Formation and optical absorption of Bi2S3 colloids in glasses

Journal of Non-Crysl;llline North-Holland. kmlerdanl

FORMATION

LEI

Solids 95 & 96 (1987)

601

AND OPTICAL

WEICUO

YIN

OF BiZS3

ABSORPTION

BAOZHONC

Institute

Shanghai

601 - 608

of

COLLOIDS

IN GLASSES

AND HLIANC XIHUAI

Ceramics,

Sinica,

Academia

Shanghai

200050,

China

By selgfting p5ase-separable glass system as the base glass and by introducand 5 ions as coloring agents ing Eli from BiZO, and ZnS respectively, we obLained a colored glass of SiO 43 0 -Al 0 -Na20 with semiconductor Bi S colloids as colorant. Optical a 8 sorp2?. ion 27o this glass is similar to t 63e Bi2S3 polycrystals. Effects of composition and heat treatment on the optical absorption of glasses are also studied. TEt4 photographs in the paper show the phase separation and Lhe formation of 81~5~ colloids in Na20-E203 phase when the glasses are heat-treated.

1.

INTRODUCTION Based

band

on

the

consideration

solid,

of

oration

selenium,

of

that

It

colorants

that

plays

From

in order then

oration

on, of

infrared

of

in

(3)

semiconductor main

basis is

for to

the

and oxidizing),

Cd!%

electron in and the

are

can

which

they

of Many with

slmllar

absorption with

same

col-

the

series

new

absorption

the

fluorence

glasses, inert

of

to

edges

revealed

the

and

relevent spectrum the

as

presence

have

a larger

0022-3093/87/$03.50 0 Elsevier Science Publishers (North-Holland Physics Publishing Division)

B.V.

are during

so small

that

and

to build

up the

theoretical

an reasonable

scheme

we advance

glass

glasses compounds

are

compounds

semiconductors as base

new filter

semiconductor

difficulties

with form

coloration”! on

colloids

TEM have

getting of

colorants

these

system

the

the

col-

coloration”.

accordance

and

in

evaporation

these

the

in

and of

glasses.

the

glass

several

optical

the

state”

research

semiconductor

show

defraction

remaining

of

of

col-

196Os,

“semi-conductor

“semiconductor (1)

energy

the

“colloidal

same optical

glasses

in

in

can

early

mechanism

made

of

of

not

phase,

guidance

with

colorants

dispersive

the

doped

the

separable

we successfully

the of

colloidal

the

experimental

and

mechanism:

the

traditional

the

the

determines mechanism in

not

the

further

the

production

phasephase

from

value

To overcome

introduce

it

difficulties

cause

be struck.

he called

the

X-ray,

glasses

ruby

show

colloids

which

the

both

decomposition

-melting,

order

studied

and

technological

oxidation,

not

glasses

coefficients

crystal.

range

and

and

made

under

glasses

(2)

role,

have

support the

temperature

The

main

crystals,

crystals. CdSe

the

authors

results size

definite

“semi-conductivity

glasses

short

anLimony

Lhe

glasses2--9,

filter

corresponding

and

to distinguish

many

these

experimental

its

is

the

sunlmarized

copper

concluded

oration”

that

Xi-huai

Huang

the

(lessdecomposing, themselves, to concentrate

solubility,

the

glass

glasses

can

that

evaporizing

and the facilitaing

to select colorants

in

the

forma-

tion

oF semiconductor

Formation

the

colloids. optical

and

In

the

absorption

present

paper

OF Bi2Sj

colloids

we report

in

the

resrarch

on

Na20-A1203-E1203-Si02

glass.

2.

EXPERIMENTAL 2.1

Preparation

and

1) Selection

heat

Na20-A1203-8203-Si02 glass

system

glass

possesses

study

it

High

For

6-Bh.

2)

in

lh,

Preparation

with

crucible

and

chemical at

melts

heat

Bi203

Furnance.

Glass For

Samples’

melts

were

SO-40min,

heat

poured

then

treatment

controlled

the

ZnS were

and

electric

we can

cleraly

were

H3E03 Furnance

plate,

mixed

at

and

cast

containing

fully

mixed

For

a steel

with

6-Flh

plate,

the

1420-

annealed

and in

glass

a silica

electric

a Harbour

annealed

and

cast

Batches

in

poured

at

stove. a electric

in

temperature

and

controller.

program

that

This

chemical

good

stove.

was processed

temperature

by

on

Al(OH)>

a Harbour

1400-142O’C

cooled

temperature(3-5’C/min),

of

at

so

Eli2S3 colloids

of and

melted

the

and

region.

colloids.

on a steel

poured

with

treatment

purity

1350-13L10°C,

500-52O’C

were

In this

forming

properties

Na2C03,

in

glass.

base

glass

properties

purity

cryclble

cooled

the

by semiconductor

chemical

then

as

large

in

UV-Lransmission

a Rh-Pt

Glass

For

place mechanical

caused

quartz,

melted

500-52O’C

a good

has

SiO2

and

was selected

take

Lechnological,

absorption

purity

1450?

doped

also

optical

the

together

at

a good

can

glass

base

system

separation

samples

of

of

glass

phase

durability,

treatment

preparation

and

strove, were

duration

Samples

were

the all

rising

rate

automatically with

cooled

the

stove. 2.2

Measurement

of

The absorption taining

and

glasses

measured

at

polished

with

room

of For

the

with

spectrometer

Philips OF base with

spectra

at

diFFerant

by

spectrometer

of

eroded

thin

glasses

and

and/or

W-5270

and

the

Bi2Sj

duration

conwere

samples

SV-50A,

transmission

through

in

1X HF solution

OF the

enough

For

size

were

a modulation

For

electron

the

and

replica

30s

in

were

and

beam

point

tech-

order

to

transmission

3mmXZOpm for

glasses(Face-scanning

EDAX 9100 glasses

base

lmm.

Samples to

of

temperatures

was made

were

Ar + ions

ESR spectra FE-lx

samples

replica

Microcompositions

deterimined

of

microstructure.

werebombardedby through.

temperature

a thickness

Samples

elucidate

transmission

heat-treated

TEN observation niqe.

Samples

to

penetrate

analysis)

were

instrument. determined

at

magnetic

Field

15’C of

with

X wave

100 Khz.

band

JES

3.

EXPERIMENTAL

3.1

Base

With

RESULTS

glass

the

substitution

of

A1203

64Si02(19-x)E1203(6+x)A120311Ns20 large ing

of

amount

at ‘1

bubble

1420-145O’C.

for

and

sand,

We can

get

glasses

and

good

tion

edges show

for

‘2,

Fig.2

two

shows

transition signals

may

glasses,

and

the

metal result

from the

the

8 for

ESR spectra or

in

with the

remaining

the

high

glasses

contain

viscosity

melL-

when

compositions.

following

‘3,

earth

UV-absorption

*l,

1850

2210

peaks

1910

and

*4.

UV-absorp-

1850-2500

are

8 for

*2 and

*l,

‘3

Between

of

and

ions

*2,

8.

positions

structural

the

al

glass

of

rare

glass

of

located

peaks,

1925

ions

so may

are

absorption

2190x

spectra

glasses

the

Nag0

*4 64Si0219B2036A120311Ns20

UV-absorption

all

of

glasses 11,

the

for

*2 64Si0220E12035A120311Ns20

*3 63Si0221E2036A120310Ns20 shows

are

glasses

64Si0221E12034A120311Ns20

Fig.1

or 8203

6203

64Si02(19+x)El2036A1203(11-x)Ns20

and

2235

8,

‘3.

As no magnetic

defects peaks.

during

added (or

1950

8

‘4.

1 v

were

the

8 and

active

glass-melting,

color

centers)

of

ESR the

2

3

1600

2100

1 4, I500

2600

Wavelength(i) Fig.1

UV-absorption the

3.2

Bi2S3

to black

show

(thick

of

IK

, I l I,, 4050

3050

Fig.2

ESR spectra

glass

base

containing

Experiments

spectra

I,

of

the

X I Ci’T

base

glass

glasses glass

that

sample)

*l,

f2,

*3,

*4 and

when heat-treated,

‘6

can

while

glass

10”s

have

be

*5,

struck

f7

yellow

from

and *8

show

eFfect

on

no

changes. also

Experiments phase

separation

glasses

are

the

content

(2)

Bi2S3

amount

of

Full of and

When

of

stripes

(this

Eli203

in

the

deposits and

ZnS are

(1)

that,

glass.

A1203

Bi

indicate

of

more

be

added.

1X ZnS is

may be related

batches, can

Zn2+ than

homogeneity obtained (3)

at

glasses

the

a strong added

to

the

the

batches,

the

to 81 3+ ions);

by decreasing

of

be improved.

glasses

bottom can

only

of

can crucible

be struck

when

large

by adding

604

Lb

reducing

agent

other

author’s

results

in

such

8s C4H406 lo.

resuts

to

be struck

temperature

duration

and

Si02 61.33 61.97 61.97 61.97

‘2’3

6.51

21.28 21.49 21.49 21.49 21.49 21.49 21.49 21.49

5.55 5.55 5.55 5.55 5.55 5.55 5.55

Fig.3,

4 and

different

heat

of

spectrum

Bi2S3

Fig.3,

From

S2-

and

in Bi3+

ions

increasing to

struck

and

treated.

In

glass

from

a high

and

in are

in Fig.9 the

glass

37.74%

Ei element In

glasses solubility,

of

beam on

3.89%

is

excessive

learn

we can concentrated and

at

in

the

in same

of

only

of

with with

glasses

the

glasses

high with

also,

treatment,

edges the

show doped

doped

heat

clearly

the

are

not

move

so sharp

visible

indicate

that

when

of

0.508%

heat-

accordingly

region.

We can

see

Bi

only

that and

this

means

elements

the

Bi,

identified.

be

their

that

in

S and 5.67%

focusing

by

S elements

black

the

which

content region

indicates

that

colloids. glasses

Na20-B203 they

can

and

colloids are

transmission).

Identified,

percents

glasses

infrared

and

Bi2S3

that

when

ldentlfied

be

by direcl

be

Na,

show

phase

can

Ei2S3

time

with

transmission

glasses

glasses to

dispersive

the

the

f7

the

glasses

and

while

replica)

in Fig.8

S can

0.206%

Al,

*4 and shows

treatment

absorption

Fig.9-11,

point

The weight

low.

heat

curves

(taken

glasses,

is

*2,

Fig.5

a “long-tail”.

in

Bi nor

glass

of

subjected

colloids

neither

1.0 0.50 -

regions,

the

by

Fig.8

black

Si,

summary

are

the

the

-

-

black,

are

Na20-B203

in

-

1.0

before

to

they

transmission

colloids

EDAX patterns

electron

that

shows

no Bi2S3

Fig.7(a)

-

0.75

near-infrared

yellow

taken

the

Na2S

.

see

and

increasing

1.0 1.0

curves

transmission

the

is

with

E12S3

C4tl606

respectively,

temperature

(Fig.7

grow

Ei2S3

0.20 0.50 0.50 0.50 0.50 0.50 -

when

polycrystals

shows

graphic

0.15 0.50 0.55 0.50 0.50 0.50 0.50 0.25

from

treatment

TEM photographs

deposit

10.88 10.99 10.99 10.99 10.99 10.99 10.99 10.99

and

to

+ LnO

glass

and

increases

containing

ZnS

12

contrast f

may be “burn-up”.

glasses

of

is

H2SCg)

temperatures,

colorants

color

transmission

visible

wavelength, Bi2S3

the

temperatures

no changes

heat

longer

as the

the

high of

Bi203

6 we can

the

are

show

at

Na20

polycrystals

4 and

transmission

Bi3+

6 show treatment

this

Na2S,

2115 + H20Cg)--*

damage

compositions

A1203

61.97 61.97 61.97 61.97

the

melling,

of

Calculated NO.

sulphur

(5)

colloids in glasws

containing

batches

reaction

the of

lo.

er al. / Bi,S,

for

(4)

evaporation

the

difficult

Weipo

are phase

combine

heat-treated in

to

which

Form

the they

Bi2S3

colorants

have

compound,

a greater

resulting

in

605

f60 l&!Tc-l 2

g$ 50 ‘lo

+

3

4

30

20 IO

6

Fig. glass

3.

7

15h;

10 12 14 16 18 Wavelength,x103 IAl

Transmission

with temperatures treatment;

for

6

curves

of

20

No.

0

22

2

Fig. 5. Transmission Bi2SJ polycrystals

different heat treatment l--Without heat Z--72O'C for 15h; 3--740%

4--

76O’C

for

12 3 4 wavelength. x104 IA)

5

spectrum (0.60 mm)

of

15h

100 90

1

I.

I

Fig. glass

6. Transmission with different

curves of No.7 heat treatment

temperatures

l--Without 2--76O’C 3--780%

Fig. glass

4.

Transmission with different

curves heat

temperatures

l--Without 2--74O’C 3--75O’C 4--7309 5--780%

for for for for

heat treatment; 15h; 15h; 20h;

10h.

of

No.3

treatment

heat for for

treatment

6h 10h

I Fig.

11.

EDAX pattern black SDOt.

of

the

Lei Weiguo et al. / Bi,.S, colloidr

606

(a)

Without

(c)

Heat

heat

treatment

treatment,

at

600x

780%

30000x

For

(b)

ah,

in ghses

Heat treatment 10000x

fig. 8. sample

KM photograph showing of glass microstructure

Heat treatment 20000x

Fig.

EDAX pattern scanning

fig.

of

face-

10.

74O'C

TEM photograph

Fig. 7. changes

9.

at

at

of-

78O'C

EDAX pattern black spot

For

the

For

of

the

flh,

ah,

in

change

the

similar

4.

results

curves

in photochromic

Bando 11

glasses.

of

has

also

obtained

glasses.

DISCUSSION

4.1

Optical

Based that

the

origin

free

changes

which

the

“long-tail”

absorption

edge

cause

Bi2Sj

(10

Preparation

technology

preparation

of

glass)

is

agent)

in glass

based

on

is

are

do

and

Inspired

to

lower

structure,

large

the

of

4.3

by

deviation

Ei2S3

for

may

phase

amount

will of

place

take

easy

to

get

the

in

inspiration. of

colorant

of

to

due

semiconductor

chemical and

one

in chemical

colloids

can

nucleate thing of

industry,

of

potential be promoted.

colorants

we can

phase

differ

system,

and

we should

collect

separation

phase

phase

the

of

melted

the

collected.

easy

the

at when

in

decomposition

be

glass

coloration

important

As a result

properties

the

be concentrated,

and

them,

photochromic the

supersaturation in

most

colorants

process

(or in

colorants

of

the

concentrating

and

a small

quantity

are

to

due

resulting

remaining

photochromic

colorants dissolve

matrix

oxidization

to

(including

of

colorants

prepartion,

this

for

glass

solubility

glass

and

extraction

the

the

glass

of

separation,

from

the

the

other’s,

concentrating

in

difference,

this

clearly

Fig.7

and

colorant

of

shows

function. Concentrating

of

odynamic

rule,

mony

glasses.

analyse

red

a

a excessive

a layer

Secondly,

has

structural

with

with

it

and

and

temperature

ratio

temperature,

the

evaporation,

structure

formation

this

from

and

foundation

we put

one

the

deposit

practical

colorants

composition, when

high

spectrum.

the

high,

the the

by

dispersive a

temperature,

that,

glass-melting,

lays

with

be sufficient Turn

to avoid

during

of

reasons,

sharp,

region,

system

colored

that

at

requires

must up.

conclusion

glass

of

fact

varies

heat-treated This

grow

at

orthorhomic

stoichiometric

the

very

infrared

12

semiconductor

the

temperature,

glass

the formation

the

following

the

1s not

near

absorption

from

The

glass.

the

to

to

related

polycrystal

the

by wt)

4.2

glass

at

to

due

“long-tail”.

the

high

arrive

is

crystal

Ei2S3

belongs

influences

rata

directly

glass

of

in

in Bi2S3

also,

further

Bi/S

we can

may be of

absorption

place

content,

results absorption

optical

carrier

take

glass

colloids.

of

the

strong

of

of

semiconductor

The

of

experimental

change

firstly,

01

absorption

on

the

Bi2S3

in

transmission

of

some

colorants

we can

other

It

make

is

also

experimental

(or use

impurities)

of

it

useful results

in to

the

by phase

preparation

understand and

facts.

this

separation of rule

is

selenium to explain

a thermand

antiand

way

is

It has

a good

way

a M. P lower

leaving

to

than

inLroduce 685’C,

a Eli excessive

ZnS is

to

during

Some authors

it

is

easy

, and

Zn

to

+ ZnS,

not

by

with

decompose

Bi2S3

Bi2S3,

rising

temperature,

compound.

difficult

evaporation

by Bi203

colorants and

13

decompose

glass-melting reported

due

that

2+

2n

struck14,

others

reported

that

glasses.

Further

research

on

10”s

its

to

strength

glasses 2+

2n

in

S 2- ions 3,14 .

prevent

field

glass

red

function

can

large

containing

selenium the

2+

were could

difficult

to

made with

be

these

from

colored

2”

glasses

be 2+

free

IS

needed.

5.

CONCLUSION

1) For

the

separable

from

ants

time

first

glass

as

Bi203

the

and

glasses

logical

procedures

similar are

industry

Bi2S3 and

colored

glass

introducing

Bi

we also

technological

selecting

by

3+

and

prepared

S2-

semiconductor

other

procedures,

so

phase as color-

ions

that

these

techno-

effective.

2) The technological the

glass

ZnS respectively,

using

colored

we obtained base

in

procedures

production

of

these

this

kinds

paper

are

guiding

of

Function

for

OF glasses.

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Huang

2)

Infrared

J.

Xi-huai, group,

3)

Infrared

4)

Chou

Yu-hua

5)

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Shi-zhuo,

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2hu

group, and

l(2)

(1962)

98.

New Inorganic

Chinese

Materials,

2(l)

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9.

New Inorganic

Ya-juan,

Materials,

5(l)

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7)

Zheng

8)

Toriumi

Cue-pei,

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Silicate

Sot.

4(l)

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J.

Chinese

Silicate

Sot.

lO(2)

11)

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R.

Kiryama,

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Black,

E.

M.

13)

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J.

Tress,

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N.

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G. West-Oram,

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Jin-wei,

J.

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Coloured

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Techn.

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Glass

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al., al.,

et

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Sheng

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