Post on 26-Feb-2021
D. RytzF.E.E. GmbH, Struthstrasse 2, D-55743 Idar-Oberstein
rytz@fee-io.de
JNCO, Cherbourg (10.06.2013)
Rôle des impuretés dans les cristaux de YAB (YAl3(BO3)4)
Menu
Matériaux NL pour l‘UV : généralités et motivation(s) pour l‘étude du YAB
Propriétés du YAB pour SHG 532/266 nm
Techniques de croissancecristalline
Absorption résiduelles dans l‘UV- Distribution longitudinale, analyses chimiques- Mesures sur poudres cristallines- RPE- Interprétation concernant Fe3+
Comment réduire le taux de Fe3+?
Autres cristaux (KABO, YAG)
Conclusions
NLO materials for UV generation
BBO LBO CLBO BiBO YCOB KBBF YAB
Toxicity --Hygroscopic -- - --Mechanical stability - -- -- ++Hardness - - + - ++
UV transmission + ++ ++ - ++ ?Phase matching cutoff (nm) 410 555 474 580 720 350 492Nonlinear coeff. deff + ++ -Angular acceptance -- +Temp. AcceptanceWalk-off -- -
Damage threshold ++ ++?Thermal dephasing - + - ?Light induced effects - + ? ? ?
Summary of NLO properties
SHG 532/266 nm
Type IAngle(°)
deff
(pm/V)Ang accmradcm
T acc(°C cm)
Walk-off(°)
BBO 47,5 1,1 0,17 5 4,8
CLBO 61,5 0,8 0,49 6,2 1,9
YAB 66,2 0,69 0,41 Approx. 6
1,9
Physical properties of YAB
Structure Trigonal, space group R32 Lattice parameters a = 9.287 A (GAB: 9.34 A; LuAB: -) c = 7.256 A (GAB: 7.31 A; LuAB: -) Density 3. 70 g/cm3 Melting noncongruent Hardness Mohs 7.5 Stability non hygroscopic Specific heat 0.75 W s g-1 K-1 Thermal coductivity 3 – 4 W m-1 K-1 Transmission 160 – 2200 nm Indices no = 1.7553 (GAB: 1,761, at 1064 nm) ne = 1.6869 (GAB: 1,689, at 1064 nm) Uniaxial negative (no > ne)
YAB, a brief history
• YAB = YAl 3(BO3)4
• First: A.A. Ballmann, US Pat. 3‘057‘677 (1962).
• N.I. Leonyuk et al. (1972 and thereafter).
• Self-doubling in NYAB = NdxY1-xAl 3(BO3)4
(L.M. Dorozhkin et al. (1981)).
(RE)AB and YAB in the literature
• Large number of references since 1981 onNd:YAB, Nd:GAB, Yb:YAB.
• Mostly for self-doubling.
• Only limited work on undoped (RE)AB:- US Patent 5‘030‘851 (Filed 1990, expired 1994),
SHG 1064/532 nm.- US Application 2006/0054864
YAB with less than 1000 ppm Mofor generation of < 350 nm.
SHG Angle vs. Fundamental
0,00
10,00
20,00
30,00
40,00
50,00
60,00
70,00
80,00
90,00
0 0,5 1 1,5 2 2,5
Wavelength (µm)
Pha
se m
atch
ing
angl
e (°)
Type I
Type II
YABλ λ/2
D. Rytz et al., Proc. SPIE6998 (2008) 699814-1 .
SHG Nonlinearity
SHG: effective nonlinear coefficients
0,0000,200
0,4000,600
0,8001,000
1,2001,400
1,600
0 0,5 1 1,5 2 2,5
Fundamental wavelength (µm)
NL
coef
ficie
nt (p
m/V
)
Type I (Phi = 0°)
Type II (Phi = 30°)
D. Rytz et al., Proc. SPIE6998 (2008) 699814-1 .
SHG 532/266 nm with YAB
• R. Maillard et al. (2010) θ = 66.2° α = 1.5 – 4.5 cm-1 L = 2.24 mm532 nm: 60 mW/ 60 ns/ 60 kHz/ 0.016 kW/ 45 µmdeff = 0.43 pm/V
• Xuesong Yu et al. (2010) α = 11.2 cm-1
532 nm: 1.54 mJ/ 10 Hz/ 15.4 mW/ 2 GW/cm2
266 nm: 0.24 mJ (15.6%)
• Qiang Liu et al.(2011) θ = 67° α = 0.67 cm-1 L = 6 mm532 nm: 42 W/ 18 ns/ 60 kHz/ 80 µm266 nm: 5.05 W (12.3%)
• H. Liu et al. (2011) θ = 66.2° α = 3.7 cm-1
deff = 1.30 cos θ = 0,56 pm/V
YAB: Transmission
B155/1 (L=0.84 mm)B155/2 (L=1.83 mm)
C291 (L=0.65 mm)E101 (L=1.12 mm)
Li 2WO4 Flux, Air Li 2O-Al2O3-B2O3, Air
YAB: the challenges
• YAB and LuAB are promising materials for UV generation.
• Phase matching conditions known and verified for several wavelengths.
• Challenge: crystal growth of high purity (high UV transmission) material.
• Damage threshold ? Light induced effects?
YAB growth (K2Mo3O10 FLUX)
Crystal E111-2
Cristal: 5.5 gFrom 175 g melt(100 ml crucible)Loss: < 4 g
Duration: 840 h (34 days)Ramp: 0.05 – 0.15°C/h
Growth Pullout1055 1006 °C
Scale: 1 cmc-axis seed
YAB growth (Li2WO4 flux)
Crystal C291-1
Cristal: 7.3 gFrom 175 g melt(100 ml crucible)Loss: < 1 g
Duration: 16 daysRamp:
Growth Pullout998 947 °C
Scale: 1 cmc-axis seed
Menu
Matériaux NL pour l‘UV : généralités et motivation(s) pour l‘étude du YAB
Propriétés du YAB pour SHG 532/266 nm
Techniques de croissancecristalline
Absorption résiduelles dans l‘UV- Distribution longitudinale, analyses chimiques- Mesures sur poudres cristallines- RPE- Interprétation concernant Fe3+
Comment réduire le taux de Fe3+?
Autres cristaux (KABO, YAG)
Conclusions
YAB fluxes (a summary)
Flux Contaminants(typical)
Absorption bands
K2Mo3O10 Mo (100 ppm)Fe (10 – 30 ppm)
245 nm280 nm370 nm420 nm
Li 2WO4 W (80 ppm)Fe (10 ppm)
same
LaB3O6 La (10%)Fe (10 ppm)
same
Li 2O-Al2O3-B2O3 Fe (10 ppm) same
Published tranmission curves for YAB
Yu et al., JCG (2010)
Thickness 0.72 mm Chen et al., AP B (2011)
T = 45% at 266 nm
Alpha = 8 cm-1 Thickness1.0 mm
T = 50% at 266 nm
YAB:B2O3:Li 2O Alpha = 5 cm-1 Liu et al., MRI (2011)
Yb:YAB:Li 2WO4:B2O3 Thickness1.0 mm
T = 58% at 266 nm
Alpha = 3.7 cm-1
YAB:Li 2B4O7:AlBO3
Published tranmission curves for YAB
Yu et al., JCG (2010)
Thickness 0.72 mm Chen et al., AP B (2011)
T = 45% at 266 nm
Alpha = 8 cm-1 Thickness1.0 mm
T = 50% at 266 nm
YAB:B2O3:Li 2O Alpha = 5 cm-1 Liu et al., MRI (2011)
Yb:YAB:Li 2WO4:B2O3 Thickness1.0 mm
T = 58% at 266 nm
Alpha = 3.7 cm-1
YAB:Li 2B4O7:AlBO3
Liu et al., OL (2011)
Alpha = 0.67 cm-1 at 266 nm
YAB:Li 2O:B2O3:AlBO3
YAB: Transmission (sample E128-5/1)
Transmission 800 nm - 185 nm
Blue: seed end
Purple: tail end
E. Recktenwald (FEE – FH Birkenfeld, 2011)
~ 240 nm
~ 300 nm
YAB: chemical analysis (GDMS)
E128-5/3-1 E128-5/3-3
Seed end Tail end
Li (ppm wt) 150 === 160Na 3.9 V 0.40Si 2.7 Λ 5.7K 1.7 V 0.27Ca 6.8 V 3.8Ti 2.4 V 0.83Cr 3.6 V 1.9Fe 10 Λ 46Ni 0.83 === 0.78Zr 1.1 === 0.88Sb 1.5 Λ 2.3Ce 1.3 === 1.4W 360 V 19
Pt < 0.5 < 0.5
Blue: seed end
Purple: tail end
ΛΛΛΛ is symbol for
increase
from seed to tail
Comparison powder / single crystal(M. Jost, M. Weibert, V. Wesemann, FEE, 2011)
0,001
0,0015
0,002
0,0025
0,003
350 370 390 410 430 450
Tran
smis
sion
Wavelength [nm]
KNbO3 single crystal A215-6(normalized signal)
KNbO3 powder
Al2O3 powder, Fe doped
200 250 300 350 400 450 500 550 600 650 700 750 800-0,01
0,04
0,09
0,14
0,19
0,24
Wellenlänge in nm
Tra
nsm
issi
on
in %
200 250 300 350 400 450 500 550 600 650 700 750 800-0,02
0,03
0,08
0,13
0,18
0,23
0,28
Wellenlänge in nm
Tra
nsm
issi
on in
% Nominally pure
100 ppm Fe2O3
1000 ppm Fe2O3
200 250 300 350 400 450 500 550 600 650 700 750 800-0,02
0,03
0,08
0,13
0,18
0,23
0,28
Wellenlänge in nm
Tra
nsm
iss
ion
in %
Al2O3 powder, Fe doped
200 250 300 350 400 450 500 550 600 650 700 750 800-0,01
0,04
0,09
0,14
0,19
0,24
Wellenlänge in nm
Tra
nsm
issi
on
in %
200 250 300 350 400 450 500 550 600 650 700 750 800-0,02
0,03
0,08
0,13
0,18
0,23
0,28
Wellenlänge in nm
Tra
nsm
issi
on in
% Nominally pure
100 ppm Fe2O3
1000 ppm Fe2O3
200 250 300 350 400 450 500 550 600 650 700 750 800-0,02
0,03
0,08
0,13
0,18
0,23
0,28
Wellenlänge in nm
Tra
nsm
iss
ion
in %
Transmission
(arb. units)
Arrow at 266 nm
200 Wavelength (nm) 800
Al2O3 powder, Cr doped
200 250 300 350 400 450 500 550 600 650 700 750 800-0,02
0,03
0,08
0,13
0,18
0,23
0,28
Wellenlänge in nmT
ran
sm
iss
ion
in %
200 250 300 350 400 450 500 550 600 650 700 750 800-0,02
0,03
0,08
0,13
0,18
0,23
0,28
Wellenlänge in nm
Tra
nsm
issi
on in
% Nominally pure
100 ppm Cr2O3
1000 ppm Cr2O3
200 250 300 350 400 450 500 550 600 650 700 750 800-0,02
0,03
0,08
0,13
0,18
0,23
Wellenlänge in nm
Tra
nsm
issio
n in
%
YAB (crystal C300-10, powder, Fe doped)
200 250 300 350 400 450 500 550 600 650 700 750 800-0,02
0,03
0,08
0,13
0,18
0,23
Wellenlänge in nm
Tra
nsm
iss
ion
in %
200 250 300 350 400 450 500 550 600 650 700 750 800-0,02
0,03
0,08
0,13
0,18
0,23
0,28
Wellenlänge in nm
Tra
nsm
iss
ion
in %
150 ppm Fe2O3
Nominally pure
Elektron Spin Resonance (ESR) MeasurementsS. Ilas, P. Loiseau, G. Aka (ENSCP Paris)
• Detection of Fe3+.
• Measurements in starting materials:
• Measurements in molten mass:
Source Charge ESR Fe3+
Al 2O3 SASOL C912007-III No signal < 5 ppm
SASOL C0517094-IV No signal < 5 ppm
Y2O3 TREIBACHER 51/00 No signal < 5 ppm
YARMOUTH 5412 No signal < 5 ppm
Li 2CO3 ALFA AESAR 75097 1000 Gauss1900 Gauss
Broad 10-20 ppm
WO3 ARAN ISLES W-977 1000 Gauss1900 Gauss
Broad, withstructure
10 – 15 ppm
Run Nb. Flux ESR Fe3+
YAB C314-1 Li – Al – B(H2 + N2)
800 Gauss1800 Gauss
Broad > 10 ppm
YAB E135-2 Li – Al – B(N2)
Weakstructure
???
YAB fluxes (a summary)
Flux Contaminants(typical)
Absorption bands Correlation withFe3+
K2Mo3O10 Mo (100 ppm)Fe (10 – 30 ppm)
245 nm280 nm370 nm420 nm
Yes
Li 2WO4 W (80 ppm)Fe (10 ppm)
same Yes
LaB3O6 La (10%)Fe (10 ppm)
same Yes
Li 2O-Al2O3-B2O3 Fe (10 ppm) same Yes
Possible origins of Fe3+ impurities
• Starting materials (oxides, better than 99.99%).
• Pt crucibles (150 ppm Fe is standard).
• Ceramics (> 100 – 500 ppm Fe ?).
• Others?
Oxide powders Fe (ppm)Li2CO3 ALFA 1 For undoped crystals
AI 99.99 3 For doped crystals
AI 99.999 0.75WO3 AI 0.06Y2O3 Treibacher < 5
AI 1 „High purity“Al2O3 SASOL 2 Possibly > 10 ppm
MV Lab 0.5
B2O3 ALFA < 0.2
Ceramics Fe (ppm)Al2O3 FRIATEC 300 - 500 Contains MgO
PLASCERA < 1000ZIRCAR Sali 50 10 ppm Ni, 0 ppm Cr!
ZIRCAR ?Al30 200-240SCHUPPUltra-board 1850
130
SiO2 ROTOSIL 45
Crucibles Fe (ppm)Pt Manufacturer A 150 (Standard)
13 (New)10 (Seed holder)
Oxide powders, ceramics, crucibles:Fe contamination
Fe2+ vs. Fe3+
Fe2+ cannot be incorporated on Al3+ site.Thus: grow crystal under reducing conditions!
Chunlei Liu, Lijuan Liu, Xin Zhang, Lirong Wang, Guiling Wang and ChuangtianChen, J. C ryst. Growth 218 (2011) 618.
Coordination Ionic radius(ppm)
Al 3+ Octahedral 67.5
Fe3+ Octahedral 63-69 < Al3+
Fe2+ Octahedral 75-77 > Al3+
Conclusions et travaux futurs concernant les cristaux de YAB (YAl 3(BO3)4)
• YAB permet de générer > 5W d‘UV à 266 nm.
• Propriétés ONL favorables.
• Croissance de cristaux (50 à 100 g) en cours.
• Réduire la contamination en Fe (priorité no. 1):– purification (matière premières, creusets, céramiques).
– croissance sous atmosphère réductrice.
• Eliminer les mâcles (priorité no. 2):– réduire la densité de mâcles dans le germe.
– favoriser la croissance des facettes prismatiques.
Acknowledgment
V. Wesemann, J. Buchen, W. Scalbert, A. GrossF.E.E. GmbH, Struthstrasse 2, 55743 Idar-Oberstein
S. Ilas, P. Loiseau, G. AkaLab. de Chimie de la Matière Condensée, ENSCP, Paris
F. Balembois1, L. Deyra1, A. Maillard 2, R. Maillard 2, Ph. Villeval3, F. Salin4
1- Lab. Charles Fabry, Institut d‘Optique, Orsay2-LMOPS, Univ. de Metz et Supelec
3-Cristal Laser, Messein4-Eolite, Pessac