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©2001 CRC Press LLC
Ce
3
+
Ti
3
+
Cr
3+
Cr
4 +
Sm
+
2
V
+
2
Wavelength ( µm)
0.5
1.0 1.5
2.0
4
(SrF )
2
(MgF )
2
(LiYF )
4
6
(BeAl O , LiSrAlF )
2
(Mg SiO )
2
Co
+
2
(MgF )
2
(Al O )
3
2
Ni
+
2
(MgF , MgO)
2
2.5
Figure 1.1.11 Reported wavelength ranges of representative tunable crystalline lasers operating
at room temperature (from the Handbook of Laser Wavelengths, CRC Press, Boca Raton, FL,
1998).
Upconversion processes make possible many additional lasing transitions and excitation
schemes. Upconversion excitation techniques include multi-step absorption, ion-ion energy
transfer, excited state absorption, and photon avalanche processes. Lasers based on
upconversion schemes are noted in the mode column of the laser tables. Transitions
involved in upconversion processes are given in Table 1.1.3 and can be identified by
reference to the relevant energy level diagrams for the ions in Figures 1.1.4–1.1.8. The
success of many of the schemes depends upon the degree of resonance of energy transfer
transitions and the rate of nonradiative transitions by multiphonon emission and thus varies
with the host crystal.
Cascade and cross-cascade lasing schemes have also been employed; transitions involved
in cascade and cross-cascade lasing schemes are summarized in Tables 1.1.4 and 1.1.5. For
examples of avalanche-pumped upconversion lasers, see References 18 and 1037.
©2001 CRC Press LLC
Table 1.1.3
Multi-step Upconversion Excitation Schemes
optical transition ⇒ ion-ion energy transfer transitions
➟
nonradiative transition
Laser
ion
Upper
laser
level
Codopant
ion Upconversion excitation scheme
Pr
3+ 3
P
0
—
Yb
3+
1)
3
H
4
→
1
G
4
2)
1
G
4
→
3
P
1 ➟
3
P
0
1)
2
F
7/2
→
2
F
5/2
(Yb
3+
)
2)
2
F
5/2
–
2
F
7/2
(Yb
3+
) ⇒
3
H
4
–
1
G
4
(Pr
3+
)
3)
1
G
4
→
3
P
1,0
Nd
3+ 4
D
3/2
— 1)
4
I
9/2
→
4
F
5/2 ➟
4
F
3/2
2)
4
F
3/2
→
4
D
3/2
1)
4
I
9/2
→
4
G
5/2 ➟
4
F
3/2
2)
4
F
3/2
→
4
D
3/2
2
P
3/2
— 1)
4
I
9/2
→
4
G
5/2 ➟
4
F
3/2
2)
4
F
3/2
→
4
D
3/2 ➟
2
P
3/2
Ho
3+ 5
S
2
Yb
3+
1)
2
F
7/2
→
2
F
5/2
(Yb
3+
)
2)
2
F
5/2
–
2
F
7/2
(Yb
3+
) ⇒
5
I
8
–
5
I
6
(Ho
3+
)
3)
2
F
7/2
→
2
F
5/2
(Yb
3+
)
4)
2
F
5/2
–
2
F
7/2
(Yb
3+
) ⇒
5
I
6
–
5
S
2
(Ho
3+
)
5
I
7
Yb
3+
1)
2
F
7/2
→
2
F
5/2
(Yb
3+
)
2)
2
F
5/2
–
2
F
7/2
(Yb
3+
) ⇒
5
I
8
–
5
I
6
(Ho
3+
)
➟
5
I
7
Er
3+ 2
P
3/2
— 1)
4
I
15/2
→
4
I
11/2
(Er
1
3+
)
2)
4
I
15/2
→
4
I
11/2
(Er
2
3+
)
3)
4
I
11/2
–
4
I
15/2
(Er
1
3+
) ⇒
4
I
11/2
–
4
F
7/2
➟
4
S
3/2
(Er
2
3+
)
4)
4
S
3/2
–
4
I
15/2
(Er
2
3+
) ⇒
4
F
9/2
–
2
K
13/2
(Er
3
3+
)
➟
2
P
3/2
4
G
11/2
— 1)
4
I
15/2
→
4
I
13/2
(fourfold) ⇒
4
G
11/2
2
H
9/2
— 1)
4
I
15/2
→
4
I
11/2
(Er
1
3+
)
2)
4
I
15/2
→
4
I
11/2
(Er
2
3+
)
3)
4
I
11/2
–
4
I
15/2
(Er
1
3+
) ⇒
4
I
11/2
–
4
F
7/2
(Er
2
3+
)
➟
4
S
3/2
4)
4
I
15/2
→
4
I
11/2➟
4
I
13/2
(Er
3
3+
)
5)
4
S
3/2
–
4
I
15/2
(Er
2
3+
) ⇒
4
I
13/2
–
2
H
9/2
(Er
3
3+
)
©2001 CRC Press LLC
Table 1.1.3—continued
Multi-step Upconversion Excitation Schemes
Laser
ion
Upper
laser
level
Codopant
ion Upconversion excitation scheme
4
S
3/2
—
—
1)
4
I
15/2
→
4
I
9/2 ➟
4
I
11/2
2)
4
I
11/2
→
4
F
5/2,7/2
→
➟
4
S
3/2
1)
4
I
15/2
→
4
I
11/2
(Er
1
3+
)
2)
4
I
15/2
→
4
I
11/2
(Er
2
3+
)
3)
4
I
11/2
–
4
I
15/2
(Er
1
3+
) ⇒
4
I
11/2
–
4
F
7/2
➟
4
S
3/2
(Er
2
3+
)
4
F
9/2
Yb
3+
Yb
3+
1)
2
F
7/2
→
2
F
5/2
(Yb
3+
)
2)
4
I
15/2
→
4
I
13/2
(Er
3+
)
3)
2
F
5/2
–
2
F
7/2
(Yb
3+
) ⇒
4
I
13/2
–
4
F
9/2
(Er
3+
)
1)
2
F
7/2
→
2
F
5/2
(Yb
3+
)
2)
2
F
5/2
–
2
F
7/2
(Yb
3+
) ⇒
4
I
15/2
–
4
I
11/2
(Er
3+
)
3)
2
F
7/2
→
2
F
5/2
(Yb
3+
)
4)
2
F
5/2
–
2
F
7/2
(Yb
3+
) ⇒
4
I
11/2
–
4
F
7/2
(Er
3+
)
➟
4
F
9/2
4
I
11/2
— 1)
4
I
15/2
→
4
I
13/2
(Er
1
3+
)
2)
4
I
15/2
→
4
I
13/2
(Er
2
3+
)
3)
4
I
13/2
–
4
I
15/2
(Er
1
3+
) ⇒
4
I
13/2
–
4
I
9/2 ➟
4
I
11/2
(Er
2
3+
)
Tm
3+ 1
I
6
Yb
3+
1)
2
F
7/2
→
2
F
5/2
(Yb
3+
)
2)
2
F
7/2
–
2
F
5/2
(Yb
3+
) ⇒
3
H
6
–
3
H
5
(Tm
1
3+
)
➟
3
F
4
3)
2
F
7/2
→
2
F
5/2
(Yb
3+
)
4)
2
F
5/2
2
F
7/2
(Yb
3+
) ⇒
3
F
4
3
F
3
(Tm
1
3+
)
➟
3
H
4
5)
3
F
3
–
3
H
6
(Tm
1
3+
) ⇒
3
F
3
–
1
D
2
(Tm
2
3+
)
6)
2
F
7/2
→
2
F
5/2
(Yb
3+
)
7)
2
F
5/2
2
F
7/2
(Yb
3+
) ⇒
1
D
2
3
P
J
(Tm
2
3+
)
➟
1
I
6
Tm
3+ 1
D
2
— 1)
3
H
6
→
3
H
4
2)
3
H
4
→
1
D
2
1)
3
H
6
→
3
H
4
(Tm
1
3+
)
2)
3
H
6
→
3
H
4
(Tm
2
3+
)
3)
3
H
4
–
3
H
6
(Tm
1
3+
) ⇒
3
H
4
–
1
D
2
(Tm
2
3+
)
Tm
3+ 3
H
4
Yb
3+
1)
2
F
7/2
→
2
F
5/2
(Yb
3+
)
2)
3
H
6
→
3
H
5 ➟
3
F
4
(Tm
3+
)
3)
2
F
5/2
–
2
F
7/2
(Yb
3+
) ⇒
3
F
4
–
3
F
2
(Tm
3+
)
➟
3
H
4
©2001 CRC Press LLC
Table 1.1.3—continued
Multi-step Upconversion Excitation Schemes
Laser
ion
Upper
laser
level
Codopant
ion Upconversion excitation scheme
Tm
3+ 1
G
4
Yb
3+
1)
2
F
7/2
→
2
F
5/2
(Yb
3+
)
2)
2
F
7/2
–
2
F
5/2
(Yb
3+
) ⇒
3
H
6
–
3
H
5
(Tm
3+
)
➟
3
F
4
3)
2
F
7/2
→
2
F
5/2
(Yb
3+
)
4)
2
F
5/2
2
F
7/2
(Yb
3+
) ⇒
3
F
4
3
F
2➟
3
H
4
(Tm
3+
)
5)
2
F
7/2
→
2
F
5/2
(Yb
3+
)
6)
2
F
5/2
–
2
F
7/2
(Yb
3+
) ⇒
3
H
4
–
1
G
4
(Tm
3+
)
Table 1.1.4
Cascade Laser Schemes
→ lasing transition
➟
nonradiative transition
Laser ion Cascade transitions
Pr
3+ 3
P
0
→
1
G
4
→
3
F
4
3
P
0
→
1
G
4
→
3
H
5
Nd
3+ 4
F
3/2
→
4
I
13/2
→
4
I
11/2
Ho
3+ 5
S
2
→
5
I
5
→
5
I
6
5
S
2
→
5
I
5
→
5
I
7
5
S
2
→
5
I
6
→
5
I
8
5
S
2
→
5
I
7
→
5
I
8
5
S
2
→
5
I
5
➟
5
I
6
→
5
I
7
5
S
2
→
5
I
5
➟
5
I
6
→
5
I
8
5
S
2
→
5
I
5
➟
5
I
6
→
5
I
7
→
5
I
8
5
S
2
→
5
F
5
➟
5
I
4
➟
5
I
5
→
5
I
6
→
5
I
7
5
I
6
→
5
I
7
→
5
I
8
Er
3+ 4
S
3/2
→
4
I
9/2
→
4
I
11/2
4
S
3/2
→
4
I
9/2
→
4
I
13/2
4
S
3/2
→
4
I
11/2
→
4
I
13/2
4
S
3/2
→
4
I
13/2
→
4
I
15/2
4
S
3/2
→
4
I
9/2 ➟
4
I
11/2
→
4
I
13/2
4
S
3/2
→
4
I
9/2 ➟
4
I
11/2
→
4
I
13/2
→
4
I
15/2
4
F
9/2
→
4
I
11/2
→
4
I
13/2
4
I
11/2
→
4
I
13/2
→
4
I
15/2
Tm
3+ 3
F
4
→
3
H
5 ➟
3
H
4
→
3
H
6
©2001 CRC Press LLC
Table 1.1.5
Cross-Cascade Laser Schemes
→ lasing transition ⇒ nonradiative energy transfer transitions
Laser ions Cross-cascade transitions
Er
3+
+ Ho
3+ 4
S
3/2
→
4
I
13/2
(Er
3+
)
4
I
13/2
–
4
I
15/2
(Er
3+
) ⇒
5
I
8
–
5
I
7
(Ho
3+
)
5
I
7
→
5
I
8
(Ho
3+
)
4
I
11/2
→
4
I
13/2
(Er
3+
)
4
I
13/2
–
4
I
15/2
(Er
3+
) ⇒
5
I
8
–
5
I
7
(Ho
3+
)
5
I
7
→
5
I
8
(Ho
3+
)
Er
3+
+ Tm
3+ 4
S
3/2
→
4
I
13/2
(Er
3+
) ⇒
4
I
13/2
–
4
I
15/2
(Er
3+
) ⇒
3
H
6
–
3
F
4
(Tm
3+
)
3
F
4
→
3
H
6
(Tm
3+
)
4
I
11/2
→
4
I
13/2
(Er
3+
)
4
I
13/2
–
4
I
15/2
(Er
3+
) ⇒
3
H
6
–
3
F
4
(Tm
3+
)
3
F
4
→
3
H
6
(Tm
3+
)
Tm
3+
+ Ho
3+ 3
H
4
→
3
H
5 ➟
3
F
4
(Tm
3+
)
3
F
4
–
3
H
6
(Tm
3+
)
⇒
5
I
8
–
5
I
7
(Ho
3+
)
55
I
7
→
5
I
8
(Ho
3+
)
3
H
4
→
3
F
4
(Tm
3+
)
3
F
4
–
3
H
6
(Tm
3+
)
⇒
5
I
8
–
5
I
7
(Ho
3+
)
55
I
7
→
5
I
8
(Ho
3+
)
Er
3+
+ Tm
3+
+ Ho
3+ 4
I
11/2
→
4
I
13/2
(Er
3+
)
4
I
13/2
–
4
I
15/2
(Er
3+
) ⇒
3
H
6
–
3
F
4
(Tm
3+
)
3
F
4
–
3
H
6
(Tm
3+
)
⇒
5
I
8
–
5
I
7
(Ho
3+
)
55
I
7
→
5
I
8
(Ho
3+
)
©2001 CRC Press LLC
Further Reading
Caird, J. and Payne, S. A., Crystalline Paramagnetic Ion Lasers, in Handbook of Laser
Science and Technology, Suppl. 1: Lasers, CRC Press, Boca Raton, FL (1991), p. 3.
Hanna, D. C. and Jacquier, B., Eds., Miniature coherent light sources in dielectric media,
Opt. Mater. 11, Nos. 2/3 (1999).
Kaminskii, A. A., Crystalline Lasers: Physical Processes and Operating Schemes, CRC
Press, Boca Raton, FL (1996).
Kaminskii, A. A., Laser Crystals, Their Physics and Properties, Springer-Verlag,
Heidelberg (1990).
Moulton, P., Paramagnetic Ion Lasers, in Handbook of Laser Science and Technology, Vol.
I: Lasers and Masers, CRC Press, Boca Raton, FL (1995), p. 21
©2001 CRC Press LLC
1.1.2 Host Crystals Used for Transition Metal Laser Ions
Table 1.1.6
Host Crystals Used for Transition Metal Laser Ions
Crystal Ti
3+
V
2+
Cr
2+
Cr
3+
Cr
4+
Mn
5+
Fe
2+
Co
2+
Ni
2+
Oxides
Al
2
O
3 • •
Ba
3
(VO
4
)
2 •
BeAl
2
O
4 • •
BeAl
6
O
10 •
Be
3
Al
2
Si
6
O
18 •
CaGd
4
(SiO
4
)
3
O
•
CaY
2
Mg
2
Ge
3
O
12 •
Ca
2
GeO
4 •
Ca
3
Ga
2
Ge
3
O
12 •
Ca
3
Ga
2
Ge
4
O
14 •
Gd
3
Ga
5
O
12 •
Gd
3
Sc
2
Al
3
O
12 •
Gd
3
Sc
2
Ga
3
O
12 •
La
3
Ga
5
GeO
14 •
La
3
Ga
5.5
Nb
0.5
O
14 •
La
3
Ga
5.5
Ta
0.5
O
14 •
La
3
Ga
5
SiO
14 •
LiNbGeO
5 •
Mg
2
SiO
4 •
MgO •
ScBO
3 •
ScBeAlO
4 •
Sr
3
Ga
2
Ge
4
O
14 •
SrGd
4
(SiO
4
)
3
O
•
YA1O
3 •
Y
2
SiO
5 •
Y
3
Al
5
O
12 • •
Y
3
Ga
5
O
12 •
Y
3
Sc
2
Al
3
O
12 •
Y
3
Sc
2
Ga
3
O
12 •
ZnWO
4 •
Halides
CsCaF
3 •
KMgF
3 • •
©2001 CRC Press LLC
Table 1.1.6—continued
Host Crystals Used for Transition Metal Laser Ions
Crystal Ti
3+
V
2+
Cr
2+
Cr
3+
Cr
4+
Mn
5+
Fe
2+
Co
2+
Ni
2+
KZnF
3 • •
LiCaAlF
6 •
LiSrAlF
6 • •
LiSrCrF
6 •
LiSrGaF
6 •
MgF
2 • •
MnF
2 •
Na
3
Ga
3
Li
3
F
12 •
SrAlF
5 •
ZnF
2 •
Chalcogenides
CdMnTe •
ZnS •
ZnSe • •
Phosphide
n-InP •
1.1.3 Host Crystals Used for Lanthanide Laser Ions
Table 1.1.7
Host Crystals Used for Divalent Lanthanide Laser Ions
Crystal Sm
2+
Dy
2+
Tm
2+
Halides
CaF
2 • • •
SrF
2 • •
Table 1.1.8
Host Crystals Used for Trivalent Lanthanide Laser Ions
Crystal Ce
3+
Pr
3+
Nd
3+
Sm
3+
Eu
3+
Dy
3+
Ho
3+
Er
3+
Tm
3+
Yb
3+
Oxides
Al
2
(WO
4
)
3 •
Ba
0.25
Mg
2.75
-
Y
2
Ge
3
O
12
•
Ba
2
MgGe
2
O
7 •
©2001 CRC Press LLC
Table 1.1.8—continued
Host Crystals Used for Trivalent Lanthanide Laser Ions
Crystal Ce
3+
Pr
3+
Nd
3+
Sm
3+
Eu
3+
Dy
3+
Ho
3+
Er
3+
Tm
3+
Yb
3+
Oxides
BaGd
2
(MoO
4
)
4 •
BaLaGa
3
O
7 •
Ba
2
NaNb
5
O
15 •
Ba
2
ZnGe
2
O
7 •
Ba
3
LaNb
3
O
12 •
Bi
4
Ge
3
O
12 • • •
Bi
4
Si
3
O
12 •
Bi
4
(Si,Ge)
3
O
12 •
Bi
12
SiO
20 •
Ca
0.25
Ba
0.75
-
(NbO
3
)
2
•
CaAl
4
O
7
•
•
CaGd
4
(SiO
4
)
3
O
•
CaLa
4
(SiO
4
)
3
O
•
CaMg
2
Y
2
Ge
3
O
12 •
CaMoO
4 • • •
Ca(NbO
3
)
2 • • • •
Ca(NbGa)
2
-
Ga
3
O
12
•
CaSc
2
O
4 •
CaWO
4 • • • • •
CaYAlO
4 •
CaY
2
Mg
2
Ge
3
O
12 • •
CaY
4
(SiO
4
)
3
O
• • •
Ca
2
Al
2
SiO
7 • •
Ca
2
Ga
2
Ge
4
O
14 •
Ca
2
Ga
2
SiO
7 •
Ca
3
Ga
2
Ge
3
O
12 • •
Ca
3
Ga
2
Ge
4
O
14 •
Ca
3
Ga
2
SiO
7 •
Ca
3
Ga
4
O
9 •
Ca
3
(Nb,Ga)
2
-
(Ga
3
O
12
•
Ca
3
(NbLiGa)
5
O
12 •
Ca
3
(VO
4
)
2 •
Ca
4
GdO(BO
3
)
3 •
Ca
4
La(PO
4
)
3
O
•
©2001 CRC Press LLC
Table 1.1.8—continued
Host Crystals Used for Trivalent Lanthanide Laser Ions
Crystal Ce
3+
Pr
3+
Nd
3+
Sm
3+
Eu
3+
Dy
3+
Ho
3+
Er
3+
Tm
3+
Yb
3+
CeP
5
O
14 •
CsLa(WO
4
)
2 •
CsNd(MoO
4
)
2 •
ErAlO
3 • • •
ErVO
4
Er(Y,Gd)AlO
3 • •
Er
2
O
3 •
Er
2
SiO
5 • • •
Er
3
Al
5
O
12 •
Er
3
Sc
2
Al
3
O
12 •
Ga
3
Al
5
O
12 •
GdAlO
3 • • • •
GdGaGe
2
O
7 •
GdP
5
O
14 •
GdScO
3 •
GdVO
4 • •
Gd
2
(MoO
4
)
3 •
Gd
2
(WO
4
)
3 •
Gd
2
O
3 •
Gd
3
Al
5
O
12 • •
Gd
3
Ga
5
O
12 • • • •
Gd
3
Sc
2
Al
3
O
12
•
• •
Gd
3
Sc
2
Ga
3
O
12 • • •
HfO
2
-Y
2
O
3 •
Ho
3
Al
5
O
12 •
Ho
3
Ga
5
O
12 •
Ho
3
Sc
2
Al
3
O
12 •
KEr(WO
4
)
2 •
KGd(WO
4
)
2
•
KGd(WO
4
)
2 • • • •
KLa(MoO
4
)
2 • • •
KLu(WO
4
)
2 • •
KNdP
4
O
12
•
KY(MoO
4
)
2
•
KY(WO
4
)
2 • • • •
K(Y,Er)(WO
4
)
2 • •
K
3
(La,Nd)(PO
4
)
2
•
K
5
Bi(MoO
4
)
4
•
[...]... )3 F Sr5 (VO4 )3 Cl Sr5 (VO4 )3 F Chalcogenides La 2 O 2 S ©2001 CRC Press LLC • 1.1.4 Tables of Transition Metal Ion Lasers Table 1.1.9 Transition Metal Ion Lasers Optical pump AL ArL D DL ErLYF ErYAG Hg KrL NdGL NdL NdYAG NdYLF NdYAP RL RS TiS TmYAP TmHoYAG W Xe — — — — — — — — — — — — — — — — — — — — Mode of operation AML — actively mode-locked cw — continuous wave p — pulsed qcw — quasi-continuous... CaF2 -CeF3 CaF2 -GdF 3 CaF2 -HoF 3 • • • • • • • • • • • • • • CaF2 -HoF 3 -ErF 3 CaF2 -LaF 3 CaF2 -NdF 3 CaF2 -ScF3 CaF2 -SrF2 CaF2 -SrF2 -BaF2 YF3 -LaF 3 CaF2 -YF 3 CaF2 -YF 3 -NdF 3 CdF 2 CdF 2 -CeF3 CdF 2 -GaF 3 CdF 2 -GdF 3 CdF 2 -LaF 3 CdF 2 -LuF 3 CdF 2 -ScF3 CdF 2 -YF 3 CdF 2 -YF 3 -NdF 3 CeCl 3 CeF3 CsGd 2 F7 CsY 2 F7 • • • • • • • • • • • • • • • • • • • • • ErF 3 -HoF 3 • ErLiF 4 GdF 3 -CaF2... KYF 4 Eu3+ D y 3+ Ho 3+ Er3+ Tm 3+ • KY 3 F10 Sm 3+ • • • • K 7 YF 5 K 5 (Nd,Ce)Li2 F10 K 5 NdLi 2 F10 LaBr 3 LaCl3 (La,Pr)Cl3 LaF 3 • • • • • • • • • LaF 3 -SrF2 LiCaAlF 6 • • • LiErF 4 • LiGdF 4 • LiHoF 4 • • • • • LiKYF 5 LiLuF 4 LiSrAlF 6 LiYF 4 • • • • • Li(Y,Er)F4 LiYbF 4 • • • • • • • • • • MgF 2 MnF 2 α-NaCaCeF 6 α-NaCaErF6 α-NaCaYF6 • • Na 0.4 Y 0.6 F2.2 PbCl 2 PrCl 3 PrF 3 SrF2 • • • • SrF2 . 1.1.4–1.1.8. The
success of many of the schemes depends upon the degree of resonance of energy transfer
transitions and the rate of nonradiative transitions. CRC Press LLC
1.1.4 Tables of Transition Metal Ion Lasers
Table 1.1.9
Transition Metal Ion Lasers
Optical pump
Mode of operation
AL — alexandrite
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