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1
Optical Properties of Borate Glasses and

Glass-Ceramics
Isabella-Ioana Oprea
Studiecentrum Soeterbeeck, Ravenstein, The Netherlands

8th - 9th October 2004
I. Oprea: Optical Properties of Borate Glasses and Glass-Ceramics •First •Prev •Next •Last •Go Back •Go To •Full Screen •Close •Quit
2
Contents
I Glass-ceramics
I Bismuth Borate Glasses Optical Properties - Results
B Refractive index
B UV-VIS and near-IR Absorption
3+
B Er Absorption and Luminescence
I Crystalized Bismuth Borate Glasses
B BiB3O6
B BiBO3
I Other systems Sr0.5Ba0.5Nb2O6, Pb2B5O9Br

I Current work
3
Glass-ceramics
I nm to µm randomly oriented crystals embedded in a glass matrix;

I produced by devitrification of glass.
4
Controlled nucleation and crystallization -

thermal treatment
1. heating the glass from room temper-

ature;
2. nucleation stage;
3. increasing temperature;
4. crystallization;
5. cooling down to room temperature.
5
Bismuth borate glass
Preparation
I melt from powder mixture: B2O3 and Bi2O3;
I homogenized at T = 700 oC;
I cooled down to room temperature at 100 oC / h.
Physical properties tuned

I varying composition xBi2O3(1 − x)B2O3, 0.25 ≤ x ≤ 0.65;
I adding dopants (Cr3+, Er3+).
6
Refractive index
7
Refractive index
I high refractive index - passive optical components;
I refractive indices increase with increasing Bismuth content;
I Sellmeier fit covering the full composition range
b1 + b2·x
n2(λ, x) = a1 + a2·x + a3·x2 + − d1·λ2 (1)
λ − c1 − c2·x
2
Coefficient Value
a1 1.9026
a2 5.7990
a3 -2.2295
b1 0.1691
b2 0.0007
c1 0.0947
c2 0.0195
d1 0.0182
8
UV-VIS and near IR absorption

16 0.45
α = 16
14
Absorption Coefficient α [cm−1]
0.4
12
Wavelength [µm]
0.35 λα=10 = 0.316 + 0.187 · x (2)
10 0.3
n→∞
position of the ultraviolet
8 0.25 oscillator defined in the Sell-
6 0.2
meier equation
0.25 0.3 0.35 0.4 0.45 0.5 0.55 0.6
Bi2O3 − Content x
4
λ0,U V = (C0 + C1 · x)1/2 (3)
2
λ0,U V = 0.165 + 0.186 · x (4)
0
0.5 1 1.5 2
Wavelength [µm]
I Bi2O3 ↑ - the absorption edge shift to longer λ.

I the optical properties in the short λ wavelength region - Bi2O3 groups.
9
1 mol% Er3+ absorption

5 0.25 Bi2O3
G11/2
0.35 Bi2O3
4.5 2 0.45 Bi O
2 3
0.55 Bi2O3
H11/2
4
0.65 Bi2O3
3.5 4
3
α [cm−1]
2.5
2
F7/2
F5/2,4F3/2
1.5
S3/2
F9/2
4
4
1
11/2
13/2
I9/2
I
4
4
0.5
H9/2
2
0
0.4 0.6 0.8 1 1.2 1.4 1.6
λ [µm]
10
Judd Ofelt theory

the effect of the crystal field of the glassy matrix around the doping ion
8 · π 3 · e2 · λ
Z
ed
αband · dλ = · χ ed · S (5)
3 · c · h · (2 · J + 1) · n2
n · (n2 + 2)2
χel = . (6)
9
X
ed
S = Ωt · Ut2 . (7)
t=2,4,6
where:
Ω2,4,6 - Judd - Ofelt parameters;
Sed - oscillator strength;
χel - effective field at the rare earth ion site in the glassy matrix;
c - speed of light, e - electron charge, h - Planck constant;
ρ - Er concentration, αband - absorption coefficient, n - host refractive index;
11
Ωt parameters function of composition

−24
x 10
8 I Ω2 - structural changes
Ω2
Ω4 around Er
Ω6
6 I Ω2 ↓ with Bi ↑ due to
Ω2,Ω4,Ω6
change of the local symme-

4 try of Er
I Ω2 Bi3+ large - dEr−O in-
2 crease
I Ω4 and Ω6 - related to long
0 range effects
0.2 0.3 0.4 0.5 0.6 0.7
Concentration
12
1 mol% Er3+ Luminescence

I silica based glasses - nar-
row spectrum
0.25 Bi2O3
1 0.35 Bi2O3 I flat emission spectra - rel-
0.45 Bi2O3
0.8 0.55 Bi2O3 ative contribution of the

0.65 Bi2O3
electric dipole transition
Intensity
0.6 increased
0.4 I magnetic-dipole transi-
tions is independent of
0.2 ligand field - sharp peak of
0 spectra at 1.53 µm
1.4 1.45 1.5 1.55 1.6 1.65 I electric dipole transitions
Wavelength [µm]
varied with the host com-
position.
13
1, 3, 10 mol% Er3+ absorption in

0.25 Bi2O3 0.75 B2O3 glasses
30
1%Er
I high amplification in a
3%Er smaller propagation path -
25 10%Er
higher Er concentration.
20
I BiB3O6 - 1000 ppm Er can
α [cm−1]
15 be incorporated
10 I limiting effect - interaction
between Er ions
5
I co-operative upconversion
0
0.4 0.6 0.8 1 1.2 1.4 1.6 - bismuth borate glasses
Wavelength [µm] not detectable.
14
Bi2O3 - B2O3 system
15
Bi2O3 - B2O3 system - thermal treatment

750
Liquidus temperature
Glass transition temperature
Crystallization onset
700
650
600
T [C]
550
500
450
400
50 55 60 65 70 75 80
mol% B2O3
16
BiB3O6
Mixture Surface (-) Phase Notes

Bulk (+)
glass - BiB3O6 1 week thermal treatment
+1000 ppm - BiB3O6 more nucleation sites
Cr3+
+1 - 10 % mol - BiB3O6 more nucleation sites
Er3+
+ 1 % mol TiO2 - BiB3O6 more nucleation sites
+ 10 % mol + ? needle -like crystals; cen-
TiO2 trosymmetric
+10 % crystal + BiB3O6 transparent; incomplete melt
powder of crystals
+10 % crystal + BiB3O6 ceramic opaque
powder pressure
sintering
17
BiB3O6 with high amount of TiO2
18
BiB3O6 crystals melted
19
BiBO3 (II)
What is known
I xBi2O3(1 − x)B2O3, 0.4 ≤ x ≤ 0.6;
I powder x-ray diffraction (M. J. Pottier, Bull. Soc. Chim. Belge 83, 235-238 (1974));
I low temperature metastable phase;

I after 24 h transforms in higher metastable phase BiBO3 (I), then in
Bi4B2O9.
Results
I stable phase as powder;
I SHG - non centrosymmetric;
I heat treatment - bulk crystallization - micrometer size crystals.
20
Recrystallized glasses xBi2O3(1−x)B2O3, for

x = 0.45 and 0.55 (Bi4B2O9 BiBO3)
1.5 1.5
Counts [arb.units]
Counts [arb.units]
1 1
0.5 0.5
0 0
10 20 30 40 10 20 30 40
2Θ [degree] 2Θ [degree]
21
BiBO3 (II)
Mixture Surface (-) Phase Notes

Bulk (+)
glass - BiBO3 uniform crystallization
+1000 - 1000 - BiBO3 luminescence shifted toward
ppm Cr3+ smaller wavelength
+ 1 % TiO2 - BiBO3 more nucleation sites
+ 10 % TiO2 + ? non - centrosymmetric
+1 - 10 % ZrO2 - ? more nucleation sites
powder melt + BiBO3 micrometer size glass ceramic
22
0.5 Bi2O3 0.5 B2O3 + 10% mol TiO2
23
0.5 Bi2O3 0.5 B2O3 + 10% mol TiO2
24
BiBO3 (II) powder x-ray
100
80
Counts [arb.units]
60
40 BiBO3 II
BiBO3 I
20
0
20 30 40 50 60
2Θ [degree]
25
BiBO3 (II) proposed structure

PROGRAM *** CELREF *** (J.LAUGIER & A.FILHOL 10/78)
ZERO LAMBDA A B C ALPHA BETA GAMMA
-0.035 1.5406 7.8975 6.9136 8.0448 90.000 104.935 90.000
VOLUME (A**3) : 424.404
H K L TH(OBS) TH-ZERO TH(CALC) DIFF.
1 0 -2 22.842 22.807 22.827 -0.019

2 0 -1 23.205 23.170 23.152 0.018
2 0 1 28.587 28.552 28.572 -0.020
1 2 -1 29.455 29.420 29.427 -0.006
3 0 0 35.308 35.273 35.256 0.017
1 1 -3 36.041 36.006 36.005 0.001
1 3 1 43.473 43.438 43.429 0.009
0 2 3 43.694 43.658 43.620 0.038
1 0 -4 45.068 45.033 45.039 -0.006
3 2 -2 45.547 45.511 45.526 -0.014
2 0 -4 46.662 46.627 46.628 -0.001
4 0 -2 47.359 47.323 47.323 0.000
4 1 -1 47.915 47.880 47.878 0.002
2 3 2 54.901 54.866 54.885 -0.019
26
Powder SHG - Phase Matching
27
BiBO3 (II) powder SHG
4.5
4
3.5
SHG Intensity [V]
3
2.5
2
1.5
1
0.5
0
0 50 100 150 200 250 300
Size [µm]
28
BiBO3 (II) glass ceramic x-ray
100
80
Counts [arb.units]
60
40
20
0
20 30 40 50 60
2Θ [degree]
29
Inhomogeneous nucleation - Ferroelectric

crystals in glass
I Glass: (1-x)(Sr0.5, Ba0.5)B4O7 + x (Sr0.5,Ba0.5)Nb2O6 where x = 0.1 - 0.3

I used as flux for growing SBN crystals;
I too many nuclei in melt;
I frozen microcrystals;
I heat treatment - low temperature phases - centrosymetric;
30
Ferroelectric crystals in glass
31
Current measurements
I 0.5 Bi2O30.5B2O3 - glass ceramics with lower size crystals;
I Confocal Laser Second Harmonic Generation Microscope - µm crystals;
I Pb2B5O9Br;
32
Confocal Laser Second Harmonic Genera-

tion Microscope
33
SHG Scan - example

1000 2.2
900 2
800 1.8
700 1.6
600 1.4
x [µ m]
500 1.2
400 1
300 0.8
200 0.6
100 0.4
0
0 100 200 300 400 500 600 700 800 900 1000
x [µ m]
34
Pb2B5O9Br
I crystals absorption edge ∼ 230 nm;
I glasses by melting Pb2B5O9Br crystals;
I absorption edge (∼ 400 nm) shifted toward longer wavelength - loss of
Br;
I refractive index; powder shg; heat treatment (100 h)
35
Conclusions
I optical properties of pure and doped bismuth borate glasses;
I recrystallization of glasses;
I BiBO3;
I current plans.

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1

Optical Properties of Borate Glasses and

Studiecentrum Soeterbeeck, Ravenstein, The Netherlands

I Other systems Sr0.5Ba0.5Nb2O6, Pb2B5O9Br

I nm to µm randomly oriented crystals embedded in a glass matrix;

Controlled nucleation and crystallization -

1. heating the glass from room temper-

Bismuth borate glass

Physical properties tuned

UV-VIS and near IR absorption

I Bi2O3 ↑ - the absorption edge shift to longer λ.

1 mol% Er3+ absorption

Judd Ofelt theory

Ωt parameters function of composition

change of the local symme-

1 mol% Er3+ Luminescence

0.8 0.55 Bi2O3 ative contribution of the

1, 3, 10 mol% Er3+ absorption in

Bi2O3 - B2O3 system

Bi2O3 - B2O3 system - thermal treatment

Mixture Surface (-) Phase Notes

BiB3O6 with high amount of TiO2

BiB3O6 crystals melted

I low temperature metastable phase;

Recrystallized glasses xBi2O3(1−x)B2O3, for

Mixture Surface (-) Phase Notes

0.5 Bi2O3 0.5 B2O3 + 10% mol TiO2

0.5 Bi2O3 0.5 B2O3 + 10% mol TiO2

BiBO3 (II) powder x-ray

BiBO3 (II) proposed structure

H K L TH(OBS) TH-ZERO TH(CALC) DIFF.

1 0 -2 22.842 22.807 22.827 -0.019

Powder SHG - Phase Matching

BiBO3 (II) powder SHG

BiBO3 (II) glass ceramic x-ray

Inhomogeneous nucleation - Ferroelectric

I Glass: (1-x)(Sr0.5, Ba0.5)B4O7 + x (Sr0.5,Ba0.5)Nb2O6 where x = 0.1 - 0.3

Ferroelectric crystals in glass

Confocal Laser Second Harmonic Genera-

SHG Scan - example

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