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Wetting and Interface Reaction of BaTiO_3 and Pb(Zr, Ti)O_3 by Ag Metal

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Shonan Institute of Technology

NII-Electronic Library Service

ShonanInstitute of Technology

MEMolRs oF SHoNAN

INenTvTs oF THcHNoLoGy

Vol.es,No.1,I991

Wettingand

Interface

Pb<Zr,Ti)O,Reaction

of

BaTi03

and

by

Ag

Metal

SunaoSUGIHARA'

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k. -t!7i v e.xOgasE: Lv(, BaTi03 2:Pb(Zr,Ti)03 tztwreLk.

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E)a)-tr7E ・ycrJk

ig

Ag Vlj f)TC,

maiLVkhs-)k.

LbiL, agag4io Ti etii'ixma.xblllkL, S"mivCfPbO EbEpti;Lk. -li, Pb{Zr,Ti)Os VcSts

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tscdea)ges2

MPptLt:.

tk,

iwhma#eeop#7ic6\ngfis

BaTi03 vc-.L・-c

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Lka

1. Introduction

In

applications of ele¢tronic ceramlcs, the

electrodes are essentially

important.

The

improvement

of bondability can be

impre-mented by an addition of a glass to an

electrode metal, and the

basic

study

for

the

interfaces

is

necessary.

There

have been a

few

studies on wetting

for

lead

borosilicate

glass-precious metali) and

Na2Si?Os

glass

to

metals likeAu,

Pt

and

Fe!'

as the

basic

ones,

in

which a wetting

has

mainly

been

discussed

from a

view

point of redox reaction.

Fur-thermore, a role of adherence oxides

in

chemical

bonding

at glass-metal

interfaces

were

discussed

as wel13).

In

this study, lead

borosilicate

glass-added

Ag was

put

on

BaTiO,

(BT)

and also on

Pb(Zr,Ti)O,

(PZT)

ceramics to study their

interfaces.

The another samples were three

kinds

of barium titanates

for

a semiconductor.

The

order of

the

processing to

form

the

semiconductors isan as-sintered

BT

first,

the

second one

is

the reduced sample, BaTi03u6

and the

final

is

the surface oxidized one

described

as

BaTi03-j,x.

The

systems were

provided

for

cross sectional analysis with a

SEM

and an

EPMA,

and the rnechanisms of

wetting are discussed as well.

* Stge}][:\geLMXst

gnbR 2 {F 10 Jl 16 Hee"l

2.

Experiments

The wetting experiments of silver

contain-ing

5,20 and 40 weight

%

of

lead

borosilicate

glass on BT and PZT was performed

in

a

vacuum of

10-2"ulO-3

Pa

in a temperature

range up to1000aC.

Wetting

behaviors

were

observed

by

a telescope and contact angles

were measured at the elevating temperature.

The

semiconductors, as-sintered BTs were

reduced at 9500C

in

thereducing atmosphere,

and then these were oxidized at the same

temperature in an air.

These

three kinds

of

barium

titanateswere provided to

inves-tigate the surface condition with an

XPS

analysis. For wetting study of the

semi-conductors, silver was put on each of them

under the same conditions as

described

above.

After wetting experirnents, the superficial

and cross sectional interfaces were

inves-tigated using a

SEM

and an

EPMA.

3.

Resuks and Discussion

1)

Effect

of Glass Frit on Wetting

Photograph.

1 shows the wetting of silver

only on

BT

and

PZT.

The

contact angles

were

90

degrees

for two cases.

Silver

was

not

detected

at the interfacesof the ceramics.

However,

BT

and

PZT

were wetted

by

the

glass-added silver. The contact angles were

46 and 43

degrees

on the

BT

and PZT,

(2)

-59-NII-Electronic Library Service

湘南工 科 大 学紀要 第 25 巻 第 1 号

a

b

Photo 1. 

Wetting

 of BaTiOs (a)and  Pb(Zr, Ti)Os

      (b)byAgat  1000°C.

a

L

b

Photo 2.  Wetting of Ag十40% glass on

     (a)and  PbZr, Ti03 bat 980°C . BaTio3 3.2 2.4 〈 1.6 」 0β 0900    920   940   960   980   1000        (℃}

Fig .1. Temperature  dependence  of  contact

     leロgth height ratio  for  Ag 十fritBaTiO3

   system 40F ; 40 weight frit・added  snver ,

     and  so on). 4.o ρ 3 工 丶 」 2ρ     1.0900    920   940   960   980   1000                                 (℃ )

Fig.2.  Temperature   dependence   of   contact

     length!height ratio for Ag十frit!Pb(Zr, Ti)03

     system (40F:40 weight % frit・added  silver,

     and  so on)・ 「

Frit

一 一   .02 、(  ⊃,  ’. ・バ’・

1

 

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の ご 卩 . ・ °9 頭 尊 書 ヂ … . . ● ”       ・ 》 『 闘 箆 〔 堕 ’ . 岬 . ’ρ     ゐ   ゜     ’     ■     ,         ‘.     ’ . °     吻 “     ム ∴ ・ ∴     .   更 曾 ’

 

 

 

 

T

Photo 3.  EPMA  analysis  for the cross sectiQnal  interfaces of Ag 十40% frit!BaTiOs .

60

(3)

Shonan Institute of Technology

NII-Electronic Library Service

ShonanInstitute of Technology

Wbttingand JntetzfaceReaction

of

BaTi03 and Pb(th,71)03byAg Mlatal

spectively,

in

the case of 40 weight

%

glass,

is

shown

for

the 40%

frit+Ag/PZT

system

for

instance,

as shown in Photo. 2. Figures in Fig.

3.

The place of 40% frit+Ag

is

land2illustratetheratios of contact

length,

hatched

and some elements

in

the

glass

L

and

height,

H on the BT and PZT, re- diffuses concentrically into the PZT base

respectively,

The

LfH

ratios

in

the

base

of which presented the

different

color

from

the

both

BT

and

PZT

showed the minimurn at original PZT after the wetting experiment.

9550C and

9500C,

respectively.

This

may

The

dotted

parts

illustratetheg!assdiffusing

be

explained

by

that the llquidlvapor inter- regions inthis figure. Lead was not

detected

face

tension will be the largest among other

in

the region

between

a,rtva2 whereas

it

was

tensions when silver

begins

to melt at 950"" detected

in

the region between aorvai.

It

is

9600C, and then becomes wetted.

After

the explained by that PbO provided

from

the

minimum, HIL ratios increase with tempera- glass diffuses

into

the

deMcient

part of

PbO

tures.

The

reasons are assumed to

be

due

in

the PZT

base.

These

phenomena will

be

to the vaporization of PbO from the glass elucidated as shown

in

Fig.

4.

As

the

first

for

both

cases, and

due

to the oxygen gas stage,

PbO

is

vaporized

from

PbZr03

in

a

by

the chemical reactions especially

in

the vacuum since

PbZr03

is

easier

decomposed

BT system, given as follows, than PbTiO,5)

in

the

PZT,

then

PbO

is

vided from the glass to react with

Zr02,

and

PbO[gl]+BaTiO, ->

PbTiO,[int]+Ba+1!2

0"

finallythe complete

PbZrO,

can

be

formed.

where

[gl]

istheglassphase and

[int]

indicates

the

interface.

Photograph.

3

shows an

EPMA

analysis

for

A

g + 4

O

%

f r i t

thecross sectional

interfaces

of the 40%

frit+

i

Ag/BT

system.

As

the result, titanium was

pbo

detected

in

the glass region.

It

is

suggested

f22

tas

thattitaniums react with

PbO

to

form

PbTi03

p b

z

r

o

in

the

interfaces

as

described

above.4) 3

The superficial analysis

by

using a

SEM

(1)

:,

i//ls

rtN

s

\

'

t/$,Iil,b,;,

uPZT

N"g

la2;

f

,,s

i/"

i

i

ti'

S

l-

i

---';tX,,,

(2'XAg+4o%frit

: i l

ae ai

{mm)

a:

PbZr03

Superficialdistancesfrom the center of the base

Fig. 3. SEM analysis of each element of the

(3)

surfaceofPZTafterwetting.

(aDNai:

glass Fig.4. Interfacereaction of Pb(Zr,Ti)Os with

diffusionlayer,dotted) Ag+40% glass assembly.

(4)

NII-Electronic Library Service

muwtIaJS(\kee

ar

25

ig

ew

1 £

-e1etpent. .Ti2pPISSEsi5eVsbepE=.leV"ile:ott saltprec:

Al-Hl-kVwwNo-'isee-cheent tt tteee e o ca N e e c = e o e

xt't't

goIJ2

f

s

f

L..is5s` s,1 s obt

Surface

exidiz

BaT

NX

rb2edueed

BaTi03

xl12 47"7e 170 150 130 110 90 469 Fig. -68 5. 467 xps 466 46S analysis cs=opex-[eo 464 463 462 46t "l6e 459 4SS 457 456 ・-5545d- 4S3152

Binding

Energy

(eV)

oi titanium in the three types of BaTi03.

2}

Effect

ef

Surface

Oxides

The

binding

energies relating to titanium

(Ti

2P)

of the surface oxidized

BT

in

parti-.

o

.

×

i

XXo

Agg,S t Flg. 3-rf 3-cs+x 3 Oxygencontent

6. Change of contact angle with relative

oxygen content in BaTi03 (BaTi03-e,

BaTiOa-fi+x)・

62

cular were

different

from the other BTs as

shown in Fig.5. The surface oxidized layer

was amounted to approximate 4oA

by

an

EPMA

analysis. Fig.

6

shows the

relation-ships among contact angles, relative oxygen

content, and wetting behaviors corresponding

to each oxide as well.

The

contact angles

reduced with the relative oxygen content or

TilO binding characteristics. It

is

suggested

that oxygen effects on the

interface

reaction

to be wetted through

formation

of silver

oxides although silver

does

not

diffuse

into

the

base.

4. Summarys

(1)

Neither

BT

nor

PZT

was wetted

by

silver with the contact angle of about

90

degrees.

Whereas

both

BT

and

PZT

were

(5)

Shonan Institute of Technology

NII-Electronic Library Service

ShonanInstitute of Technology

Wtrtting and intet:fuceReaction

of

BaTi03

wetted

by

the

frit-added

silver although the

wetting mechanisms of BT is

different

from

those of

PZT.

(2)

Titanium diffused into the glass to 2)

react with PbO initat the interfacesbetween

glass-silverand BT.

In

the glass-silver-PZT

system, PbO provided from the glass diffused 3)

into the

deMcient

part of

PbO

in

the

PZT

base

to

form

complete PbZrO,.

(3)

The surface oxides on BT of the

semi-conductor affected the wetting

behavior

of 4)

silver metal.

Acknowledgement

5)

I

would appreciate the support on the XPS

analysis

by

Dr.

T.

Amano.

Referenees

1) V.K. Nagesh, A.P. Tomsia and

J.A.

Pask:

and I'b(Zr,71)Os b.v.Ag Mketal

"Wetting

and reactions in th leadborosilicate glass-precious rnetal systems," J.Mater. Sci.,

18,2173-80

(1983).

J.

A. Pask and R.M. Fulrath: "Fundamentals

of Glass-to-Metal Bonding: VIII, Nature of

Wetting and Adherence," J. Amer. Ceram.

Sci.,45,592-96(1962).

M.P. Borom and

J.A.

Pask: "Role of

Ad-herence Oxides inthe Development of Chemical

Bonding at Glass-MetalInterface," J.Amer,

Ceram. Sci.,49,1-6

(1966).

S.Sugihara and K. Okazaki: Poster session

in the 7th InternationalSymposium on the

Application of Ferroelectrics,

Urbana-Cham-paign, IL.,

June

6-8, 1990.

K. Okazaki: Cerarnic Engineering for

Di-electrics (3rded.

Japanese).

Tokyo Gakkensha,

1983.

Fig. 2 .   Temperature   dependence   of   contact       length ! height   ratio   for   Ag 十 frit ! Pb ( Zr ,   Ti ) 03       system ( 40F : 40   weight % frit・ added   silver ,
Fig. 3. SEM   analysis   of   each   element of   the (3)

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