ceramic particles (g/cm ) (x10 - 7° C .) the same type with the cylindrical substrate 1 , fastened
CF -01 Zirconium phosphate tungstate 3 .8 - 32 thereon with a heat-resistant clip , heated up to 270° C . or
Zr2(W04)(PO4 )2
CF-02 Zirconium phosphate tungstate 3.8
3.8 - 30
295° C . in an inert gas (nitrogen ) or in the air at a rate of
containing trace amount of
55 temperature rise of 10° C . per minute , held for 15 minutes ,
iron tungstate Zr2(WO4)( PO4)2 and yielded a bonded article ( step (d )).
containing trace amount of FeWO4 The bonded article was subjected to shear stress measure
CF -03 Quartz glass 2.2 ment. Samples using a copper (Cu ) or iron ( Fe ) substrate
CF-04
SiO2
Zirconium silicate 4 .6
were heated in the inert gas ( nitrogen ) atmosphere, and
ZrSiO4 60 samples using the other substrates were heated in the air . The
CF-05 Aluminum oxide 4.0 u
?
a
Bu blending ratio between the lead - free low -melting glass com
Al2O3 position particles and the low - thermal-expansion ceramic
CF-06 Mullite 3 .2 particles in the low - temperature sealing glass paste , and the
3A1202 2SiO2 type of the low - thermal-expansion ceramic particles were
CF-07 Niobium oxide 4 .6
Nb205 65 selected in consideration of the coefficient of thermal expan
sion of the substrate to be bonded . The coefficients of
thermal expansion of the substrates used are 224x10 - per
US 9 ,950 ,948 B2
21 22
degree centigrade (aluminum (Al)), 197x10 - 7 per degree TABLE 7
centigrade (silver ( Ag )), 164x10 - 7 per degree centigrade
(copper (Cu )), 133x10 - 7 per degree centigrade (nickel (Ni)), Evaluated shear stress of bonded articles between copper substrates
127x10 -7 per degree centigrade ( iron (Fe )), 88x10 - 7 per
degree centigrade (soda - lime glass), and 81x10 -7 per degree 5
centigrade (aluminum oxide ( A1203)). Amount ( in volume percent) of
(Evaluation of Bonding ) lead -free low -melting
Each of the bonded articles prepared using the low glass composition
temperature sealing glass pastes was examined to measure
and evaluate a shear stress. In the shear stress evaluation , the 80
80 7070 60
sample having the shear stress of 30 MPa or more was Amount ( in volume percent) of
evaluated as " excellent” , the sample having the shear stress
of 20 to 30 MPa was evaluated as “ good ” , the sample having low -thermal-expansion
the shear stress of 10 to 20 MPa was evaluated as “ moder - 15 ceramic particles
ate ” , and the sample having the shear stress of less than 10
MPa was evaluated as “ rejected ” . 20 30 40
The results of the evaluation of the shear stress in the
bonded articles including the different substrates are shown VTA - 126 CF-04 Good Excellent Excellent
in Tables 5 to 11 . The evaluation results are shown in Table 20 CF -06 Good Excellent Excellent
5 for bonded articles between aluminum (Al) substrates ; in CF -07 Excellent Excellent Good
Table 6 for bonded articles between silver (Ag) substrates;
in Table 7 for bonded articles between copper (Cu ) sub VTA -131 CF -04 Good Good Good
strates ; in Table 8 for bonded articles between nickel (Ni) CF -06 Good Good Good
substrates; in Table 9 for bonded articles between iron (Fe) 25 CF - 07 Good Good Good
substrates ; in Table 10 for bonded articles between soda
lime glass substrates ; and in Table 11 for bonded articles
between aluminum oxide (A1203) substrates.
TABLE 8
TABLE 5 30 Evaluated shear stress of bonded articles between nickel substrates
Evaluated shear stress of bonded articles between aluminum substrates
Amount (in volume percent) of
Amount (in volume percent) of lead - free low -melting
lead - free low -melting glass composition
glass composition 35
70 60 50
100 90 Amount (in volume percent) of
Amount ( in volume percent) of low -thermal-expansion
low -thermal-expansion ceramic particles
ceramic particles
0 10 20 40 30 40 50
VTA - 126 CF-04 Excellent Excellent Excellent VTA - 126 CF - 03 Good Excellent Good
CF -05 Excellent Excellent Excellent CF- 06 Good Good Excellent
CF -06 Excellent Excellent Excellent CF -07 Good Excellent Excellent
VTA - 131 CF -04 Excellent Excellent Excellent VTA - 131 CF -03 Good Excellent Good
CF -05 Excellent Excellent Excellent 45 CF- 06 Good Good Excellent
CF -06 Excellent Excellent Excellent CF -07 Good Excellent Excellent
TABLE 6 TABLE 9
- 50
50 -
Evaluated shear stress of bonded articles between silver substrates Evaluated shear stress of bonded articles between iron substrates
Amount (in volume percent) of Amount (in volume percent) of

lead - free low -melting lead-free low -melting
glass composition glass composition
100 90 70 60 50
Amount ( in volume percent) of Amount (in volume percent) of
low -thermal-expansion low -thermal-expansion
ceramic particles ceramic particles
20 60 30 40 50
VTA - 126 CF -04 Excellent Excellent Excellent VTA -126 CF-01 Excellent Excellent Excellent
CF -05 Excellent Excellent Excellent CF- 02 Excellent Excellent Excellent
CF -06 Excellent Excellent Excellent CF-03 Good Good Excellent
VTA - 131 CF -04 Excellent Excellent Excellent VTA - 131 CF -01 Excellent Excellent Excellent
CF -05 Excellent Excellent Excellent CF -02 Excellent Excellent Excellent
CF -06 Excellent Excellent Excellent CF -03 Good Good Excellent
US 9 , 950 , 948 B2
23 24
TABLE 10 expansion as compared with CF -04 and CF -06 . In contrast ,
the samples using VTA - 131 did not offer a significant
Evaluated shear stress ofbonded articles
between soda -lime glass substrates difference in shear stress among blending ratios, unlike the
samples using VTA - 126 . This is probably because the
Amount ( in volume percent) of 5 samples using VTA - 131 were heated and bonded at a higher
lead - free low -melting
glass composition
temperature, and this accelerated the oxidation of copper
(Cu) by VTA - 131.
60 50 40 30 With reference to Table 8 , the tested bonded articles
Amount (in volume percent) of between nickel (Ni) substrates employed low -thermal- ex
low -thermal-expansion 10 pansion ceramic particles CF -03, CF -06 , and CF - 07 ( see
ceramic particles Table 4 ) in different contents ( amounts ) of 30 to 50 volume
40 50 60 70 percent and employed the lead -free low -melting glass com
positions VTA - 126 and VTA - 131 in different contents of 70
VTA -126 CF -01 Good Excellent Good Rejected to 50 volume percent. The samples offered good or higher
CF - 02 Good Excellent Good Rejected 15 results under all the conditions and offered similar results
VTA - 131 CF -01 Good Excellent Good Rejected
CF -02 Good Excellent Good Rejected even when using either of VTA -126 and VTA - 131. The
samples using CF -03 , when containing CF -03 in a content
(amount) of 40 volume percent, had a highest shear stress
and offered a very high bond strength and very good
TABLE 11 20 adhesion to the nickel (Ni) substrates . The data demon
Evaluated shear stress of bonded articles strated that the samples using CF -06 and CF - 07 in increas
between aluminum oxide substrates ing contents ( amounts ) had a higher (increasing ) shear stress
and offered a higher bond strength and better adhesion to the
Amount (in volume percent) of nickel (Ni) substrates . This is probably because the samples
lead - free low -melting came to have a coefficient of thermal expansion conformable
glass composition
to that of nickel (Ni).
60 50 40 30 With reference to Table 9 , the tested bonded articles
Amount ( in volume percent) of between iron (Fe) substrates employed the low -thermal
low -thermal- expansion expansion ceramic particles CF -01 to CF -03 (see Table 4 ) in
ceramic particles
30 different contents (amounts ) of 30 to 50 volume percent and
40 50 60 70 employed the lead - free low -melting glass compositions
VTA - 126 CF -01 Good Excellent Good Rejected VTA - 126 and VTA - 131 in different contents of 70 to 50
CF -02 Good Excellent Good volume percent . The samples offered good or higher results
VTA - 131 CF-01 Good Excellent Good under all the conditions and offered similar results even
CF -02 Good Excellent Good Rejected 35 when using either of VTA - 126 and VTA - 131. The data
demonstrated that the samples using CF -01 and CF - 02 had
aa high shear stress
high shear stress regardless of
of their contents (amounts) and
With reference to Table 5 , the tested bonded articles
between aluminum (Al) substrates employed the low - ther offered a very high regardless
bond strengththeir
andcontents
very good(amounts
adhesion to
mal-expansion ceramic particles CF -04 or CF - 05 (see Table 40 iron (Fe). This is probably because as follows. CF -01 and
4 ) in different contents (blending amounts) of 0 to 20 volume CF-02 have coefficients of thermal expansion as ones of the
lowest in the ceramic particles in Table 4 and still have good
percent and employed the lead -free low -melting glass com wettability with and adhesion to VTA -126 and VTA - 131 .
position VTA - 126 or VTA - 131 in different contents of 100 The resulting low -temperature sealing glass frits can easily
to 80 volume percent. The data demonstrated that these have efficiently lowered coefficients of thermal expansion
samples offered excellent results under all the conditions , 45 conformable to the coefficient of thermal expansion of the
had a very high bond strength and very good adhesion to iron (Fe ) substrates. The data also demonstrated that the
aluminum (Al), and offered similar results even when using samples using CF- 03 did not have so significant results as
either of VTA - 126 and VTA - 131. With reference to Table 6 , compared with the samples using CF -01 and CF- 02 , had an
the bonded articles between silver (Ag ) substrates also increasing shear stress , and offered a higher bond strength
offered excellent results , and the constitutive glass frits had 50 and better adhesion to the iron (Fe ) substrate with an
a very high bond strength and very good adhesion to silver increasing content (amount ) of CF -03. This is also because
(Ag), as with aluminum ( Al) . the samples came to have a coefficient of thermal expansion
With reference to Table 7 , the tested bonded articles conformable to that of iron (Fe).
between copper (Cu ) substrates employed the low -thermal With reference to Table 10 , the tested bonded articles
expansion ceramic particles CF -04 , CF - 05 , and CF -06 (see 55 between soda - lime glass substrates employed the low -ther
Table 4 ) in different contents (blending amounts ) of 20 to 40 mal-expansion ceramic particles CF -01 and CF -02 (see
volume percent and employed the lead -free low -melting Table 4 ) in different contents ( amounts ) of 40 to 70 volume
glass compositions VTA - 126 and VTA - 131 in different percent and employed the lead - free low -melting glass com
contents of 80 to 60 volume percent. These samples offered positions VTA - 126 and VTA - 131 in different contents of60
good or higher results under all the conditions. The glass 60 to 30 volume percent. There was little difference in shear
frits employing VTA - 126 , when further containing an stress between CF -01 and CF -02, and between VTA - 126 and
increasing content (amount ) of CF - 04 or CF - 06 , offered a VTA - 131. The samples offered good or higher results under
higher bond strength and better adhesion to copper (Cu). all the conditions when containing CF -01 or CF -02 in the
This is because the glass frits came to have a coefficient of content ( amount ) of 40 to 60 volume percent and VTA - 126
thermal expansion conformable to that of copper (Cu ). In 65 or VTA - 131 in the content ( amount) of 60 to 40 volume
contrast, the glass frits using CF -07 offered opposite results . percent. The samples , when containing CF -01 or CF -02 in a
This is because CF -07 has a very low coefficient of thermal content of 50 volume percent, had a largest shear stress and
US 9,950,948 B2
25 26
offered a very high bond strength and very good adhesion to particles were prepared . Pairs ofmetal substrates of the same
the soda - lime glass substrates. The samples, when contain kind were bonded using the conductive materials, and how
ing CF -01 or CF -02 in the content (amount) of 60 volume themetal substrates were bonded was evaluated with electric
percent or more ,had a lower shear stress and were evaluated resistance (contact resistance ) between the metal substrates .
as rejected at a content of 70 volumepercent. This is because 5 The lead - free low -melting glass composition used herein
as follows. Assume that glass frits contain VTA - 126 or was VTA - 130 (see Tables 2 and 3 ) , and the metal particles
VTA - 131 in an excessively low content (amount) with were four different particles of silver (Ag), copper (Cu ),
respect to the content ( amount) of CF -01 or CF -02. In this aluminum (Al), and tin ( Sn ). The metal substrates were
case , the glass frits soften and flow unsatisfactorily as substrates of aluminum (Al), silver (Ag), and copper (Cu ).
low - temperature sealing glass frits, have inferior adhesion 10 Each evaluation sample was prepared in the following
and bonding properties to the soda - lime glass substrates , and manner. Initially , a conductive glass paste containing the
fail to have a good shear stress. With reference to Table 11 , lead - free low -melting glass composition particles , the metal
the bonded articles between aluminum oxide (A1, 03) sub - particles , and a solvent was prepared . This was applied to
strates also offered shear stress evaluation results similar to both of a pair of the substrates, dried ,preliminarily fired . The
those of the bonded articles between soda -lime glass sub - 15 both substrates were then laminated , heated , and thereby
strates . This is because the aluminum oxide (A1,0z) and bonded .
soda - lime glass have coefficients of thermal expansion at (Preparation of Conductive Glass Paste )
similar levels. These results and considerations demon - The lead - free low -melting glass composition particles , the
strated that it is important to design low -temperature sealing metal particles , and the solvent were blended and mixed to
glass frits to contain the lead - free low -melting glass com - 20 give each conductive glass paste . The lead - free low -melting
position according to the embodiment of the present inven - glass composition particles used herein were VTA - 130 in the
tion in a content (amount) of volume percent or more, and form of particles having a particle diameter of about 10 um .
low -thermal-expansion ceramic particles in the content The metal particles were spherical (globular ) silver (Ag )
(amount ) of 60 volume percent or less. The tested bonding particles having an average particle diameter of about 1. 5
between the soda- lime glass substrates and between the 25 um , spherical copper (Cu ) particles having an average
aluminum oxide (A1, 0z) substrates employed the low -tem - particle diameter of about 20 um , spherical aluminum (Al)
perature sealing glass paste containing diethylene glycol particles having an average particle diameter of about 10
n -butyl ether acetate as a solvent and ethyl cellulose as a um , and spherical tin (Sn ) particles having an average
resin binder. For further testing, bonded articles were pre particle diameter of about 25 um . The solvent was a - terpi
pared by preparing a low -temperature sealing glass paste 30 neol, added with isobornylcyclohexanol as a viscosity modi
containing a -terpineol as a solvent and isobornylcyclohexa - fier. The lead - free low -melting glass composition particles
nol as a viscosity modifier instead of the above components, and the metal particles were blended in five different blend
and performing heating in the air . The prepared bonded ing ratios (in volume percent) of 100 : 0 , 80 : 20 , 60 :40 , 40 :60 ,
articles were subjected to shear stress evaluation in a similar and 20 : 80 to prepare corresponding conductive glass pastes .
manner and were found to readily have a higher shear stress. 35 The conductive glass pastes were prepared so as to have a
This is because the low -temperature sealing glass frit at the solids content of about 80 mass percent. The “ solids con
junction (bonded portion ) contained smaller amounts of tent” refers to the total content of the lead - free low -melting
residual air bubbles. The data indicate that a -terpineol is as glass composition particles and the metal particles .
the solvent effective not only in an inert gas atmosphere , but ( Preparation of Evaluation Sample )
also in the air. 40 The contact resistance between each pair of metal sub
These data demonstrated that the low -temperature sealing strates was measured by preparing an evaluation sample as
glass frit according to the embodiment of the present inven - in Experimental Example 3 by the procedure of Experimen
tion effectively contains 40 to 100 volume percent of the tal Example 3 . Specifically , this experimental example
lead -free low -melting glass composition according to the employed the evaluation sample and its preparation method
embodiment of the present invention and 0 to 60 volume 45 similar to those illustrated in FIG . 2 .
percent of the low -thermal- expansion ceramic particles . The Initially, a cylindricalmetal substrate 1 ' including a bond
data also demonstrated that the low - thermal- expansion ing plane 2 ' and having a diameter of 5 mm and a thickness
ceramic particles can be selected from zirconium phosphate of 5 mm was prepared ( step (a )).
tungstate ( Zr , (WO . ) (POL) , ), quartz glass (SiO ), zirconium Next, the bonding plane 2 ' of the cylindricalmetal sub
silicate (ZrSiO2), aluminum oxide (A1,0z), mullite 50 strate 1 ' was coated with a low -temperature sealing glass
(3A1, 02. 2SiO2) , and niobium oxide (Nb , 05) each in particle paste 3 ' by dispensing (step (b )).
form . In particular, the low -temperature sealing glass frit The resulting article was dried at 120° C . to 150° C . in the
more effectively contains zirconium phosphate tungstate air. This was placed in an electric furnace , heated up to 220°
( Zr- (WO2)( POA), ) and /or a compound containing mainly C . at a rate of temperature rise of 10° C . per minute in an
zirconium phosphate tungstate (Zr , (WO ) (POA),) so as to 55 inert gas (nitrogen or argon ), held for 15 minutes, heated up
still less undergo thermal expansion . The content of this to a temperature higher than the softening point T , of the
component is preferably to 50 volume percent. The low - contained lead -free low -melting glass composition by about
temperature sealing glass paste according to the embodiment 40° C . at the same rate of temperature rise as above , held for
of the present invention may contain a solvent that can be 10 minutes , and thereby formed a low -temperature sealing
selected from a -terpineol and diethylene glycol n -butyl 60 glass frit 4' on the bonding plane 2' of the cylindrical metal
ether acetate , of which a - terpineol is more effective . substrate 1 ' ( step ( c )) . This experimental example employed
the lead - free low -melting glass composition VTA - 130 , and
Experimental Example 4 the heating was performed up to a temperature of 280° C .
that is higher than the softening point T by about 40° C . The
In this experimental example , conductive materials con - 65 resulting article was placed on a plate metal substrate 5
taining the lead- free low -melting glass composition accord having a thickness of 1 to 3 mm and including a material of
ing to the embodiment of the present invention and metal the same type with the cylindrical metal substrate 1', fas
US 9 ,950 ,948 B2
28
tened thereon with a heat-resistant clip , heated up to 280° C . containing not Ag particles, but VTA - 130 alone offered a
in an inert gas (nitrogen ) at a rate of temperature rise of 10° low contact resistance . Even when a conductive glass paste
C . per minute held for 30 minutes, and yielded a bonded further containing Ag particles was used , VTA - 130 pro
article (step (d )). moted necking among the Ag particles as in the A1/ A1
The bonded article was subjected to measurement of 5 bonding, and this achieved a contact resistance on the order
contact resistance between metal substrates. of 10 - 2 /mm² in wide ranges of VTA - 130 content and Ag
(Evaluation of Bonding ) content with little dependency on the contents . In the Cu /Cu
Each of the prepared bonded articles was examined to bonding , the necking of the Ag particles mainly contributes
measure contact resistance (electric resistance ) between the to the formation of conduction paths , unlike the A1/A1
metal substrates by the four probemethod . As a comparison , 10 bonding and Ag/ Ag bonding . Thus , the contact resistance
bonding ofmetal substrates using a lead -free tin solder was decreased with an increasing content of Ag particles and
also performed . The contact resistance of bonded articles reached the order of 10 -02/mm2 at a content of Ag particles
bonded with the solder was 3 .2x10 - 3 2 /mm² for bonding of 30 volume percent or more.
between the aluminum ( Al) substrates (A1/A1 bonding), Separately, A1/A1 bonding, Ag/Ag bonding, and Cu/Cu
4 . 7x10 - 2 /mm² for bonding between the silver (Ag ) sub - 15 bonding were performed using conductive materials each
strates (Ag/Ag bonding ), and 5 .0x10 - 2 /mm2 for bonding containing the lead - free low -melting glass composition
between the copper (Cu ) substrates (Cu/Cu bonding ). The VTA - 130 and Cu metal particles. FIG . 4 shows how the
A1/A1bonding had a contact resistance higher than those of contact resistance varies depending on the contents of VTA
the Ag/Ag bonding and the Cu /Cu bonding by about three 130 and Cu in the conductive materials . In the A1/Albonding
orders of magnitude . This is because a natural oxide layer 20 and Ag/Ag bonding, the contact resistance gradually
having a high electric resistance was formed on the Al increased with an increasing Cu content and a decreasing
substrate surfaces . VTA -130 content and significantly decreased at a Cu content
Typically, Al/Al bonding , Ag/Ag bonding, and Cu/Cu of 40 volume percent or more and a VTA -130 content of 60
bonding were performed using conductive materials each volume percent or less. In contrast , the contact resistance
containing the lead - free low -melting glass composition 25 reached the order of 10 - Q2 /mm² at the Cu content of about
VTA -130 and Ag metal particles. FIG . 3 illustrates how the 30 volumepercent or less and the VTA - 130 content of about
contact resistance varies depending on the contents of VTA - 70 volume percent or more . In the Cu /Cu bonding, the
130 and Ag. In the A1/ A1 bonding and Ag/Ag bonding , the contact resistance once decreased with an increasing Cu
contact resistance reached the order of 10 - 2 /mm² within a content and a decreasing VTA - 130 content, but significantly
wide range of the contents of VTA -130 and Ag with little 30 increased at a Cu content of 40 volume percent or more and
dependency on the contents . In contrast, in the Cu /Cu a VTA - 130 content of 60 volume percent or less , as in the
bonding, the contact resistance decreased with an increasing Al/Al bonding and Ag/Ag bonding . The Cu /Cu bonding
Ag content and a decreasing VTA - 130 content and reached offered a higher contact resistance as compared to the A1/ A1
the order of 10 - 22 /mm² at the Ag content of about 30 bonding and Ag/Ag bonding. This phenomenon occurred
volume percent or more and the VTA - 130 content of about 35 because VTA - 130 softens, flows, and thereby oxidizes the
70 volume percent or less. In the A1/A1 bonding , VTA - 130 Cu particles and Cu substrates to form an oxide layer on
reacted with the Al substrates to remove a natural oxide layer their surfaces.
on the Al substrate surfaces and to form AlzV or another Al/Al bonding , Ag/Ag bonding , and Cu/Cu bonding were
alloy between Al and V at the interface . VTA - 130 , as reacted also performed using conductive materials each containing
with Alto release V (vanadium ), underwent precipitation of 40 the lead - free low -melting glass composition VTA - 130 and
metal Ag therefrom . When the Al substrates were bonded at Almetal particles . FIG . 5 illustrates how the contact resis
a small distance therebetween , the precipitated metal Ag tance varies depending on the contents of VTA -130 and Al
established connection between the Al substrates. For this in the conductive materials. In the A1/ Al bonding, Ag/ Ag
reason , even a glass paste containing not Ag particles , but bonding , and Cu / Cu bonding using VTA - 130 and the Al
VTA - 130 alone offered a low contact resistance . In addition , 45 particles , the contact resistance varied and behaved in a
testing data demonstrated that, when a glass paste further similar manner as in the samples using Cu metal particles ,
containing Ag particles was used , VTA - 130 reacts with the but was lower as compared with the samples using the Cu
Ag particles to promote the necking among the Ag particles. metal particles. In particular in the A1/A1bonding and Ag/Ag
This is probably because Ag has certain solubility in VTA - bonding, the contact resistance reached the order of 10 - 6
130 and , upon bonding by heating, is dissolved in VTA - 130 50 2 /mm² at an Al content of about 60 volume percent or less
that softens and flows as a result of heating. Ag is precipi- and a VTA - 130 content of about 40 volume percent or more .
tated with temperature fall and causes necking among the Ag In the Cu /Cu bonding, the contact resistance was higher as
particles . In the A1/Al bonding , the above -mentioned two compared with the A1/Albonding and Ag / Ag bonding, as in
reactions relating to the lead - free low -melting glass compo the samples using the Cu particles, but lower as compared
sition according to the embodiment of the present invention 55 with the samples using the Cu particles. This is because the
probably contributed to a contact resistance on the order of Cu particles are more susceptible to oxidation by the lead
10 -6 2 /mm² in wide ranges of the VTA - 130 content and Ag free low -melting glass composition according to the
content with little dependency on the contents . The contact embodiment of the present invention . The samples herein
resistance in the Ag/ Ag bonding behaved in a similar had a higher contact resistance as compared with the
manner to the Al/Al bonding . This is because the second 60 samples using the Agmetal particles at the Al content of 40
reaction in the A1/ Al bonding, namely , the reaction between volume percent or more and the VTA -130 content of 60
the Ag particles and VTA - 130 also occurred with respect to volume percent or less . This is because the Ag particles are
the Ag substrates, and metal Ag was precipitated at the more susceptible to necking by the lead - free low -melting
interface between the Ag substrate and VTA - 130 . When the glass composition as compared with the Al particles .
Ag substrates were bonded with a small distance therebe - 65 A1/A1bonding , Ag/Ag bonding, and Cu /Cu bonding were
tween , the precipitated metal Ag established connection also performed using conductive materials each containing
between the Ag substrates. For this reason , even a glass paste the lead - free low -melting glass composition VTA - 130 and
US 9,950,948 B2
29 30
Sn metal particles. FIG . 6 illustrates how the contact resis Experimental Example 5
tance varies depending on the contents of VTA - 130 and Sn
in the conductive materials . The contact resistance in the In this experimental example, conductive materials each
Ag/Ag bonding and Cu /Cu bonding using VTA -130 and the containing a lead - free low -melting glass composition
Sn particles offered similar results to the samples using the 5 according to the embodiment of the present invention and
Ag metal particles. In the Ag/ Ag bonding, the contact metal particles were prepared . Using the conductive mate
resistance reached the order of 10 - 12 /mm ' in wide ranges rials , an electrode/ interconnection was formed on different
of contents of VTA - 130 and Sn with little dependency on the substrates and was examined to evaluate electric resistance
contents . In the Cu /Cu bonding, the contact resistance interconnect resistance ) and adhesion to the substrates. The
reached the order of 10 - 2 /mm2 at the Sn content of 20 10 lead - free low -melting glass composition and the metal par
volume percent or more and the VTA - 130 content of 80 ticles used herein were respectively VTA - 141 ( see Tables 2
volume percent or less . These are because metal Sn has a and 3) and silver (Ag) particles. The substrates used were an
melting point of 232° C ., and particles thereof melt upon aluminum oxide ( A1,02) substrate , a borosilicate glass sub
bonding by heating to bond to the Ag substrates or Cu 6 strate , a silicon (Si) substrate , a ferrite substrate , and a
substrates, as with a solder. In the A1/ Al bonding, the Al polyimide substrate . Each evaluation sample was prepared
substrate surface bears a natural oxide layer. Owing to this, in the following manner. Initially , a conductive glass paste
the bonding with the solder failed to give good conductivity, containing the lead - free low -melting glass composition par
but the samples containing both VTA - 130 and Sn could offer ticles , the metal particles , and a solvent was prepared . The
a lower contact resistance by the presence of VTA - 130 . The 20 conductive glass paste was applied to each substrate , dried ,
contact resistance behaved as follows. The contact resis and preliminarily fired to form an electrode/interconnection .
tance increased with an increasing Sn content and a decreas- (Preparation of Conductive Glass Paste )
ing VTA - 130 content, but decreased at the Sn content of The lead - free low -melting glass composition particles , the
about 60 volume percent or more and the VTA - 130 content metal particles, and the solvent were blended , mixed , and
of about volume percent or less . 25 yielded a series of conductive glass pastes. The lead - free
These results and considerations demonstrate that the low -melting glass composition particles used herein were
lead - free low -melting glass composition according to the VTA - 141 particles having a particle diameter of about 10
embodiment of the present invention can be expanded into um , and the metal particles were spherical silver (Ag )
conductive materials and corresponding conductive glass particles having an average particle diameter of about 1. 5
pastes so as to form conductive junctions to establish 30 um . The solvent was a -terpineol, added with isobornylcy
connection ( conduction ) between metal substrates . In this clohexanol as a viscosity modifier. Table 12 shows blending
experimental example, VTA - 130 has been described repre ratios between the lead -free low -melting glass composition
sentatively as a lead -free low -melting glass composition VTA - 141 particles and the Ag metal particles. Seven differ
according to an embodiment of the present invention . Obvi ent conductive glass pastes were prepared in the blending
ously , other lead - free low -melting glass compositions 35 ratios given in Table 12 . The conductive glass pastes were
according to embodiments of the present invention can also prepared so as to have a solids content of about 80 mass
develop similar performance. Likewise , Ag, Cu, Al, and Sn percent. The " solids content” refers to the total content of the
have been described representatively as metal particles to be lead - free low -melting glass composition particles and the
contained in conductive materials or corresponding conduc - metal particles.
tive glass pastes . It should be noted , however, that the 40 ( Preparation of Evaluation Sample )
present invention can provide similar performance on not Using the seven conductive glass pastes EP -01 to EP - 07
only these metals, but also on alloys of them . Solder is as in Table 12 , electrodes /interconnections were formed in
generally applied to forma conductive junction between an interconnection pattern illustrated in FIG . 7 . With refer
metal substrates . In consideration of differentiation from the ence to FIG . 7 , a substrate 6 used herein was any of the
solder, Ag particles and Al particles are effective as themetal 45 aluminum oxide (Al,0z) substrate , borosilicate glass sub
particles to be contained in the conductive material or in the strate, silicon ( Si) substrate , ferrite substrate , and polyimide
corresponding conductive glass paste . The solder hardly substrate . Interconnections 7 to 13 correspond respectively
establish good conductive junction on Al substrates and to EP -01 to EP - 07 in Table 12 . Initially , the individual
other metal substrates bearing a natural oxide layer on the conductive glass pastes were applied onto each of the
surface . In contrast, the conductive material and conductive 50 substrates by a screen process printing to form patterns of a
glass paste according to the embodiments of the present size of 2 mm by 30 mm , and dried at 120° C . to 150° C . in
invention can establish good conductive bonding ( conduc- the air . The patterns in this process had a thickness of 30 to
tive junction ) even on such metal substrates . This is archived 40 um . This was placed in an electric furnace , heated up to
by the action of the constitutive lead -free low -melting glass 220° C . at a rate of temperature rise of 10° C . per minute ,
composition according to the embodiment of the present 55 held for 30 minutes, further heated up to a temperature
invention. higher than the softening point T , of the corresponding
The data demonstrated that the conductive material and lead- free low -melting glass composition by about 50° C . at
corresponding conductive glass paste according to embodi- the same rate of temperature rise as above , held for 20
ments of the present invention are very effective for the minutes , and thereby formed interconnections 7 to 13 on the
low - temperature formation of conductive junctions in vari- 60 substrate 6 . This experimental example employed the lead
ous electronic components . When a portion to be bonded or free low -melting glass composition VTA -141, and the
sealed may have conductivity , the conductive material and samples were heated up to 300° C ., i.e., a temperature higher
corresponding conductive glass paste according to embodi than the softening point T , by about 50° C .
ments of the present invention are usable also as a low (Evaluation of Interconnect Resistance )
temperature sealing glass frit and a corresponding low - 65 As described above, the interconnections 7 to 13 were
temperature sealing glass paste as described in Experimental formed on each substrate using the seven conductive glass
Example 3 . pastes EP -01 to EP -07 having blending ratios given in Table
US 9 ,950 ,948 B2
31 32
12 . The interconnect resistance of each of the interconnec type of the substrates at a lead -free low -melting glass
tions was measured by the four probe method . composition having the VTA - 141 content of 10 volume
percent or more and a Ag metal particles content of 90
TABLE 12 volume percent or less, as is demonstrated by the data of
5 EP -02 to EP -07 in Table 13. However, the samples suffered
Content (amount ) of lead - free low -melting glass composition
and metal particles in electrode/ interconnection from an interconnection peeling , were evaluated as rejected ,
and were considered to have an insufficient adhesion at the
Lead - free VTA - 141 content of 5 volume percent and the Ag contentof
low -melting Ag
Electrode glass composition metal particles 10
95 volume percent. These results demonstrated that the
interconnection VTA - 141 (in (in volume lead-free low -melting glass composition in the conductive
number volume percent) percent) Remarks material satisfactorily softens and flows upon the intercon
EP-01 ?
Interconnection 7 nection formation and is thereby bonded to and brought into
in FIG . 7 intimate contact with the substrate ; but that the glass com
EP -02 ö &
Interconnection 8
in FIG . 7
15 position , if present in an excessively low content, insuffi
EP -03 á
Interconnection 9 ciently comes into contact with the substrate . This demon
in FIG . 7 strated that the conductive material preferably contains the
EP-04 .
Interconnection 10 lead - free low -melting glass composition in the content of 10
EP- 05 et? §
in FIG . 7
Interconnection 11
in FIG . 7
volume percent or more . It should be noted , however, that
even a conductive material containing the lead - free low
EP -06 $ 8 Interconnection 12 melting glass composition in the content of 5 volume
in FIG . 7 percent can sufficiently possibly offer a good adhesion if a
EP-07 Interconnection 13 refinement such as pressurizing upon the interconnection
in FIG . 7
formation can be made.
25
( Evaluation of Adhesion ) TABLE 13
The interconnections 7 to 13 were subjected to a peel test Electrode /interconnection peel test results
to evaluate adhesion to the substrates. A peeling tape was
applied to each interconnection on the substrate and then Electrode/
peeled off. A sample suffering from neither peeling of the 30 inter Borosilicate
glass Polyimide
interconnection from the substrate nor break was evaluated connection Al2O3 Silicon Ferrite
number subst
substrate substrate substrate substrate substrate
as " accepted ” . In contrast , a sample suffering from peeling
and /or break in the interconnection was evaluated as EP -01
EP -02
Rejected Rejected
Accepted Accepted
Rejected Rejected Rejected
Accepted Accepted Accepted
" rejected ” . EP -03 Accepted Accepted Accepted Accepted Accepted
Typically, interconnections were formed on each substrate 35 EP - 04 Accepted Accepted Accepted Accepted Accepted
using conductive materials each containing the lead -free EP -05 Accepted Accepted Accepted Accepted Accepted
low -melting glass composition VTA - 141 and the Ag metal EP -06 Accepted Accepted Accepted Accepted Accepted
particles . FIG . 8 illustrates how the interconnect resistance EP - 07 Accepted Accepted Accepted Accepted Accepted
of the interconnections varies depending on the contents of
VTA - 141 and Ag in the conductive materials. The tested 40 As is demonstrated above , the lead - free low -melting glass
substrates were five substrates, i.e., an Al2O3 substrate , a compositions according to the embodiment of the present
borosilicate glass substrate , a Si substrate , a ferrite substrate , invention can be expanded effectively into conductivemate
and a polyimide substrate . However, little difference in rials and corresponding conductive glass pastes to form
interconnect resistance among the substrates was found . The electrodes/interconnections at a low temperature . In this
interconnect resistance decreased with an increasing Ag 45 experimental example , VTA - 141 was used and described as
content and a decreasing VTA - 141 content and reached the a representative lead - free low -melting glass composition .
order of 10 - 6 cm at the Ag content of 70 to 95 volume Obviously ,however, other lead - free low -melting glass com
percent and the VTA - 141 content of 30 to 5 volume percent. positions according to embodiments of the present invention
The interconnect resistance reached its minimum level at the can develop performance at similar levels . Likewise , the Ag
Ag content of about 85 to about 90 volume percent and the 50 particles were used in this experimental example as metal
VTA - 141 content of about 10 to about 15 volume percent. particles to be contained in conductive materials and corre
The lead -free low -melting glass composition according to sponding conductive glass pastes . Also obviously, the pres
the embodiment of the present invention can satisfactorily ent invention is not limited thereto and can be applied also
soften and flow , and thereby promotes the necking of Ag to Ag alloys, Cu , Al, and Sn , and alloys of them . The above
particles upon the interconnection formation , as is described 55 evaluations and considerations demonstrated that the con
above. Thus, the present invention enables the formation of ductive materials and corresponding conductive glass pastes
electrodes/interconnections at such a low temperature (e.g ., ??
300° C . in this experimental example ), where the resulting effective for the low -temperature formation of electrodes/
electrodes /interconnections have a remarkably low intercon - interconnections in various electronic components.
nect resistance . The five different substrates, i. e ., the Al,Oz 60
substrate , borosilicate glass substrate , Si substrate , ferrite Experimental Example 6
substrate , and polyimide substrate were investigated in this
experimental example . It can be easily surmised that the In this experimental example , vacuum - insulating double
present invention is applicable also to other substrates . glass panels were prepared representatively as a glass -sealed
Table 13 shows the peel test results of the interconnec - 65 component according to an embodiment of the present
tions formed on the substrates. The samples were evaluated invention . Specifically , the vacuum - insulating double glass
as accepted and offered a good adhesion with respect to any panels were prepared using a pair of soda- lime glass sub
US 9, 950, 948 B2
33 34
strates , and a low -temperature sealing glass frit according to soda -lime glass substrate 15 , where the heat-reflecting film
an embodiment of the present invention . Whether and how 22 has been previously formed typically by vapor deposi
the low - temperature sealing glass frit according to the
embodiment of the present invention can be applied was The soda -lime glass substrates 15 and 16 used in this
evaluated . In this experimental example , a low -temperature 5 experimental example each had a size of 900 by 600 by 3
sealing glass paste was used to form the low -temperature mm . The soda - lime glass substrate 15 bore the heat-reflect
sealing glass frit. ing film 22, and the soda - lime glass substrate 16 included the
FIG . 9A is a schematic plan view of the prepared vacuum evacuation port 20 . The panel included the spherical beads
insulating double glass panel. FIG . 9B is an enlarged view
19 having a diameter of a little under 200 um in the seal
of a cross -section taken along the line A - A of FIG . 9A in a 10 portion
portion adjacent to a seal portion . 14 and the spacers 18 so as to allow the distance
As illustrated in FIG . 9A , the vacuum - insulating double between the soda -lime glass substrates 15 and 16 , namely ,
glass panel includes a soda -lime glass substrate 15 and the thickness of the space 17 , to be about 200 um . The
spherical beads 19 included soda -lime glass . The low
another soda -lime glass substrate 16 ( see FIG . 9B ) disposed
as overlying the substrate with a gap (space). The panel also 15 temperature sealing glass frit used in the seal portion 14
includes a seal portion 14 in a circumferential portion of the included the lead - free low -melting glass composition VTA
substrates 15 and 16 . The panel includes plural spacers 18 146 ( see Tables 2 and 3 ) and the low -thermal-expansion
between the two substrates 15 and 16 . The spacers 18 are ceramic particles CF -01 (see Table 4 ) in a blending ratio in
two - dimensionally disposed and spaced uniformly . The volume percent of 50 :50 . The spherical beads 19 were
soda -lime glass substrate 16 includes an evacuation port 20 . 20 contained in the seal portion 14 in a content of 1 volume
The gap between the two substrates 15 and 16 has been percent with respect to the volume of the low -temperature
evacuated through the evacuation port 20 using a vacuum sealing glass frit ; and were contained in the spacers 18 in a
pump (not shown ). The evacuation port 20 is capped with a content of 20 volume percent with respect to the volume of
cap 21 . the low - temperature sealing glass frit.
As illustrated in FIG . 9B , the panel includes a space (the 25 (Preparation of Low - Temperature Sealing Glass Paste )
gap ) 17 between the pair of soda - lime glass substrate 15 and The lead- free low -melting glass composition according to
16 including the seal portion 14 in the peripheral portion the embodiment of the present invention in the form of
( edge portion ). The space 17 is maintained under vacuum . particles , the low -thermal- expansion ceramic particles, and
The seal portion 14 has been sealed using the low -tempera - a solvent were blended ,mixed , and yielded low -temperature
ture sealing glass frit according to the embodiment of the 30 sealing glass pastes. The lead - free low -melting glass com
present invention . The vacuum -insulating double glass panel position particles used herein were VTA - 146 particles hav
can be expanded typically into architectural window panes ing a particle diameter of about 10 um ; and the low -thermal
and doors of commercial-use refrigerators and freezers . The expansion ceramic particles were CF -01 ( zirconium
low - temperature sealing glass frit according to the embodi phosphate tungstate ) particles having a particle diameter of
ment of the present invention used to form the seal portion 35 about 30 um . The solvent was a -terpineol, added with
14 contains , in addition to the lead - free low -melting glass isobornylcyclohexanol as a viscosity modifier. The lead - free
composition according to the embodiment of the present low -melting glass composition particles VTA - 146 and the
invention , low - thermal-expansion ceramic particles so as to low - thermal- expansion ceramic particles CF -01 were
have a coefficient of thermal expansion conformable to the blended in a ratio in volume percent of 50 :50, and the
coefficient of thermal expansion of the soda -lime glass 40 low -temperature sealing glass pastes were prepared so as to
substrates 15 and 16 . The soda -lime glass substrates 15 and have a solids content of 75 to 80 mass percent, where the
16 have heat resistance up to a temperature of about 500° C ., " solids content” refers to the total content of VTA - 146 and
and the seal portion 14 may be formed at a temperature equal CF -01. The low -temperature sealing glass pastes further
to or lower than that temperature. The soda -lime glass contained soda - lime glass spherical beads having a particle
substrates 15 and 16 are susceptible to failure upon rapid 45 diameter of about 180 to about 200 um in a content of 1
heating or rapid cooling. To prevent this , heating and cooling volumepercent for the low -temperature sealing use and 20
in the sealing have to be performed gradually . The sealing is volume percent for the spacers. The contents herein are each
preferably performed at a temperature as low as possible so with respect to the solids content.
as to produce the vacuum - insulating double glass panel with ( Preparation of Vacuum - Insulating Double Glass Panel)
better productivity . In addition , the soda -lime glass sub - 50 The vacuum - insulating double glass panel was prepared
strates 15 and 16 are susceptible to failure upon deformation . in this experimental example by a method that will be
To prevent this , the plural spacers 18 are disposed in the described with reference to FIGS . 10A to 12 .
space 17 maintained under vacuum . For allowing the space FIG . 10A illustrates the soda -lime glass substrate 16
17 to have an adequate thickness , it is effective , for example, bearing the seal portion 14 and the spacers 18 , where the
to introduce spherical beads 19 having approximately iden - 55 glass substrate 16 is to constitute the vacuum - insulating
tical particle diameters into the spacers 18 and the seal double glass panel illustrated in FIGS. 9A and 9B .
portion 14 . The spacers 18 can be fixed using the low - As illustrated in FIG . 10A , the prepared low - temperature
temperature sealing glass frit according to the embodiment sealing glass pastes were applied to the peripheral portion
of the present invention , as with the seal portion 14 . For (corresponding to the seal portion 14 ) and the inside (cor
obtaining the space 17 maintained under vacuum , the evacu - 60 responding to the spacers 18 ) of the soda - lime glass sub
ation port 20 is previously formed in the soda - lime glass strate 16 each by dispensing and dried at 120° C . to 150° C .
substrate 16 , and the space 17 is evacuated through the in the air . The resulting article was heated up to 220° C . at
evacuation port 20 using a vacuum pump. After the evacu - a rate of temperature rise of 7° C . per minute in the air , held
ation , the evacuation port 20 is capped with the cap 21 so as for 30 minute , further heated up to 300° C . at the same rate
to maintain the space 17 under vacuum . The panel, when 65 of temperature rise as above, and held for 30 minutes to
applied as an architectural window pane, may further allow the seal portion 14 and the spacers 18 to be bonded to
include a heat -reflecting film 22 on the inner surface of the the soda - lime glass substrate 16 .
US 9 ,950,948 B2
35 36
FIG . 10B is a cross -sectional view taken along the line addition , the low -temperature sealing glass frit and /or cor
A -AofFIG . 10A . As illustrated in FIG . 10B , the seal portion responding low -temperature sealing glass paste according to
14 and the spacers 18 each include the spherical bead 19 . the embodiment of the present invention , when used ,
FIG . 11A illustrates the soda - lime glass substrate 15 to enables sealing to be performed at a remarkably low tem
constitute the vacuum - insulating double glass panel in FIG . 5 perature and can significantly contribute to better produc
9B . FIG . 11B is a cross - sectional view taken along the line tivity of such vacuum - insulating double glass panels.
A - A of FIG . 11A . As above , a vacuum - insulating double glass panel has
As illustrated in FIGS. 11A and 11B , the soda - lime glass been described in this experimental example representa
substrate 15 bears the heat -reflecting film 22 on one side tively as a glass - sealed component according to an embodi
thereof. 10 ment of the present invention . Specifically, the low -tempera
FIG . 12 illustrates a final step of themethod for preparing ture sealing glass frit and /or corresponding low -temperature
the vacuum -insulating double glass panel illustrated in sealing glass paste containing the lead - free low -melting
FIGS. 9A and 9B . glass composition according to the embodiment of the
With reference to FIG . 12 , the soda-lime glass substrates present invention was applied to the vacuum -insulating
and 16 were faced toward each other, aligned , and fastened 15 double glass panel. The results demonstrated that the low
with plural heat-resistant clips . This was subjected to a heat temperature sealing glass frit and corresponding low - tem
treatment with evacuation and sealed . perature sealing glass paste containing the lead -free low
FIG . 13 is a graph illustrating a sealing temperature melting glass composition according to the embodiment of
profile in the heat treatment. the present invention can be effectively applied to a seal
According to the sealing temperature profile in FIG . 13 , 20 portion of a glass - sealed component and provides a glass
the panel was heated up to a temperature adjacent to the sealed component having reliability and productivity both at
softening point of the used lead - free low -melting glass satisfactory levels. Obviously, the glass frit and correspond
composition . In this experimental example , the panel was ing glass paste can be effectively expanded also into glass
heated up to 250° C . equal to the softening point of VTA - 146 sealed components other than the vacuum -insulating double
at a rate of temperature rise of 7° C . per minute in the air and 25 glass panel.
held for 30 minutes . While evacuating the inside through the
evacuation port 20 using a vacuum pump , the panel was Experimental Example 7
heated up to 280º C . at a rate of temperature rise of 7° C . per
minute , and held for 30 minutes to be sealed . In this experimental example, a display was prepared
As illustrated in FIG . 12 , the seal portion 14 and the 30 representatively as a glass- sealed component according to
spacers 18 were compressed and came into intimate contact the embodiment of the present invention . Whether and how
with the two soda -lime glass substrates 15 and 16 . The the low -temperature sealing glass frit according to the
evacuation port 20 was then capped with the cap 21 and embodiment of the present invention is applicable was
yielded a vacuum - insulating double glass panel. In this determined and evaluated . The display included a multiplic
experimental example, ten vacuum - insulating double glass 35 ity of organic light- emitting diodes (OLEDs) between a pair
panels were prepared in the above manner . of borosilicate glass substrates. This experimental example
(Evaluation Results of Prepared Vacuum - Insulating employed a low -temperature sealing glass paste to form the
Double Glass Panels ) low - temperature sealing glass frit .
Initially , the ten vacuum -insulating double glass panels FIG . 14A is a schematic plan view of an OLED display
prepared in this experimental example were visually 40 according to an embodiment of the present invention . FIG .
inspected . As a result , they were found to have no visual 14B is a cross - sectional view taken along the line A - A of
defects such as fracture or cracking . The spherical beads 19 FIG . 14A .
in the seal portion 14 and in the spacers 18 allowed the With reference to FIG . 14A , the OLED display includes
soda - lime glass substrates 15 and 16 to be held at an a borosilicate glass substrate 23 , another borosilicate glass
approximately uniform distance (thickness of the space 45 substrate 24 ( see FIG . 14B ) disposed as overlying the
therebetween ). Specifically , the obtained vacuum -insulating borosilicate glass substrate 23 with a gap , and a seal portion
double glass panel had a predetermined space 17 . The panel 14 formed using the low -temperature sealing glass frit
was further subjected to a helium leak test and was found according to the embodiment of the present invention in a
that the panel inside was maintained under vacuum , and the peripheral portion of the borosilicate glass substrates 23 and
panel peripheral portion was hermetically sealed . 50 24 . The OLED display includes OLEDs 25 between the
For the determination of the reliability of the seal portion borosilicate glass substrates 23 and 24 .
14 , three of the prepared vacuum - insulating double glass The OLEDs 25 are susceptible to deterioration by the
panels were immersed in warm water at 50° C . for 30 days . presence of water and /or oxygen . To prevent this , it is
As a result , it was found that the inside of all the three panels important for the peripheral portion , i.e., the seal portion 14
could be maintained under vacuum without migration of 55 of the borosilicate glass substrates 23 and 24 to be hermeti
water thereinto . cally sealed with the low -temperature sealing glass frit
Other three of the vacuum - insulating double glass panels containing the lead - free low -melting glass composition
were subjected to 1000 cycles of a thermal cycle test in the according to the embodiment of the present invention . The
range of - 50° C . to + 100° C . Also in this test, all the three low -temperature sealing glass frit according to the embodi
panels could maintain the inside under vacuum . These 60 ment of the present invention used in the seal portion 14
results demonstrated as follows. Assume that the low -tem - contains, in addition to the lead - free low -melting glass
perature sealing glass frit and / or corresponding low -tem - composition according to the embodiment of the present
perature sealing glass paste according to the embodiment of invention , low -thermal- expansion ceramic particles so as to
the present invention is applied to a vacuum -insulating have a coefficient of thermal expansion conformable to the
double glass panel. In this case , the vacuum -insulating 65 coefficient of thermal expansion of the borosilicate glass
double glass panel can include a seal portion offering substrates 23 and 24 as much as possible . The low - tempera
satisfactory thermal insulation and having high reliability . In ture sealing glass frit to be applied to the seal portion 14 in
US 9, 950, 948 B2
37 38
this experimental example included the lead - free low -melt generation and thereby allow the lead - free low -melting glass
ing glass composition VTA -134 ( see Tables 2 and 3 ) and the composition to readily soften and flow . The laser beam 26
low - thermal- expansion ceramic particles CF - 02 (see Table traveled at a speed of 10 mm /second in the peripheral
4 ) in a ratio in volume percent of 45:55 . The low -tempera portion to bond the borosilicate glass substrates 23 and 24 in
ture sealing glass frit in this experimental example was 5 the peripheral portion through the seal portion 14 . Thus , the
formed from a low -temperature sealing glass paste further OLED display was prepared .
containing high viscosity a - terpineol as a solvent. In this experimental example , five OLED displays were
(Preparation of Low - Temperature Sealing Glass Paste ) prepared in the above manner. The sealing was performed
The lead - free low -melting glass composition according to using the laser beam so as to prevent or mitigate thermal
the embodiment of the present invention in the form of 10 damage on the OLEDs and to provide better productivity .
particles , the low -thermal- expansion ceramic particles , and (Evaluation Results of Prepared Organic Light-Emitting
the solvent were blended , mixed , and yielded the low - Diode (OLED ) Displays)
temperature sealing glass paste . The lead - free low -melting Initially, one of the prepared OLED displays was sub
glass composition particles used herein were VTA - 134 par - jected to a lighting test and found to properly illuminate . The
ticles having an average particle diameter of about 1 um , and 15 sample OLED display also had good adhesion and bonding
the low -thermal-expansion ceramic particles were CF -02 properties in the seal portion . Next, the OLED display was
particles having an average particle diameter of about 3 um . subjected to a high- humidity /temperature test ( saturated
CF -02 is a compound including mainly zirconium phosphate pressure cooker test) at 120° C ., 100 % relative humidity , and
tungstate . The solvent was a -terpineol, added with isobor - 202 kPa for one day, 3 days, and 7 days . As a comparative
nylcyclohexanol as a viscosity modifier. The low -thermal- 20 example, an OLED display including a portion sealed with
expansion ceramic particles CF - 02 contained iron tungstate a resin was also subjected to the test. The resin - sealed
(FeW04) in the zirconium phosphate tungstate particles so p ortion had a line width of about 5 mm and a thickness of
as to efficiently absorb a red semiconductor laser beam to about 15 um . Both the OLED displays properly illuminated
thereby generate heat, as described later. The lead -free in the one -day high -humidity /temperature test, but the resin
low -melting glass composition VTA - 134 particles and the 25 sealed OLED display suffered from significant deterioration
low -thermal-expansion ceramic particles CF - 02 were in illumination in 3 - day and longer high - humidity /tempera
blended in a ratio in volume percent of 45: 55 . The low - ture tests. This is because water and / or oxygen migrated
temperature sealing glass paste was prepared so as to have from the resin -sealed portion into the OLED display and
a solids content of about 80 mass percent, where the “ solids impaired the OLEDs. In contrast, the OLED display accord
content” refers to the total content of VTA - 134 and CF -02. 30 ing to the embodiment of the present invention did not suffer
(Preparation of Organic Light- Emitting Diode (OLED ) from deterioration in illumination of the OLEDs and had
Display ) good test results even in the 7 - day high - humidity / tempera
The OLED display in this experimental example was ture test. The result indicated that the OLED display can
prepared by a method as illustrated in FIGS. 15A to 17 . maintain good hermeticity . In addition , the OLED display
FIG . 15A illustrates one of a pair of substrates in the 35 after the high - humidity /temperature test was examined to
OLED display . FIG . 15B is a cross - sectional view taken evaluate the adhesion and bonding properties of the seal
along the line A - A of FIG . 15A . portion and was found to offer not so significant deteriora
As illustrated in FIG . 15A , the prepared low -temperature tion as compared with the resin -sealed OLED display and to
sealing glass paste was applied to a peripheral portion of the have adhesion and bonding properties similar to those before
borosilicate glass substrate 23 by a screen process printing 40 the test.
and dried at 120° C . to 150° C . in the air . This was heated As above, the organic light-emitting diode (OLED ) dis
up to 220° C . at a rate of temperature rise of 7° C .per minute play has been described in this experimental example rep
in the air , held for 30 minutes , further heated up to 300° C . resentatively as a glass -sealed component according to an
at the same rate of temperature rise as above , and held for embodiment of the present invention . Specifically , the low
30 minutes. This gave the seal portion 14 in the peripheral 45 temperature sealing glass frit and corresponding low -tem
portion of the borosilicate glass substrate 23 . The seal perature sealing glass paste each containing the lead -free
portion 14 was formed in the peripheral portion of the low -melting glass composition according to the embodiment
borosilicate glass substrate 23 so as to have a line width of of the present invention were applied to the OLED display .
about 2 mm and a thickness after firing of about 15 um . The results demonstrated that the low -temperature sealing
FIG . 16A illustrates the other of the pair of substrates to 50 glass frit and corresponding low -temperature sealing glass
constitute the OLED display . FIG . 16B is a cross - sectional paste each containing the lead - free low -melting glass com
view taken along the line A - A of FIG . 16A . position according to the embodiment of the present inven
As illustrated in these figures, a multiplicity of OLEDs tion can be effectively applied to a seal portion of a glass
was formed on the borosilicate glass substrate 24 . The sealed component and provides a glass -sealed component
number of the OLEDs 25 corresponds to the number of 55 having high functions including reliability and being
picture elements. As illustrated in FIG . 17, the borosilicate
obtained with excellent productivity . In addition , the results
glass substrate 24 bearing the OLEDs 25 was arranged to of the experimental example obviously demonstrate that the
face the borosilicate glass substrate 23 bearing the seal glass frit and corresponding glass paste can also be
portion 14 , and a laser beam 26 was applied in an inert gas expanded into glass - sealed components that are susceptible
(nitrogen ) from the borosilicate glass substrate 23 side 60 to thermal damage . Such glass -sealed components are exem
toward the seal portion 14 . The laser beam 26 used herein plified by lighting apparatuses bearing OLEDs; and organic
was a red semiconductor laser beam having a wavelength of solar cells.
805 nm so that the laser beam is efficiently absorbed by the
lead - free low -melting glass composition and the low -ther Experimental Example 8
mal-expansion ceramic particles in the low - temperature 65
sealing glass frit according to the embodiment of the present In this experimental example , a solar cell including sili
invention . The absorbed laser beam may contribute to heat con (Si) substrates having pn bonding was prepared repre
US 9 ,950,948 B2
39 40
sentatively as an electrical/ electronic component according (Al) particles having an average particle diameter of about
to an embodiment of the present invention . Whether and 3 um in a blending ratio in volume percent of 10 : 90 .
how a conductive material according to an embodiment of (Preparation of Conductive Glass Paste )
the present invention is applicable to electrodes /intercon - The lead - free low -melting glass composition according to
nections of the solar cell was examined and evaluated . The 5 the embodiment of the present invention VTA - 102 or VTA
conductive material in this experimental example was 125 in the form of particles, the silver (Ag ) oraluminum (Al)
formed using a conductive glass paste . metal particles, and a solvent were blended , mixed , and
FIG . 18A is a schematic view of a light -receiving surface yielded conductive glass pastes . The conductive glass paste
( front surface of the prepared solar cell . FIG . 18B is a to form the front electrodes / interconnections 28 and the
schematic view of the rear surface (backside ) of the solar 10 output electrodes/ interconnections 30 employed VTA - 102
cell. FIG . 18C is a cross -sectional view taken along the line particles having an average particle diameter of about 1 um
A - A of FIG . 18A . and spherical Ag particles having an average particle diam
As illustrated in FIG . 18A , the solar cell includes front eter of about 1.5 um in a blending ratio in volume percent
electrodes/ interconnections 28 and an antireflection film 31 of 15 : 85 . The solvent used was a -terpineol, added with
on the light- receiving surface of the silicon substrate (Si 15 isobornylcyclohexanol as a viscosity modifier . The conduc
substrate ) 27 . tive glass paste to form the collector electrode/interconnec
As illustrated in FIG . 18B , the solar cell includes a tion 29 employed VTA - 125 particles having an average
collector electrode/interconnection 29 and output electrodes particle diameter of about 1 um and spherical Al particles
interconnections 30 on the rear surface . having an average particle diameter of about 3 um in a
As illustrated in FIG . 18C , the solar cell includes a pn 20 blending ratio in volume percent of 10 : 90 . The solvent used
junction 181 adjacent to the light-receiving surface of the was a - terpineol, added with isobornylcyclohexanol as a
silicon substrate 27 . The front electrodes/interconnections viscosity modifier. Each of the conductive glass pastes had
28 , collector electrode/ interconnection 29 , and output elec - a solids content of about 80 mass percent, where the " solids
trodes /interconnections 30 are formed using the conductive content” refers to the total content of the lead - free low
material according to the embodiment of the present inven - 25 melting glass composition particles and the metal particles.
tion . (Preparation of Solar Cell)
A conventional solar cell has been prepared in the fol - The solar cell as illustrated in FIGS. 18A to 18C was
lowing manner. Front electrodes / interconnections 28 and prepared by a method that will be described below .
output electrodes /interconnections 30 are formed using a The silicon substrate 27 ( 150 by 150 by 0 .2 mm ) used
lead - containing conductive glass paste containing silver 30 herein bore the antireflection film 31 on the light- receiving
( Ag) particles and lead - containing low -melting glass com - surface . The above -prepared conductive glass paste contain
position particles. A collector electrode/interconnection 29 is ing VTA -102 particles and Ag particles was applied to the
formed using a lead - containing conductive glass paste con - light- receiving surface of the silicon substrate 27 by a screen
taining aluminum (Al) particles and lead -containing low process printing and dried at 120° C . to 150° C . This was
melting glass composition particles . These lead - containing 35 heated in a tunnel furnace up to 220° C . at a rate of
conductive glass pastes are applied to the both sides of a temperature rise of about 20° C . per minute , held for 10
silicon substrate 27 typically by a screen process printing , minutes, further heated up to 290° C . at the same rate of
dried , fired at 500° C . to 800° C . in the air, and yield temperature rise as above , and held for 5 minutes to form the
electrodes/interconnections on the both sides of the silicon front electrodes/interconnections 28 on the light-receiving
substrate 27 . Unfortunately , the conventional solar cell not 40 surface of the silicon substrate 27. Next, the above -prepared
only contains hazardous lead , but also has various disad conductive glass paste containing VTA - 102 particles and Ag
vantages as follows. Typically , such high - temperature firing particles was applied to the rear surface of the silicon
to form the electrodes/ interconnections causes the solar cell substrate 27 by the screen process printing and dried at 120°
to warp significantly and thereby causes the silicon substrate C . to 150° C . The above-prepared conductive glass paste
27 to be susceptible to failure (breakage ). The high -tem - 45 containing VTA - 125 particles and Al particles was applied
perature firing also induces a reaction between Al in the by the screen process printing and dried at 120° C . to 150°
collector electrode/ interconnection 29 and Ag in the output C . This was fired under the same heating conditions as in the
electrodes /interconnections 30 to form brittle intermetallic formation of the front electrodes/ interconnections 28 and
compounds. The brittle intermetallic compounds , if receiv - thereby formed the collector electrode /interconnection 29
ing stress in a focused manner , may cause the silicon 50 and the output electrodes/interconnections 30 on the rear
substrate 27 to be susceptible to defects such as cracks. surface of the silicon substrate 27 . The front electrodes/
In this experimental example , the silicon substrate 27 interconnections 28 received two thermal hystereses. This
including the pn junction was a solar - cell-use single - crystal allowed the front electrodes /interconnections 28 to have
silicon substrate having a size of 150 by 150 by 0 .2 mm . In good electrical connection to the silicon substrate 27 . The
addition , a silicon nitride ( SIN ) antireflection film 31 was 55 front electrodes /interconnections 28 , collector electrode /in
formed on the light-receiving surface of the silicon substrate terconnection 29, and output electrodes /interconnections 30
27 . The antireflection film 31 had a thickness of about 100 were formed in the above manner and yielded a solar cell
nm . The front electrodes /interconnections 28 and the output according to an embodiment of the present invention . In this
electrodes/interconnections 30 were formed using a conduc - experimental example , ten solar cells were prepared in the
tive material. The conductive material contained the lead - 60 above manner.
free low -melting glass composition VTA - 102 (see Table 1) (Evaluation Results of Prepared Solar Cells)
and spherical silver (Ag ) particles having an average particle Initially, the ten solar cells prepared in this experimental
diameter of about 1 .5 um in a blending ratio in volume example were visually inspected . As a result , the silicon
percent of 15 : 85 . The collector electrode/ interconnection 29 substrate 27 , as well as the front electrodes / interconnections
was formed using another conductive material. This con - 65 28, collector electrode / interconnection 29, and output elec
ductive material contained the lead - free low -melting glass trodes/ interconnections 30 formed on the silicon substrate
composition VTA -125 (see Table 1) and spherical aluminum 27 , offered no defects such as fracture and cracking, no
US 9 ,950,948 B2
41 42
significant warpage , and no appearance disadvantages. This component according to an embodiment of the present
effect was achieved by the lead - free low -melting glass invention . Whether and how the conductive material and the
compositions according to the embodiments of the present low -temperature sealing glass frit according to embodiments
invention . Specifically, the electrodes/ interconnections of the present invention are applicable to conductive junc
could be formed at a significantly low temperature. Next, the 5 tions and /or seal portions of the package was examined and
prepared ten solar cells were further examined and found to evaluated . In this experimental example , the conductive
have electrical connection between the silicon substrate 27 material and the low - temperature sealing glass frit were
and the front electrodes/interconnections 28 and to establish formed respectively using a conductive glass paste and a
ohmic contact between the silicon substrate 27 and the low - temperature sealing glass paste .
collector electrode/interconnection 29 and between the sili
con substrate 27 and the output electrodes / interconnections 10 resonator
FIGS. 19A to 19F illustrate how to prepare the quartz
package . FIG . 19G is a schematic cross - sectional
30 . The ten solar cells were further examined using a solar view of the prepared quartz resonator package.
simulator to evaluate the generation efficiency . As a result ,
the solar cells were found to have a generation efficiency of The quartz resonator package illustrated in FIG . 19G
about 18 % as high as the generation efficiency of conven includes a ceramic substrate 33 and a quartz resonator 32 .
tional equivalents, even though the solar cells were prepared 15 The ceramic substrate 33 includes interconnections 34 . The
at a remarkably low temperature . To determine the reliabil- quartz resonator 32 is disposed over the ceramic substrate 33
ity , three of the prepared solar cells were immersed in warm via conductive junctions 35 . The interconnections 34 and the
water at 50° C . for 5 days and examined to measure the conductive junctions 35 are electrically connected to each
generation efficiency in a similar manner as above. The other. This allows the quartz resonator 32 to be electrically
conventional solar cell suffered from corrosion of the elec - 20 connected to the outside. The package further includes a
trodes/interconnections and had significantly lower genera ceramic cap 36 to protect the quartz resonator 32. The
tion efficiency of about 12 % to about 13 % . In contrast, the ceramic cap 36 is hermetically bonded to a peripheral
solar cells prepared in this experimental example little portion of the ceramic substrate 33 in the seal portion 37 .
suffered from corrosion of the electrodes/interconnections The conductive junctions 35 are formed using the conduc
and offered approximately no deterioration in generation 25 tive material according to the embodiment of the present
efficiency . This is probably because the specific reaction of invention, and the seal portion 37 is formed using the
the lead - free low -melting glass composition according to the low -temperature sealing glass frit according to the embodi
embodiment of the present invention with Ag or Al can give ment of the present invention .
solar cells having such high reliability , as described in The quartz resonator package is prepared in the following
Experimental Example 4 . or 30 manner .
Next, an overlap portion of the collector electrode/ inter
connection 29 and the output electrodes/ interconnections 30 nections 34, the
Initially
is
ceramic substrate 33 bearing the intercon
prepared (FIG . 19A ). Next, the conductive
on the rear surface was disintegrated and examined . As a
result, the overlap portion was found to include no brittle glass paste is applied onto the interconnections 34 , dried ,
intermetallic compound that is formed by the reaction heated in the air or in an inert gas to allow the lead -free
between Ag and Al. Thus, the silicon substrate 27 came to 35 low -melting glass composition in the conductive glass paste
resist defects such as cracking even when receiving stress in to soften and flow to thereby form the conductive junctions
a focused manner. In addition , the silicon substrate 27 35 (FIG . 19B ).
significantly less suffered from warpage , and this contrib - The quartz resonator 32 is arranged on the conductive
uted less failure of the solar cell when handled typically junctions 35 (FIG . 19C ), heated in an inert gas or in a
upon assemblage into a module . Thus, the brittle interme- 40 vacuum to allow the lead - free low -melting glass composi
tallic compounds were prevented from forming and the solar tion in the conductive junctions 35 to soften and flow again
cell less suffered from warpage . This is because the solar cell to thereby establish electric connection .
according to the embodiment of the present invention can be Independently , the ceramic cap 36 is prepared ( FIG . 19D ).
fired at a significantly low temperature (290° C .) as com - The low -temperature sealing glass paste is applied to a
pared with the firing temperatures ( 500° C . to 800° C .) of the 45 peripheral portion of the ceramic cap 36 (FIG . 19E ), dried ,
conventional solar cells . and heated in the air to allow the lead - free low -melting glass
As above, the solar cell has been described in this
experimental example representatively as an electrical/elec composition
soften and
in the low -temperature sealing glass paste to
flow to thereby form the seal portion 37.
tronic component according to an embodiment of the present The ceramic substrate 33 bearing the quartz resonator 32
invention . Specifically, the solar cell included electrodes /
interconnections formed using the conductive material and 50 and the conductive junctions 35 ( see FIG . 19C ) is arranged
corresponding conductive glass paste each containing the as illustrated in FIG . 19F to face the ceramic cap 36
lead - free low -melting glass composition according to the including the seal portion 37 (see FIG . 19E ) and heated in
embodiment of the present invention . The conductive mate an inert gas or in a vacuum while applying some load 38 to
rial and corresponding conductive glass paste each contain - allow the lead - free low -melting glass composition in the seal
ing the lead - free low -melting glass composition according to 55 portion 37 to soften and flow again . This gives the quartz
the embodiment of the present invention can be effectively resonator package (FIG . 19G ).
applied to electrodes /interconnections of not only such solar T he process may be performed carefully so as to prevent
cells, but also various electrical/electronic components . The the conductive junctions 35 from separating from the quartz
conductive material and corresponding conductive glass resonator 32 and the interconnections 34 . For this reason , the
paste can provide electrical/ electronic components that have 60 ceramic cap 36 and the ceramic substrate 33 are preferably
higher functions such as reliability and excel typically in sealed at a temperature equal to or lower than the softening
productivity and yield . point of the lead - free low -melting glass composition in the
conductive junctions 35 . Specifically , the lead - free low
Experimental Example 9 melting glass composition to be contained in the low
65 temperature sealing glass paste preferably differs from , and
In this experimental example , a quartz resonator package has a softening point lower than , the lead - free low -melting
was prepared representatively as an electrical/electronic glass composition to be contained in the conductive glass
US 9 ,950 ,948 B2
43 44
paste . The two lead - free low -melting glass compositions Next, the quartz resonator 32 was arranged on the formed
may have a difference in softening point between them of conductive junctions 35 , heated up to 330° C . at a rate of
20° C . or higher, and preferably 40° C . or higher . temperature rise of 20° C . perminute in an inert gas (argon ),
(Preparation of Conductive Glass Paste and Low - Tem and held for 10 minutes to connect the quartz resonator 32
perature Sealing Glass Paste ) 5 to the conductive junctions 35 ( FIG . 19C ).
In this experimental example, the lead -free low -melting Independently, the prepared low -temperature sealing
glass composition to be contained in the conductive glass glass paste was applied to the peripheral portion of the
paste was VTA - 142 having a softening point of 280° C . (see ceramic cap 36 by the screen process printing and dried at
120° C . to 150° C . in the air ( FIGS. 19D and 19E ) . This was
Tables 2 and 3 ); and the lead - free low -melting glass com
position to be contained in the low -temperature sealing glass 10 heated up to 220° C . at a rate of temperature rise of 10° C .
paste was VTA - 132 having a softening point of 240° C . (see to 280º C . atinthe
per minute the air , held for 20 minutes , further heated up
same rate of temperature rise as above , and
Tables 2 and 3 ). VTA -142 and VTA - 132 have a difference in held for 10 minutes to form the seal portion 37 in the
softening point of 40° C . and enable sealing without prob peripheral portion of the ceramic cap 36 . The heating
lems such as separation of the conductive
conductive junctions
junctions 35so .. This
This 15 temperature of 280º C . is higher than the softening point of
means that the conductive junctions 35 and seal portion 37 VTA - 132 by 40° C
both at satisfactorily levels can be obtained at once. The ceramic cap 36 bearing the seal portion 37 was
Initially, particles of a lead -free low -melting glass com arranged so as to face the ceramic substrate 33 connected to
position according to an embodiment of the present inven the quartz resonator 32 . The resulting article was placed in
tion , metal particles, and a solventwere blended ,mixed , and 20 a dedicated fixture and applied with a load (FIG . 19F ). This
yielded the conductive glass paste for the formation of the was heated up to 280º C . at a rate of temperature rise of 10°
conductive junctions 35 . The lead -free low -melting glass C . per minute in a vacuum , held for 10 minutes to seal the
composition particles used herein were VTA - 142 particles ceramic cap 36 and the ceramic substrate 33 , and yielded the
having an average particle diameter of about 3 um ; the metal quartz resonator package (FIG . 19G ). In this experimental
particles were spherical silver ( Ag) particles having an 25 example , twenty - four quartz resonator packages were pre
average particle diameter of about 1. 5 um ; and the solvent pared in the above manner.
was a -terpineol. The paste was further added with isobor - (Evaluation Results of Prepared Quartz Resonator Pack
nylcyclohexanol as a viscosity modifier. The VTA - 142 par - ages )
ticles and the Ag particles were blended in a ratio in volume Initially, eighteen of the quartz resonator packages pre
percent of 30 :70 . The conductive glass paste was prepared 30 pared in this experimental example were visually inspected
so as to have a solid content of about 80 mass percent, where using a stereoscopic microscope . As a result , the packages
the " solids content” refers to the total content of VTA - 142 offered little misregistration of the ceramic cap 36 upon
and Ag. sealing , did not offer defects such as devitrification due to
Separately, particles of a lead -free low -melting glass crystallization , fracture, and cracking in the seal portion 37 ,
composition according to an embodiment of the present 35 and had no defects in appearance .
invention , low -thermal -expansion ceramic particles, and a Next, whether the conductive junctions 35 in the sealed
solvent were blended , mixed , and yielded the low - tempera - ceramic cap 36 was electrically connected to the quartz
ture sealing glass paste for the formation of the seal portion resonator 32 and to the interconnections 34 was examined
37 . The lead- free low -melting glass composition particles by a conduction test from the interconnections 34 on the rear
used herein were VTA - 132 particles having an average 40 surface of the ceramic substrate 33 . The results verified that
particle diameter of about 3 um ; the low -thermal- expansion the quartz resonators went into action in all the prepared
ceramic particles were CF -01 (zirconium phosphate tung - quartz resonator packages . In addition , five of the prepared
state ) particles having an average particle diameter of about quartz resonator packages were subjected each to a helium
10 um (see Table 4 ); and the solvent was a - terpineol. The leak test and were found that the package inside was
paste was further added with isobornylcyclohexanol as a 45 maintained under vacuum , and the peripheral portion was
viscosity modifier. The VTA - 132 particles and the CF- 01 hermetically sealed with the seal portion 37 . To verify the
particles were blended in a ratio in volume percent of 70 :30 . reliability of the seal portion 37 , five of the prepared quartz
The low -temperature sealing glass paste was prepared so as resonator packages were each subjected a high -humidity /
to have a solids content of about 80 mass percent, where the temperature test ( saturated pressure cooker test) at 120° C .,
" solids content” refers to the total content of VTA - 132 and 50 100 % relative humidity , and 202 kPa for 3 days . The
CF -01. samples were subjected to the helium leak test again and
(Preparation of Quartz Resonator Package ) were found that all the quartz resonator packages after the
The quartz resonator package was prepared in this experi - high -humidity /temperature test maintained the hermeticity
mental example by a method that will be illustrated specifi - and adhesion of the seal portion 37 .
cally below . The ceramic substrate 33 and the ceramic cap 55 The results demonstrated as follows. Assume that a con
36 used in this experimental example were both made of ductive material and/or a corresponding conductive glass
aluminum oxide (a -A1,03). paste each containing a lead - free low -melting glass compo
The prepared conductive glass paste was applied onto the sition according to an embodiment of the present invention
interconnections 34 in the ceramic substrate 33 by dispens - is applied to a conductive junction ; and that a low -tempera
ing and dried at 120° C . to 150° C . in the air (FIGS. 19A and 60 ture sealing glass frit and /or a corresponding low -tempera
19B ). This was heated up to 220° C . at a rate of temperature ture sealing glass paste each containing a lead - free low
rise of 20° C . per minute in the air, held for 20 minutes, melting glass composition according to an embodiment of
heated up to 330° C . at the same rate of temperature rise as the present invention is applied to a seal portion . This can
above, and held for 10 minutes to form the conductive give quartz resonator packages that have high reliability
junctions 35 on the interconnections 34 of the ceramic 65 after consideration of influence on the environmental bur
substrate 33. The heating temperature 330° C . is higher than den . In this experimental example , the conductive material
the softening point of VTA - 142 by 50° C . and others are applied to a quartz resonator package repre
US 9, 950, 948 B2
45 46
sentatively as an electrical/electronic component and a 8 . A low -temperature sealing glass frit comprising:
glass -sealed component according to an embodiment of the the lead -free low -melting glass composition according to
present invention . Obviously , however, the conductive mate claim 1 ; and
rial and corresponding conductive glass paste , low -tempera low - thermal-expansion ceramic particles ,
ture sealing glass frit , and corresponding low -temperature 5 wherein a content of the lead - free low -melting glass
sealing glass paste according to embodiments of the present composition is 40 ormore volumepercent and less than
invention can be effectively expanded not only into such 100 volume percent, and
quartz resonator packages , but also into many of electrical/ a content of the low -thermal- expansion ceramic particles
electronic components and glass -sealed components each is greater than 0 volume percent and 60 or less volume
including a conductive junction and /or a seal portion . percent .
In Experimental Examples 6 to 9 , the vacuum - insulating 9. The low -temperature sealing glass frit according to
double glass panels , OLED displays, solar cells , and quartz claim 8,
wherein the low - thermal-expansion ceramic particles
resonator packages have been described representatively as include at least one selected from the group consisting
glass -sealed components and electrical/ electronic compo - 15 of zirconium phosphate tungstate , quartz glass , zirco
nents according to embodiments of the present invention . nium silicate , aluminum oxide , mullite and niobium
Obviously , however, the present invention is not limited to oxide .
these examples and can be applied to many of glass -sealed 10 . A low -temperature sealing glass paste comprising:
components and electrical/ electronic components such as particles formed of the lead -free low -melting glass com
image display devices, personal digital assistants , IC20 position according to claim 1 ;
ceramic packages , semiconductor sensors , multilayer low -thermal -expansion ceramic particles ; and
capacitors , LEDs, and multilayered circuit boards. a solvent .
11 . The low -temperature sealing glass paste according to
What is claimed is : claim 10 ,
1. A lead - free low -melting glass composition comprising: 25 wherein the low -thermal-expansion ceramic particles
a principal component which includes a vanadium oxide , include at least one selected from the group consisting
a tellurium oxide and a silver oxide; and of zirconium phosphate tungstate, quartz glass, zirco
an additional component which includes at least one nium silicate , aluminum oxide , mullite and niobium
selected from the group consisting of oxides of ele oxide , and
ments in Group 13 of periodic table , 30 wherein the solvent includes at least one of a -terpineol
wherein a content of Teo , is 1 to 2 times as much as a and diethylene glycol n -butyl ether acetate .
content of V205, and 12 . A conductive material comprising :
wherein a content of the additional component is 0 .1 to the lead -free low -melting glass composition according to
3 . 0 mole percent. claim 1 ; and
2 . The lead - free low -melting glass composition according 35 metal particles ,
to claim 1, further comprising an optional secondary com wherein a content of the lead - free low -melting glass
ponent which includes at least one selected from the group composition is 5 ormore volume percent and less than
consisting of BaO , WO3 and P205, wherein the content of 100 volume percent, and
V20 , is 17 to 27 mole percent. a content of the metal particles is greater than 0 volume
3 . The lead - free low -melting glass composition according 40 percent and 95 or less volume percent.
to claim 1 , 13. The conductive material according to claim 12 ,
wherein a content of the optional secondary component is wherein the metal particles include at least one selected
O to 13 mole percent. from the group consisting of silver, silver alloys, cop
4. The lead -free low -melting glass composition according per, copper alloys, aluminum , aluminum alloys, tin and
to claim 1 , 45 tin alloys .
wherein the content of V205 is 17 to 27 mole percent, 14 . A conductive glass paste comprising :
the content of Teo , is 34 mole percent or more, and particles formed of the lead - free low -melting glass com
a content of Ag2O is more than 0 mole percent and up to position according to claim 1 ; and
40 mole percent. a solvent.
5 . The lead - free low -melting glass composition according 50 15 . The conductive glass paste according to claim 14 ,
to claim 1 , further comprising metal particles.
wherein the additional component includes at least one 16 . The conductive glass paste according to claim 15 ,
selected from the group consisting of B203, Al2O3, wherein the metal particles include at least one selected
Ga_03 and In203, and from the group consisting of silver, silver alloys, cop
wherein the content of the additional component is 0 . 1 to 55 per, copper alloys, aluminum , aluminum alloys , tin and
2 .0 mole percent in terms of oxide. tin alloys .
6 . The lead -free low -melting glass composition according 17 . The conductive glass paste according to claim 14 ,
to claim 1 , wherein the solvent includes at least one of a -terpineol
having a softening pointof 280° C . or lower, the softening and diethylene glycol n - butyl ether acetate.
point being determined by differential thermal analysis 6018 . A glass - sealed component having a seal portion
as a second endothermic peak temperature . including 40 to 100 volume percent of a lead - free low
7 . The lead - free low -melting glass composition according melting glass phase ,
to claim 6 , wherein the lead -free low -melting glass phase includes a
having a crystallization onset temperature higher than the principal component including a vanadium oxide , a
softening point by 60° C . or more, the crystallization 65 tellurium oxide and a silver oxide,
onset temperature being determined by the differential a content of Teo , is 1 to 2 times as much as a content of
thermal analysis. V205, and
US 9 ,950, 948 B2
47 48
wherein the lead - free low -melting glass phase further
includes an additional component including at least one
selected from the group consisting of B203, Al2O3,
Ga203 and In203, and
a content of the additional component in the lead - free 5
low -melting glass phase is 0 . 1 to 2 .0 mole percent.
19 . The glass - sealed component according to claim 18 ,
being one of a vacuum - insulating double glass panel and
a display panel.
20 . An electrical/electronic component comprising at least 10
one unit selected from the group consisting of electrodes,
interconnections, and conductive junctions ,
wherein the unit includes 5 or greater volume percent and
less than 100 volumepercent of a lead - free low -melting
glass phase , and greater than 0 volume percent and 95 15
or less volume percent of metal particles,
the lead - free low -melting glass phase including a princi
pal component, a secondary component and an addi
tional component,
wherein the principal component includes a vanadium 20
oxide, a tellurium oxide and a silver oxide ,
a content of Teo , being 1 to 2 times as much as a content
of V2O5, and
wherein the additional component includes at least one
selected from the group consisting of B203, Al2O3, 25
Ga_ 03 and In2O3, and
a content of the additional component in the lead - free
low -melting glass phase being 0 .1 to 2.0 mole percent,
the metal particles including at least one selected from the
group consisting of silver , silver alloys , copper, copper 30
alloys, aluminum , aluminum alloys , tin and tin alloys .
* * * * *

Low-temperature sealing glass frit composition

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MAIMOTOMONTANT UIT DIE HI HINDI HII

(12) United States Patent (10) Patent No.: US 9 ,950,948 B2

(51) Int. CI.

10-5 --- - AI/ALLA

Mihaita?1tz MARATHON arbe

. . . . . . . . . . . . . . .. ... . . . . . . . :.! ! ! ! . . 9001

KITZELULIT TIZITZZZTITITIZITETIT 7777TTTTTTTIIIIIIIIIIIIITETIT

IN AIR WITH EVACUATION

AAceptd ceptd Aceptd Aceptd Aceptd Aceptd Rejcted

(°C)tCheamrpctaeriustec tcopreaymsnilzeotaurn TS 215 220 219 218

Aditonal compnet mole

number vor | Teo Aggo Baowo. | P205 | Alzoz Gazoz In2O3

| VTA - 126 20 .0 38.0

| VTA – 135 20 .0 40 .0 26 .5 13.0 1 - - - 10. 5

Alu Accepted Accepted Comparative Example

Amount (in volume percent) of Amount (in volume percent) of

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