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ARTICLE IN PRESS

Progress in Quantum Electronics 28 (2004) 249–303


www.elsevier.com/locate/pquantelec

Review

Cr4+-doped crystals: their use as lasers and


passive Q-switches
Yehoshua Kalisky
R&D Department, Nuclear Research Center, Negev, P.O. Box 9001, Beer-Sheva 84190, Israel

Abstract

This review provides an overview on the subject of Cr4+-doped solids and their
numerous applications in laser physics, technology, and industry. The transition metal
ions have spectral properties which make them favorable candidates for active lasing
ions. In particular, the Cr4+-doped crystal has the unique characteristics of being
both a saturable absorber for the 1.06 mm laser emission of Nd:YAG as well as being a
tunable mid-IR laser in the spectral range of E1.3 to E1.6 mm with significant practical
implications.
The review covers the basic spectroscopic concepts and particularly the spectroscopic
properties, structural characteristics, and physical parameters of Cr4+ doped various solids.
The effects on the laser performance and on the quantum efficiency of non-radiative relaxation
from the first excited state level will be critically reviewed, and possible proposed models will
be introduced and analyzed.
Knowing the spectroscopic properties, the physical parameters, and the crystal field effects
on the position of the energy levels, we shall discuss the use of various Cr4+-doped solids such
as forsterite and garnets as room temperature, tunable mid-IR lasers in the spectral range
1.3–1.6 mm, with emphasis on the crystal field and coordination effects on the spectroscopy
and laser performance of Cr4+-doped solids.
The last section deals with the role of several Cr4+-doped garnets as saturable absorbers in
various Nd- and Yb-doped crystals, both in lamp- and diode-pumped systems. We shall also
focus on understanding the physics of the saturation process in saturable absorbers for

E-mail address: kalisky@netvision.net.il (Y. Kalisky).

0079-6727/$ - see front matter r 2004 Published by Elsevier Ltd.


doi:10.1016/j.pquantelec.2004.09.001
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250 Y. Kalisky / Progress in Quantum Electronics 28 (2004) 249–303

improving the utilization of these materials. Several systems of passively Q-switched systems
and their current applications will be discussed.
r 2004 Published by Elsevier Ltd.

PACS: 42.55.Xi; 42.55.Rz; 42.60.Gd; 42.60.V

Contents

1. General introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250

2. Spectroscopy of Cr3+ ions: general concepts . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251


2.1. Spectroscopy: optical transitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 254
2.2. Structure and crystal growth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255

3. Physical parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257


3.1. Non-radiative relaxation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257
3.2. Polarization effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261

4. Lasers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262
4.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262
4.2. External effects on laser performance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
4.2.1. Coordination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
4.2.2. Crystal field . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264
4.2.3. Crystal field effect on Cr3+ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264
4.2.4. Crystal field effect on Cr4+ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
4.3. Laser performance of some Cr4+-doped hosts . . . . . . . . . . . . . . . . . . . . . . 268
4.3.1. Free-running, pulsed or CW operation mode . . . . . . . . . . . . . . . . . 268
4.3.2. Mode-locked ultrafast lasers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 271
4.4. Thermal effects in a laser system and resonator design . . . . . . . . . . . . . . . . 272
4.5. Effect of spectroscopy and physical parameters on laser performance . . . . . . 273

5. Passive Q-switching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 275


5.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 275
5.2. Saturation of Cr4+ doped crystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 276
5.3. ESA spectra. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 284

6. Passively Q-switched lasers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285


6.1. Lamp-pumped lasers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285
6.2. Diode-pumped systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 292

7. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 296

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 298

1. General introduction

Cr4+ belongs to the family of transition metal elements with 3-d valence electronic
levels. More precisely, it belongs to the d-block elements, which can lose their
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valence s-electrons as well as d-electrons, thus yielding various oxidation states. The
energetic position of the d- orbitals depends strongly on the applied crystal field. The
five degenerate d- orbitals in the free-ion configuration split into a set of three
orbitals, dxy, dyz, dzx, and two orbitals, dz2 and dx2 y2 ; under the influence of crystal
field. These orbitals are denoted also as t2g and eg, respectively. The relative energetic
position of t2g and eg, or in other words, the ligand field splitting, depends on the
coordination of the transition metal, and hence, the coordination and the strength of
the crystal field affect the spectroscopic characteristics and the optical transitions of
Cr ions. In order to understand the basic concepts of the ligand field theory and, in
particular, those properties related to optical transitions, we start with a brief
summary of Cr3+ ions.

2. Spectroscopy of Cr3+ ions: general concepts

The spectroscopic properties of Cr3+-free ions or doped systems have been studied
extensively and summarized in numerous publications (see for example, Refs. [1–3]].
In a doped system, the Cr ion is surrounded by anion lattice points (also called
ligands). When the Cr3+ is in octahedral symmetry, the t2g electrons (located in the
dxy, dyz, and dzx orbitals) are directed between the point charges of the ligands, while
the eg electrons dz2 ; dx2 y2 orbitals) are directed toward the negative lattice point
charges. Fig. 1a and b presents the electron density distribution of the 5d orbitals
and the relative energetic positions of t2g and eg orbitals in various symmetries,
respectively. As a result of the electrostatic repulsive forces, eg orbitals are of higher
energy than the t2g orbitals. This fact explains, as will be discussed below, the
broadening of octahedrally coordinated Cr3+ emission and its tunability. In
tetrahedral symmetry, the t2g orbitals point directly to the negative ligands, and
therefore, the three t2g orbitals have higher energy than the two eg orbitals.
The rotating electron has angular momentum, which is perpendicular to the
circular plane of motion. This angular momentum is a vector denoted by L, as well
as by its three-dimensional components Lx, Ly, Lz such that its value is given by
jLj ¼ ðLx þ Ly þ Lz Þ1=2 : In the case of one electron, the value of the total angular
momentum is given by L2 ¼ lðl þ 1Þ_2 where l=0, 1, 2,y and the z component of
the angular momentum is given by Lz ¼ ml _; ml ¼ l; l þ 1; . . . ; l  1; l; where l is
the angular momentum quantum number and ml is the magnetic quantum number,
or the quantum number of the z component of the angular momentum. The angular
momentum has degeneracy of 2l+1 in the absence of magnetic or electric field. In
the presence of external fields, the 2l+1 degeneracy with respect to m is removed.
The rotating electron also has spin angular momentum denoted by the vector S,
with magnitude of S 2 ¼ sðs þ 1Þ_2 ; where s is the spin quantum number, s ¼ 1=2:
The z component of the spin angular momentum is given by S z ¼ ms _; where ms ¼
1=2 is defined as the quantum number of the z component of the spin angular
momentum.
For a many-electron atomic system, the total orbital angular momentum and spin
angular momentum is a result of contribution of the individual electrons as will be
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252 Y. Kalisky / Progress in Quantum Electronics 28 (2004) 249–303

Fig. 1. (a) The relative energies of the five d orbitals in octahedral and tetrahedral symmetries. (b) The
electron density distribution of the five d orbitals.

discussed below. The total angular momentum is a sum over the individual electrons:
L=Sli, y, where li is the orbital angular momenta of individual electrons and L are
the orbital angular momenta of the atoms. For the z component of the angular
momentum, Lz, we have a similar summation over all i electrons: Lz ¼ Sl zi ¼ Smli _;
where mli is the magnetic quantum number of the ith electron. Also for an atomic
system, the magnetic quantum numbers are defined as M L ¼¼ Smli _; with values for
ML, in the range, L, y,+L. The orbital quantum number of an atom is defined as
L=l1+l2, l1+l21, y, |l1l2| for a two-electron system with orbital momentum
quantum numbers of l1 and l2 for the two electrons.
The total spin angular momentum is a contribution of the individual spin angular
momenta: S=Ssi, with si defined as the spin angular momenta of single electrons.
Similar to the case of the orbital angular momentum, the z component Sz of the total
spin angular momentum of an atom is the sum of the z components of the individual
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electrons: Sz=Sszi, where szi is the contribution of the ith electron to the z component
of the spin angular momentum, and the summation is done over i electrons. Since
szi=msi_, the z component of thePtotal spin angular momentum is given by:
Sz=Sszi=Smsi _=MS_. Here M S ¼ msi ; and the values S are given by S=S,y,
+S, where S is the spin quantum number i of the system. The spin quantum number
S will have values of S=s1+s2, s1+s21,y, |s1s2|, for a two-electron system, with
spin quantum numbers s1 and s2 of the two individual electrons.
The total angular momentum J of an atom is the vector sum of the orbital
momenta and spin angular momenta of the individual electrons, li and si,
respectively. Its quantum number J will have certain values which depend on the
different interactions inside a multi-electron system. In principle, there are three
types of interactions: orbital–orbital (ll interaction), spin–spin (ss interaction) and
spin–orbit (ls interaction). The relative position of an atomic state depends on the
relative contribution of these interactions. In the case when ls interaction is weaker
than the ll or ss interactions (for atoms with Zo40), the spin orbit interaction will
result from coupling of the total orbital and spin angular momentum as follows: the
ll and ss interactions become dominant and interact independently to produce total
(resultant) orbital angular momentum L and total spin angular momentum S. These
independent angular momenta interact to give the total angular momentum J of the
system: J=L+S. The resultant L and S vectors are less coupled with one another
than the individual vectors, and their resultant is given by J. Similarly, the z
component of J is given by: Jz=Lz+Sz. As emphasized here, these momenta interact
via LS coupling or Russell–Saunders coupling, to form the total angular momentum
J. This coupling can be described schematically as: (s1, s2,y) (l1, l2,y)-(S,L)=J.
Here the quantum number J of the total angular momentum of an atom has the
following values: L+S, L+S1, y, |LS|, with values ranging from J to +J. In
an analogous way to the orbital angular momentum, the magnetic quantum number
MJ is given by: MJ=ML+MS, J=J,y,+J.
In the case of Cr3+, which has more than one electron in the d-shell electronic
configuration, the states discussed above will have different electronic energies
depending on the L, S, and J quantum numbers, and will be characterized by the
following term symbol, 2S+1LJ, where the values of S, J, and L were defined
previously, and 2S+1 is the spin multiplicity. In the following term symbol the total
orbital angular momentum L is represented by the letters S,P,D,F,G, y for different
L values: L=0, 1,2,3,4,y, respectively. We should mention here that since the
electron spins do not interact directly with the ligands, the spin multiplicity of a state
is unaffected by the splitting under crystal field interaction.
In the absence of any field, the ion is in a free state and the d orbitals are
degenerate. In an octahedral or tetrahedral symmetry, the five d orbitals are no
longer degenerate. They belong to different irreducible representations of the
octahedral point group (Oh) eg, which belongs to the GEg irreducible representation,
and t2g which belongs to the GT2g irreducible representation will interact differently
with their octahedral environment [4,5].
The ligand field description of Cr3+ in octahedral coordination can be described
by Russell–Saunders terms of the free ion and the group theoretical representation of
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the symmetry sites in octahedral symmetry [6]. Let us now examine how the splitting
of the free ion states by the surrounding ligands depends on the mutual ion–ligand
interaction. This brief discussion is relevant to dn electronic configuration with Td or
Oh symmetry. We also assume that each ligand is a point charge, and that the
metal–ligand interaction is purely electrostatic. The analysis of energy-level position
is carried out under several limiting conditions as will be discussed below:
Infinitely weak interaction: In this case, there is a separation into Eg and T2g states,
with a separation which is a function of Do, which is defined as the energy separation
between the two levels.
Infinitely strong interaction: In the case of an infinitely strong interaction, we
assume that the inter-electronic repulsions in the transition metal ion are small as
compared to the infinite crystal field. In the case of infinite interaction, the splitting
in the free-ion states is much larger than the separation of each free-ion state. In the
case of the d2 state in an octahedral symmetry, there are three possible states namely,
t22g ; t12g e1g ; e2g : The energy separation is denoted by Do or 10Dq. Also, the t22g level is
occupied by two electrons (Hund’s rule) to form the lowest lying level. The next
highest state will be t22g e1g ; and it will be followed by e2g state.
Intermediate interaction: In the case of an intermediate (strong) interaction, the
electronic repulsions become significant perturbations and they affect the config-
uration states. As a result of these perturbations the states will split into strong-field
states. The methodology to find the new electronic states and their energies is to treat
the inter-electronic repulsion as an infinitely strong interaction.

2.1. Spectroscopy: optical transitions

We start this section with a brief discussion on general concepts in the


spectroscopy of transition metal ions. For this purpose, we illustrate the concepts
using Cr3+ as an example.
The spectra of Cr3+, both in the UV and the visible spectral regime, result from
optical transitions among d–d orbitals. These transitions occur from the ground state
to excited states, or from various excited states, to the ground state. These states
depend on the coupling of the orbital and spin angular momenta, and are
characterized by the SLJ quantum numbers. The spectroscopic transitions in atomic
and molecular systems are induced by electric vectors of electromagnetic radiation
with atomic or molecular dipoles. The electric dipole transition probability in the
atomic or molecular system, from state n to state m is defined by the square of the
transition dipole moment, mnm, which is defined by the following integral:
Z
mnm ¼ Cn mCm dt; (1)

where Cn and Cm are the wave functions of the n and m states, and m is the dipole
moment operator moment of the atomic or molecular system defined by, m ¼ Sqiri :
In this equation, qi is the ith charge, ri is the radius vector separating the positive and
negative charges, and the summation is over all the electrons and the nuclei of the
system. When mnm a0; spectral lines which result from the power radiated by the
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electric–dipole of the atom will be observed; however, these transitions (termed as


electric–dipole allowed transitions) are governed by two main selection rules:
1. Spin selection rule
2. Laporte selection rule.

The spin selection rule states that in any transition between different states there
exists DS ¼ 0: That is, no transition can occur between states of different multiplicities.
Transitions that violate this rule are generally weak and usually ignored.
The Laporte rule states that electric dipole transitions between states of the same
parity (u or g) are forbidden. This can be summarized by noting that u-g and g-u
transitions are allowed while g-g and u-u transitions are forbidden. Since the
transitions in the chromium ions are among d states, e.g. among states of the same
parity, they are Laporte forbidden. The Laporte rule results from the symmetry of the
surroundings as well as from the Born–Oppenheimer approximation which assumes
that during electronic transitions there is no vibrational change. However, due to the
molecular vibrations, the surrounding will not always be symmetrical, and the
forbidden transitions will occur. These are weak transitions with oscillator strength of
the order of E104. It is important to note here that there are two other types of
transitions which will not be discussed since they are not relevant to the optical
properties of Cr4+- doped solids. The first type is the charge transfer transition which
can be described as transfer of electrons from the neighboring ligands to the metal ion
(and vice versa). These transitions are allowed and are of higher intensities and energies
than the d–d transitions. The second type of transition is at occurring within the ligand
electronic states. Since they are irrelevant, they will be ignored. There are also selection
rules associated with L and J quantum numbers, namely, DL ¼ 0; 71, (except for
L=0 to L=0 transitions) and DJ ¼ 0; 71, (except for J=0 to J=0 transitions).
The dependence of the energy-level position and hence, the d–d spectrum on the
applied crystal field in 3d elements was analyzed by Tanabe and Sugano, and also
called Tanabe–Sugano correlation diagrams [6].
The Tanabe–Sugano correlation diagrams are based on the quantum mechanical
treatment of the energy levels of a dn system (n is the number of electrons), under two
fields: inter-electronic repulsions and medium crystal field strength. It was found that
under medium field strength, the splitting of each state of the d manifold depends on
the field strength measured by Do or Dt and also on the electronic repulsion
parameters also known as Racah parameters, denoted by B and C. In the
Tanabe–Sugano theory it is assumed that C is proportional to B and that the
proportionality constant has a fixed value for each diagram. However, the diagrams
are independent of B since both the energy of each state (E) and the crystal field
strength (Do or Dt ) are normalized to B.

2.2. Structure and crystal growth

Cr4+, which has a d2 configuration, occupies tetrahedral sites in garnets. The 4+


oxidation state is stabilized by addition of Mg2+ or Ca2+ as charge compensating
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ions in the most commonly used crystals. The 3T2-3A2 electronic transition, which
is believed to be the near-IR transition is the magnetic dipole allowed in tetrahedral
(Td) symmetry, and becomes electric–dipole-allowed transition due to the lack of
inversion symmetry tetragonal distorted tetrahedron with D2d symmetry.
Garnets have the general structure of A3C2B3O12, where A, C, and B are different
lattice sites with different oxygen coordination, namely, dodecahedral, octahedral, and
tetrahedral, respectively. The Cr4+ emission that results from sites with Td symmetry is
not polarized, due to the cubic symmetry of the garnets. The garnets are grown by the
Czochralski method using a high-frequency induction-heated iridium crucible. The
growth rate is usually about 3 mm/h with a rotation rate of 20 rpm. The crystals are
grown along the [1 1 1] crystallographic axis. Although the garnets have cubic symmetry,
we shall see in the following sections that Cr4+:YAG exhibits some polarization
properties due to the distorted tetrahedrally coordinated Cr4+ sites with D2d symmetry.
The forsterite crystal Mg2SiO4 doped with Cr4+ is another candidate for
room temperature-tunable solid-state lasers in the IR, as can be expected from
fluorescence properties. It has an orthorhombic structure with space group Pbnm,
and as a result, polarized optical spectrum. Early publications identified the active
center emitting in the infrared as the ‘‘center’’ [7], but other publications based on
pure spectroscopic arguments confirmed that it should be Cr4+ in tetrahedral
coordination [8,9]. It was found that Cr4+ substitutes the tetrahedrally coordinated
Si4+ ions (distorted tetrahedral sites) while Cr3+ substitutes the Mg2+ octahedral
sites [10]: M1 with inversion symmetry (Ci) and M2 with mirror symmetry (Cs). The
octahedral M1 and M2 sites of Cr3+ form a medium field system with 2E-4T2 sharp
line emission at low temperature. Since there is a mismatch between the size of Cr3+
and that of Mg2+, it results in strain on the (CrO4)4 tetrahedron and hence site
distortion. Also, the charge imbalance in the Cr3+, Mg2+ substitution creates lattice
defects and distortion, which is a favorable condition for efficient electric dipole-
induced transitions. At high temperatures (200–300 K), there is thermalization and
thermal equilibrium between 4T2 and 2E levels which leads to broadband emission,
via 2E, 4T2-4T2 transition. It was found that the occupation ratio of Cr3+ in the
two sites is given by M1:M2=3.2 [11]. Since the M2 sites lack inversion symmetry, it
is expected that the Cr3+ that occupies these sites will exhibit electric–dipole-allowed
transitions. On the other hand, Cr3+ that occupies the M1 sites (with inversion
symmetry) will exhibit much weaker phonon-assisted optical transitions.
A similar picture is observed in Cr4+: Y2SiO5 (Cr:YOS). This is a monoclinic
biaxial crystal with three lattice parameters and three polarization axes that are
presented in Table 1. It has two octahedral (Y3+) sites and one tetrahedral site
(Si4+). The tetrahedral site of Cr4+ in YOS is less distorted than that of forsterite;
therefore, the symmetry site of Cr4+ in YOS is higher and the electric dipole
transition moment 3T2-3A2 is lower than in other silicates. This crystal has two
main intrinsic advantages: first, the substitution of Si4+ site by Cr4+ ions does not
require charge compensation due to the charge match between Cr4+ and Si4+ ions.
Second, unlike the forsterite and the garnets, the Cr3+ ionic radius is incompatible
with the Y3+ in the octahedral site, and therefore the trivalent oxidation state of
Cr3+ is unstable and it cannot occupy the octahedral site [12,13].
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Table 1
Major physical and experimental parameters of various Cr4+-doped crystals.

Lattice Lattice Constant t (300 K) t (15 K) sem lmax Dl


(Å) (ms) (ms) (1019 cm2) (nm) (nm)

LuAG (Lu3Al5O12) 11.91 5.6 27.7 3.4 1370 232


2.7 [24]
YAG 12.01 4.1 30.1 3.3 1378 224
Y3Sc3xAl5xO12
x=0.22 12.05 4.1 21 3.1 1397 233
x=0.48 12.09 3.3 15.5 3.3 1407 237
x=1.2 12.22 2.0 8.4 4.1 1468 268
x=1.5 12.27 1.5 5.1 4.5 1508 303
x=1.72 12.31 1.4 4.9 1593 298
Y3Ga5O12 12.28 1.9 11 4.3 1456 238
Gd3Ga5O12 12.38 2.2 16 4.5 1442 231
Gd3Sc2Al3O12 12.39 1.7 5.9 4.8 1599 276
Y3Sc2Al3O12 12.42 1.3 4.9 5.2 1561 279
Gd3Sc2Ga3O12 12.55 2.0 6.1 3.6 1582 299
Mg2SiO4 a=4.76 2.7 29 1.44 1235 150
b=10.22
c=5.99
Ti:Al2O3 a=4.736 3.1 4.5 760 250
c=13.003
Y2SiO5 a=10.41 0.6 15.2 o2 1230 250
c=6.72
c=12.49

3. Physical parameters

3.1. Non-radiative relaxation

Spectroscopic measurements of Cr4+- doped various crystals such as garnets


(YAG, scandium-based garnets, LuAG), Y2SiO5 (YOS), and several groups in
Europe and USA have extensively studied forsterite (Mg2SiO4) [7,8,10,13–18]. A
very similar study was carried out in Mn2+- doped various apatites [19]. The Mn2+
also belongs to the 3d2 group and its emission cross-section, emission wavelength
and spontaneous lifetime are very similar to that of Cr4+. A desirable characteristic
of any laser material is high radiative rate, and consequently low non-radiative rate,
and low spontaneous (radiative) lifetime, according to the classical treatment of
Einstein. The energy density inside the cavity due to 2-1 transition is related to the
induced and spontaneous emission rates by:
A21 1
rðnÞ ¼ ; (2)
B21 ehu=kt  1
where rðnÞ is the energy density of the electromagnetic field inside the cavity at the
center frequency n; B21 is the stimulated emission rate and A21 is the spontaneous
emission rate from excited state 2 to lower state 1, and is of the defined also as:
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ðA21 Þ1 ¼ tsp ; where tsp is the spontaneous lifetime or the total radiative lifetime of
the emitting level.
The induced emission rate of the 2-1 transition at radiation field n is given by:

l2 gðnÞ
W i ðnÞ ¼ I n; (3)
8pn2 hntsp

Where l is the laser wavelength in vacuum, n is the electromagnetic frequency, n is


the refraction index, I n is the intensity of the emission field at frequency n; tsp is the
spontaneous fluorescence lifetime, W i ðnÞ is the induced emission rate, and gðnÞ is the
line shape function. We note here tsp ¼ tr ; the radiative lifetime that will be defined in
Eq. (4) below.
The total emission rate (W) is a combination of both the radiative and non-
radiative rates, and is given by the following equation:

W ¼ W r þ W nr ¼ 1=t ¼ 1=tr þ 1=tnr ; (4)

where Wr and Wnr are the radiative and non-radiative rates, respectively, and tr and
tnr are the radiative and non-radiative lifetimes, respectively. The non-radiative rate
and the quantum efficiency are correlated with the energy gap between the
metastable state and adjacent ground state, as well as with the number of bridging
phonons. The non-radiative rate is also temperature dependent via the phonon
occupation number. For the near-IR emission of Cr4+- doped various garnets we
shall mainly use the data of Kuck et al. [14].
Table 1 presents major laser-related physical and experimental data: lattice
constant, lifetime, emission cross-section, peak emission wavelength, and emission
bandwidth, of various Cr4+- doped garnets, forsterite, and yttrium orthosilicate
(YOS), at room temperature. The value of the emission cross-section for YOS was
obtained indirectly. The effective stimulated emission cross-section in the visible and
IR spectral regime for various polarization axes is given by sem  sesa o5
1020 cm2 ; where sesa is the excited state absorption (ESA) cross-section [20]. The
values for sesa were measured by several authors in the visible and near-IR [21–23]
and range between sesa ¼ 2:4 1019 to 11 1019 cm2 for EJb and EJc,
respectively. This implies that sem o2:4 1019 cm2 or roughly this value since we
made several assumptions as to the wavelength and polarization, sem o2
1019 cm2 : For comparison, we also present in the table the relevant data for
Ti:sapphire.
As can be seen from Table 1, YAG and LuAG have the smallest lattice constant,
therefore the highest crystal field strength and the largest energy gap among various
garnets. Consequently, both LuAG and YAG have the lowest non-radiative rates
and the highest emission lifetimes. Eilers et al. [16] studied and analyzed the
spectroscopic properties of Cr4+:YAG and LuAG, and indicated the unique
properties of Cr4+:LuAG relative to other Cr4+-doped garnets. They also
emphasized the role of the promoting modes (non-totally symmetric phonons) in
mixing the electric dipole character into the magnetic allowed transitions, and
therefore the contribution of the radiative rates to the total emission rate.
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The lifetimes of the IR emission in garnets (which is also the laser transition) at
room temperature range between 5.6 and 3.1 ms time domain while at low
temperature (15 K), the values are between 30.1 and 4.9 ms, depending on the lattice
constant and the crystal field. The stimulated emission cross-section of Cr4+- doped
garnets is between 3.1 1019–5.2 1019 cm2, comparable to the value of
4.5 1019 cm2 for Ti:Al2O3, and much higher than the value for Cr4+:Mg2SiO4
crystal.
The emission quantum efficiency, defined as Z ¼ W r =W ; shows a decrease with the
increase of temperature, due to phonon coupling with the 3d electronic levels.
However, the quantum efficiency is increased slightly with the temperature between
15–130 K before decreasing again as a function of temperature. The total decay rate
can be described by [14]:
W ¼ W r þ W nr ¼ W r ðRvib ; E vib Þ þ W nr ðRnr ; _o; S; pÞ: (5)
In this equation, Rvib, is the radiative decay rate at 0 K, Evib is the energy of the non-
symmetric phonon, Rnr is the non-radiative decay constant, _o is the symmetric
phonon energy, S is the temperature-dependent Huang–Rhys parameter, and p is the
number of phonons needed to bridge the energy gap between excited- and ground-
state levels. The parameter S is an indication to the non-radiative coupling between
two levels, and in the case of transition metal ions its value (SE1–3) indicates
intermediate coupling.
The radiative decay depends on the temperature via the non-totally symmetric
phonons which couple the allowed magnetic dipole transition 3T2-3A2 with the
non-symmetric phonons, and therefore induce electric dipole transitions. The energy
gap and the number of bridging phonons are the most important parameters in
the determination of the quantum efficiency both in rare-earth and in transition
metal ions.
The quantum efficiency behavior with temperature [14] shows that even at low
temperature the non-radiative decay is dominant. The values of quantum efficiency
increase from 15 to 130 K and then, above 130 K decrease. This behavior, which is
similar for all Cr4+- doped garnets, indicates that the coupling of the non-totally-
symmetric phonons and hence the radiative decay rates dominate below 130 K, and
therefore the quantum efficiencies increase. Above 130 K the symmetric phonons and
consequently the non-radiative rates dominate, and quantum efficiencies decrease.
In Cr4+:Y2SiO5, lifetime measurements show a very significant quenching that
starts at 77 K. The strong fluorescence quenching occurs even at low temperatures as
opposed to the case of garnets. This indicates that the standard multi-phonon
relaxation processes cannot be the only mechanism for non-radiative decay in such
crystals. Non-radiative processes can be described by a combined processes namely,
multi-phonon and exchange mechanism. Furthermore, non-radiative decay may be
described more accurately by combining the Mott theory and empirical parameters.
In this description, non-radiative decay requires several activation energies to reach
the cross-over between the first excited state and the ground state as described by the
single configuration coordinate model. The various activation energies correspond to
two different temperature regimes, as was observed and analyzed by Deka et al. [25].
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As can be observed from Table 2, the large number of phonons necessary for
bridging the zero-phonon line energy gap indicates slow non-radiative rates and high
quantum efficiencies, which is opposite to the experimental observations. The
coupling between the two states is intermediate or strong, and therefore the non-
radiative rate cannot be described by the simple energy gap law in the form of
DE
p_o where DE is the energy gap and o is the phonon energy. Bartram et al.
[26] proposed a model where several vibrational frequencies from several electronic
states participate in the non-radiative coupling, thus enhancing the inter-state
coupling and the non-radiative processes.
Table 2 [14] presents the phonon energies (symmetric), the emission quantum
efficiencies at room temperature, and the number of bridging phonons for various
Cr4+- doped garnets. In this table we also include data for forsterite and YOS. The
emission quantum efficiences of forsterite and YOS were calculated from the
radiative and spontaneous fluorescence lifetime data [17,25]. The quantum
efficiencies of Cr4+- doped crystals are much lower than that of Ti:sapphire
(60%) [27]. The number of bridging phonons for forsterite was calculated from
relevant data in Ref. [10]. The number of bridging phonons for YOS was obtained
from experimental data in Refs. [12,25].
From Tables 1 and 2 we observe that the IR spectral characteristics of Cr4+-doped
garnets and forsterite are very sensitive to the crystal field strength: there is a spectral
blue shift as the crystal field strength increases (namely, with the reduction in the
lattice constant). Also, the crystal field strength is inversely proportional to the non-
radiative decay rates. This is reflected clearly in various garnets by the longer lifetime
of the higher number of bridging phonons, and higher quantum efficiency as the
crystal field strength increases. Also by removing the symmetry of the Cr4+ sites, the

Table 2
Phonon energies, quantum efficiencies at room temperature, and number of bridging phonons for several
garnets and forsterite crystals.

Host _o (cm1) Z (300 K) (%) p

LuAG (Lu3Al5O12) 427 33 18.4


YAG 393 [28] 22–15 19.9
Y3Sc3xAl5xO12
x=0.22 428 21 18
x=0.48 431 18 17.8
x=1.2 437 13 16.9
x=1.5 457 11 15.7
Y3Ga5O12 414 12 17.9
Gd3Ga5O12 395 8 19
Gd3Sc2Al3O12 450 9 15.5
Y3Sc2Al3O12 445 10 15.3
Gd3Sc2Ga3O12 435 10 15.8
Mg2SiO4 320 [10] 9.3 28
Y2SiO5 309 [25] E3-5a 28
a
Calculated from the data in Fig. 7 in Ref. [25].
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Table 3
The Si–O bond length in Cr4+:Mg2SiO4 [29].

Crystal axis Si–O length (Å)

a 1.6149
b 1.65530
c (two atoms) 1.66353

Laporte selection rule can be removed, and therefore the transition dipole moment is
allowed since the optical transitions occur between states of different symmetries. In
forsterite or in YOS, the tetrahedrally coordinated length of SiO4 is distorted: the
forsterite has Si–O bond length along a-axis that is shorter than the Si–O bonds
along b- and c-axis, as can be observed in Table 3. The distances between the various
oxygen atoms in forsterite are also different: the distance between oxygen atoms
lying (approximately) in the plane perpendicular to the a- axis is shorter by 7%,
relative to the distance between the oxygen atoms along the a-axis and those in the b
and c planes, and the Si atom is not centered [29]. As stated before, the YOS has an
additional advantage relative to garnets or forsterite, since Cr4+ occupies the
tetrahedral Si site without any Cr3+ in the octahedral sites, and no charge
compensation is needed contrary to the case of garnets.

3.2. Polarization effects

Distorted tetrahedrally coordinated Cr4+ sites in YAG are also accounted for
optical anisotropy in Cr4+:YAG. As a result of this distortion, there are three
different groups of Cr4+ ions oriented along the three orthogonal crystallographic
axes of YAG [1 0 0], [0 1 0], and [0 0 1]. Eilers et al. [28] found that the emission of
Cr4+:YAG is anisotropic. They found that when the polarization vector of the
polarized emission intensity is parallel with the excitation polarization vector, the
emission intensity will reach one maximum value. The strength of the transition
dipole moment of the optical transition from the ground state to the first excited
state also depends on the dipole moment orientation and the propagation direction
vector of the laser beam with the crystallographic axes [1 0 0], [0 1 0], or [0 0 1]. For
two Cr4+:YAG samples, the anisotropic regime was observed in the saturation
regime, starting from intensities between 6 MW/cm2 for the linearly polarized
1064 nm light that propagates along [0 0 1], and at 80 MW/cm2 when the laser light
propagates along [1 1 1] [30].
Under uniaxial pressure there are spectroscopic characteristics that are specific to
the crystallographic axes. This optical anisotropy is reflected by the anisotropy of the
absorption and emission properties of Cr4+:YAG as a function of the pumping
polarization even at low pumping intensities such as 50 kW/cm2 under CW
operation, where the thermally induced birefringence was not observed [28,31].
Liu et al. proposed a twisted mode cavity to compensate for polarization-dependent
internal loss, which results in polarization-dependent processes such as ground-state
absorption and ESA at the laser wavelength and thermally induced birefringence
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loss. (The fluorescence intensity in Cr4+:YAG is polarization independent and


therefore, the laser gain is approximately isotropic.) They also obtained narrow laser
line width peaking at 1453 nm (Dl
0:03 nm FWHM) relative to the free-running
mode peaking at 1449 nm, with line width of, Dl
20 nm FWHM.
Others [32] assume that intensity-induced birefringence in Cr4+:YAG is
responsible for the polarization effects at saturation. They applied numerical
modeling of the Cr4+ polarization and assume that approximately only 1/3 of the
Cr4+ ions are accessed by a linearly polarized laser beam aligned along a
crystallographic axis. It is also possible to control the polarization state of
Cr4+:YAG by selectively pumping the crystal within its absorption (0.8–1.2 mm)
band, with a polarization vector that coincides with one of the orientations of the
crystal. Since the equilibrium between the three crystallographic states is removed,
the crystal exhibits linear anisotropy and under additional CW, low radiation, it is
predicted that a transition to other polarization states will occur [33].
Recent analysis of the optical transitions in Cr4+:YAG under plane polarized
pump light at 1.064 mm yielded new insight into the energy-level scheme of Cr4+ in
the distorted symmetry (D2d point group of symmetry) [34]. The spectroscopic model
of Cr4+ in D2d local symmetry suggests that the optical transition centered at
E1000 nm results from the 3B1(3A2)-3A2(3T1) transition contrary to the previous
assignment of 3B1(3A2)-3E(3T2) transition. Moreover, the energy positions of the
excited states 3A2(3T1) and 3E(3T2) are close to each other; therefore, the weak
3
A2(3T1) and 3E(3T2) transition is masked by the much stronger 3B1(3A2)-3A2(3T1)
transition. In the case of D2d local symmetry with S4 symmetry axis, the absorption
cross-section depends on the polarization of the pump beam relative to the
crystallographic axes. For a polarized beam with electrical vector parallel to S4 local
symmetry axis (p polarization) or perpendicular to S4 (s polarization), the ground-
state absorption cross-sections are sp ¼ ð3:9  5Þ 1018 cm2 and ss ¼ ð1:5  1:9Þ
1019 cm2 ; respectively.

4. Lasers

4.1. Introduction

Rare-earth and transition metal ions that are doped in a solid host have been
operated successfully as solid-state lasers for several decades. Solid-state lasers based
on ions such as Nd3+, Ho3+, Tm3+, Er3+, and many other rare-earth ions doped in
crystals such as Nd:YAG, Nd:YVO4, Nd:YLF, or various glasses are currently
standard products of the laser industry. These lasers possess narrow emission line
widths and therefore emit coherent radiation at very specific wavelengths. The
spectral range of these lasers can be extended by using non-linear optical elements in
two ways: the first one is the frequency conversion technique such as second-
harmonic generation (SHG) or third-harmonic generation, while the second one is
frequency shifting like optical parametric oscillation (OPO) or stimulated Raman
scattering. Both methods require complex optical and mechanical systems as well as
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high peak power density at the non-linear optical element. On the other hand,
tunable lasers with their broadband emission in the near-IR (800–1100 nm) or
mid-IR (1100–1600 nm) may provide a solution to the narrow bandwidth limitation
of the currently used lasers based on rare-earth ions. The room temperature
tunable lasers that cover the visible and mid-IR spectral range are Ti:sapphire
(790–1100 nm), Cr:alexandrite (600–810 nm), Cr:LiSAF or Cr:LiCAF (750–950 nm),
Cr4+:Mg2SiO4 (forsterite) (1100–1300 nm), and Cr4+:YAG (1200–1550 nm). Var-
ious types of Cr4+-doped garnets span the spectral range of 1200–1850 nm [14]. The
broadband emission of lasers based of transition metal ions stems from the special
structure of the electronic levels (d orbitals) as was discussed previously. The room
temperature laser operation of tetrahedrally coordinated Cr4+-doped various
crystals is well established in hosts such as YAG [35,36], LuAG [24], Mg2SiO4
[7,8,17], Y3Sc3xAl5xO12 and Y2SiO5 [15].
Similar to what was discussed above, there are other Cr4+-doped crystals:
Cr4+:SrAl2O4, Cr4+:CaAl2O4, [37] Cr4+-doped aluminate and silicate glasses [38],
Cr:Gd2SiO5 (Cr:GSO) [23], Cr4+: Ca2Al2SiO7 (Cr:CAS) [39], Ca2Ga2SiO7 (CGS)
[40], or Cr4+:LiAlO2[41], which present spectroscopic properties and potential use as
broadband lasers in the near-IR. The overall absorption strength in CAS is greater
than in CGS. The near-IR emission of CAS and CGS is significantly quenched over
a wide temperature range (14–300 K), and was explained in terms of strong
electron–phonon coupling as well as energy transfer to traces of rare-earth ion traps
in the crystalline host. As for Cr4+:LiAlO2, they are tetrahedrally coordinated lattice
sites only, which are useful in inhibiting the loss mechanism in the crystal, and ideal
for spectroscopic studies of various transition metal ions in a four-fold coordination.

4.2. External effects on laser performance

We should emphasize here two main factors that determine the position and the
spectral width of the optical transition and hence the laser wavelength: the
appropriate site coordination and the crystal field.

4.2.1. Coordination
The width of the optical transitions results from the types of orbitals that
participate in the optical transition and the coordination of the transition metal ion.
If in the excited state, some of the d orbitals point directly to the surrounding atoms
of the host (ligands), inter-electronic repulsion will occur, and therefore the excited
state will be shifted relative to the equilibrium position of the ground state. The
increase of the inter-nuclear distance between the transition metal and the ligands
causes a distortion of the crystalline structure via host vibrations, or in other words,
the excited electronic state is coupled with the crystalline vibrational modes. The
relative change of the equilibrium position of the ground and excited states is the
source for the broadband transitions of transition–metal ions. When the equilibrium
position is unchanged, the vibronic coupling is weak and the electronic transition is
sharp, similar to the case of rare-earth-doped ions, or the R lines of the ruby laser.
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4.2.2. Crystal field


Unlike the rare-earth ions which have shielded 4f orbitals, the d orbitals of the
transition–metal ions are influenced by the external crystal field. The position of the
various electronic states of the transition metal ions under the influence of a crystal
field depend on the crystal field strength according to the Tanabe–Sugano theory [6],
and this is presented in the Tanabe–Sugano correlation diagrams, as will be
explained below. Therefore, it is possible to design a crystal host where specified
optical transitions will be dominant.

4.2.3. Crystal field effect on Cr3+


As an example, the configuration diagram of Cr3+-doped systems (Fig. 2) shows
that in the spin-forbidden transition 2E-4A2, the transition is between t2g orbitals,
which are pointed between the ligands in octahedral coordination. Therefore, the
excited state 2E is stabilized, and is not coupled with the vibrational modes of the
crystalline host. Therefore, there is almost no change in the equilibrium distance of
the ion–ligand both in the ground and excited states, and the 2E-4A2 transition will
show sharp line. In the spin-allowed transition, 4T2-4A2, the 4T2 state contains
components of eg orbitals that point toward the ligands, and form the unstable anti-
bonding MO (molecular orbitals). The Cr–ligand interaction of the electronic

Fig. 2. Configuration coordinate diagram of the ground state 4A2 and the excited state 4T2 of Cr3+-doped
solids in the intermediate interaction field.
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orbitals in the 4T2 excited state causes distortion in the crystalline structure due to
electronic repulsion, as well as increase in the Cr–ligand inter-nuclear distance, in
other words, a strong electron phonon coupling and broadening of this transition.
We note also that due to the electron–phonon coupling of the 4T2 state, this level is
much more sensitive to the crystal field strength than the 2E state. This can also be
observed from the Tanabe–Sugano correlation diagram presented in Fig. 3. By a
proper choice of the solid-state host composition, we can control the crystal field
strength and hence the energetic position of the 4T2 state relative to 2E. In Fig. 3 we
observe that in a low crystal field the 4T2 level is below 2E and the optical spectrum
will be broadband. On the other hand, in a strong crystal field, the 4T2 state will be
above 2E, and the dominant transition will be the narrowband 2E-4A2 transition.

4.2.4. Crystal field effect on Cr4+


The Tanabe–Sugano correlation diagram for a d2 system such as a Cr4+ ion is
presented in Fig. 4a. In the case of tetrahedrally coordinated Cr4+-doped solids the
Cr4+ IR emission results from the 3T2-3A2 transition. The 3F ground-state level of
the free-ion splits into three components in an ideal Td (tetrahedral) site:
3
F 3A2+3T2+3T1. In a distorted tetrahedron (D2d symmetry), it results in further
orbital splitting: 3T2 splits into 3B2 and 3E, 3T1 splits into 3A2 and 3E, and 3A2

Fig. 3. Energy-level diagram as a function of the ligand field strength in units of Racah parameter B for
the octahedrally coordinated d3 system (such as Cr3+).
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Fig. 4. (a) Energy-level diagram as a function of the ligand field strength in units of Racah parameter B
for the tetrahedrally coordinated d2 system (such as Cr4+ ion). (b) Energy-level scheme of the
tetrahedrally coordinated Cr4+ ion in Td and D2d, and in D2d symmetry+spin–orbit splitting. The solid
lines are the electric-dipole-allowed transitions, the dashed arrow indicates partially allowed transitions,
and the dash-dotted lines are the magnetic-dipole-allowed transitions (taken from Ref. [43]).

(ground level) becomes 3B1. However, the room temperature absorption spectra of
various Cr4+-doped garnets (YAG, LuAG, YGG, GGG, etc.) or mixed scandium-
based garnets (GSAG, YSGG, GSGG, mixed YSAG) [28,42] indicate that there are
optical transitions in the UV and visible part of the spectra. They observed several
groups of absorption peaks, namely, 300–500 nm 3B1(3A2)-3T1(3P), 550–700 nm
3
B1(3A2)-3T2(3F), and 700–1000 nm 3B1(3A2)-3T1(3F). The magnetic-dipole-
allowed transition 3A2-3T2 (or more precisely, into the 3E and 3B2 crystal field
components) has an absorption peak about 1100–1200 nm and is therefore very weak
[28,42]. The energy-level scheme of Cr4+-doped garnets is presented in Fig. 4b. A
very similar picture was observed in Cr4+:Y2SiO5 [12,13]. This transition is masked
by the strong, electric-dipole-allowed transition around 1000 nm. As was noted
previously, the relative positions of the energy levels of transition metal ions depend
on the crystal field strength. The metastable level can be either 1E or 3T2, depending
on the strength of the crystal field in the tetrahedral site. The high or low crystal field
is the field above or below the cross-over point of the two states, respectively. In a
low crystal field, the transition is expected to be between 3T2-3A2 states, with a
short fluorescence lifetime (spin-allowed transition) and broadband emission due to
strong electron–phonon coupling. In a high crystal field, where the electron–phonon
coupling is weak and the transition is spin forbidden, we expect a long lifetime and
narrowband emission due to the 1E-3A2 transition. The crystal field strength
parameter Dq/B was calculated for several crystals.
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The value of Dq/B in YAG is 1.78 [28], which is similar to that is YOS (Dq/
B=1.8) and Mg2SiO4 (Dq/B=1.99) [18,25]. These values correspond to the relatively
strong crystal fields where we have intermediate states that are very close to the
cross-over points between 3T2 and 1E levels in the Tanabe–Sugano diagram, or even
mixed states of 3T2 and 1E states. However, the strong orbital splitting of 3T2 into 3E
and 3B2 brings the 3B2 level below the 1E level, and this makes the Cr4+ behave as a
low crystal field system. A different interpretation for Cr4+:YOS spectroscopy was
suggested by Hommerich et al.[12]. They assigned the metastable level 3T2 and its
spin–orbit components to low crystal field, Cs symmetry site. This observation was
also confirmed by uniaxial stress experiments. Since the Cs site is only slightly
distorted, the spin–orbit splitting is small and not observed [44]. New evidence
[45–47] suggests that there is oxidation–reduction equilibrium between oxidation
states of the chromium ion, namely, Cr3+ and Cr4+, and this equilibrium depends
on the temperature and ambient atmosphere. The oxidation of Cr3+ into Cr4+ is
obtained by recombination of atmospheric oxygen with negatively charged vacancy
in the lattice and electron transfer from octahedrally coordinated Cr3+ in the lattice
surface to generate the octahedrally coordinated Cr4+. This process is enabled by
diffusion of the oxygen vacancies to the lattice surface. Then an intra-lattice,
thermally activated cation exchange occurs, in which Cr4+ exchanges position with
Al3+ yielding tetrahedrally coordinated Cr4+. Absorption in the range
2450–2900 cm1 in Cr4+:YAG is attributed to local vibrations of the charge
compensator ion Ca2+ or Mg2+ with the oxygen vacancy [47].
The tetrahedral site in garnets is distorted and this lowers the site symmetry and
yields splitting and mixing of the various energy levels. As a result of the site
distortion, electric–dipole moment is induced in transitions that were originally
magnetic-dipole allowed and were expected to be weak or forbidden. The same
arguments apply to the weak magnetic-dipole-allowed transition 3B2(3T2)-3B1(3A2 ).
This transition is the laser transition of Cr4+-doped crystals. It is a weak optical
transition and is masked by the strong transition around 1000 nm. At low
temperature (12 K), sharp structures due to vibronic transitions were observed in
various garnets mentioned above[42]. They assigned the zero-phonon lines for
various electronic states of Cr4+ in D2d symmetry as well as the splitting due to the
spin–orbit coupling and due to the coupling of energy levels with the phonon modes
of the ion–ligand complex. This is very similar to the vibronic mode assignment
(local and host phonons) of Cr4+:Mg2SiO4 energy levels, using Raman scattering
measurements [48,49]. Kuck et al. [42] also measured the energies of the phonon
modes. The phonon modes that participate in the emission process are important for
efficient laser operation. Four phonon modes are coupled to the transition where the
highest-energy phonon, denoted by n3 is expected to be the dominant phonon in the
non-radiative process. Table 4 presents the zero-phonon lines of 3B2(3T2)-3B1(3A2)
transition, the spin–orbit splitting, DE SO ; of 3B2(3T2) excited state and of the four
phonon energies for several Cr4+-doped garnets based on the above references. For
comparison, we also included data for yttrium orthosilicate [12,25].
In the tetrahedral coordination, the t2g orbitals point toward the ligands. Since
both the ground and excited states contain t2g orbitals, we expect strong
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Table 4
Zero-phonon lines of 3B2(3T2)-3B1(3A2) transition, phonon energies, and spin-orbit splitting of Cr4+
doped LuAG, YAG, YGG, GGG, and YOS.

Parameter LuAG YAG YGG GGG YOS

Zero-phonon line (cm1) 7896 7814 7511 7503 8709


7927 7842 7531 8744
DESO (cm1) 31 28 30 28 35
Phonon energies (cm1) 298 295 347 293 E309
152 173 149 122
335 330 292 334
397 390 400 407

electron–phonon coupling, distortion of the tetrahedral symmetry in the excited


state, and a change in the equilibrium position of the ground and excited states. The
relative shift between the equilibrium position of the ground and excited states
results in the broad bandwidth of the optical transition between the relevant levels.
Cr4+ emission results from the 3T2-3A2 transition in tetrahedral symmetry. The
emission of Cr4+ is broad due to strong electron–phonon coupling which results
from the t2g nature of the 3T2 excited levels.

4.3. Laser performance of some Cr4+-doped hosts

The absorption and fluorescence emission of Cr4+-doped crystals such as


forsterite, garnets, or other silicate crystals indicate that these materials, while
pumped by Nd:YAG laser at 1.06 mm, can be used as tunable solid-state lasers
in the near-IR spectral range. Unlike other transition metal ion lasers such as V2+,
Ni2+, or Co2+ which operate at cryogenic temperatures, solid-state lasers based on
Cr4+-doped crystals operate in pulsed or CW modes at room temperature. The
Cr4+-doped crystal lasers are operated in two main modes.

4.3.1. Free-running, pulsed or CW operation mode


The free-running mode is the basic operation mode, with longitudinal pumping by
Nd:YAG at 1.06 mm. This simple operation mode is applied in Cr4+-doped forsterite
or garnets mainly for chemical detection and diagnostics in the spectral range
of 1.1–1.55 mm. The pioneering work on free running operation was conducted
during the years 1988–1993, and the main results are summarized briefly below and
in Table 5.
Linear resonator: The most commonly used Cr4+-doped crystals are forsterite and
garnets. Table 6 presents the main thermal and optical characteristics of Mg2SiO4
and YAG that are relevant to laser operation.
The first demonstration of a Cr:forsterite (Cr:Mg2SiO4 (laser was obtained by
longitudinal pumping into the visible absorption bands by using a Q-switched
Nd:YAG at 532 nm. This laser was operated in free-running and pulsed modes, and
at room temperature [8]. This simple linear laser cavity with longitudinal pumping
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Table 5
Main free-running laser results of Cr4+ doped crystals. All the lasers were pumped at 1.06 mm unless noted
differently.

Crystal Slope efficiency (%) Bandwidth or Refs Remarks


tunability (nm)

Cr:Mg2SiO4 1.4 22–27 [8] Pulsed, pumped at


532 nm
Cr:Mg2SiO4 1.8 30 [7] Pulsed
Cr:Mg2SiO4 10 60 [29] Pulsed
Cr:Mg2SiO4 21–22.8 180 [50,51] Pulsed, various output
couplers
Cr:Mg2SiO4 6.8 12 [53] CW operation
Cr:Mg2SiO4 38a 150 [52] CW, V-cavity
Cr:Mg2SiO4 42711 N/A [54] CW
Cr:YAG 10b 100 [55] Pulsed
Cr:YAG 3–4b 100 [58] Pulsed
Cr:YAG 22 210 [28] pulsed
Cr:YAG 11.7 120 [28] Quasi-CW
Cr:YAG 28 287 [15] Quasi-CW
Cr: YSAG (x=0.5) 10 234 [15] Quasi-CW
Cr: Ca2GeO4 5–6 22 [56] Pulsed
Cr:Y2SiO5 6.3 10 [57] Pulsed , operated at 77 K
12.4 23 Pulsed pumped at
532 nm
a
The extrapolated limiting slope efficiency is estimated to be 65%.
b
Pump to laser conversion efficiency.

Table 6
Main thermal and optical characteristics of Mg2SiO4 and YAG [17,54,59,60].

Formula Cr:Mg2SiO4 Y3Al5O12

Cr4+ ion density (cm3) E3–6 1018 E1 1018


Density (g/cm3) 3.22 4.56
Melting point (1C) 1890 1970
A
Hardness ( ) 7 8.5
Refraction index 1.635 1.82
Thermal expansion coeff. a 9.5 10–6 8.0 10–6
Thermal conductivity, (W/m K) (at 300 K) 5–8 11–13
dn/dT (K1) 2.8 106 7.3 106
Tunability (mm) 1.11.35 1.35-1.55
sem (cm2) 1.44 1019 3.3 1019
tr (ms) 25 25.4-30.6
t (ms) (at 300 K) 2.7 4.1a
Loss coeff (cm1) 0.02 0.02
a
Other values are in the range 3.4–4.6 ms.

yielded laser emission peaking at 1235 nm, 22–27 nm bandwidth (FWHM), and with
1.4% slope efficiency. Further pumping using Q-switched Nd:YAG in the 3T2
absorption band at 1064 nm [7] produced better results in terms of slope efficiency
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and spectral bandwidth. In this case the output coupler was of R ¼ 98%; and the
1.06 mm pumping beam was focused in front of the sample. Using a very similar
experimental setup and pumping with Q-switched Nd:YAG laser at 1.06 mm, it was
also possible to obtain lasing emission from Cr4+:YAG crystals (with Ca2+ ion as
charge compensator), with maximum conversion efficiency of E10% [55,58].
Verdun et al. [29] used the same linear configuration but adjusted a few critical
parameters that are essential for efficient laser operation. They optimized the pump
beam, the cavity mode size, the output coupling mirror, and the pump beam focusing
and obtained tunable laser (1220–1280 nm) with 10% slope efficiency. Further
improvement in the pulsed laser performance was obtained by focusing the pumping
beam inside the sample, and optimizing the pump and the cavity volume modes
[50,51]. This improved configuration yielded maximum slope efficiency up to 22.8%
and continuous tunability over the 1167–1345 nm spectral range in forsterite. For
Cr4+:YAG at room temperature, a slope efficiency of 22% and continuous tenability
over 1320–1530 nm was reported [59]. Room temperature of free-running CW
Cr:forsterite with 6.8% slope efficiency and 12 nm bandwidth was reported at the
same time by Petricevic et al. [53]. Significant improvement in thermal management,
and a proper pump to mode volume matching, led to significant increase in the room
temperature CW, Cr:forsterite laser performance, namely, slope efficiency of
42711% [54]. Using Nd:YAG with a long pumping pulse (quasi-CW pumping)
yielded improved laser performance with slope efficiency of 28% [15]. Garnets like
Y3ScxAl5xO12 or YSAG (0pxp1.5) were also operated in a quasi-CW pump
mode. These garnets exhibited spectral wavelength shift into the infrared, from llas ¼
1420 nm for x ¼ 0; to llas ¼ 1584 nm for x ¼ 1:5; as well as maximum slope efficiency
of 10% for x=0.5 [15]. Very low laser efficiency, slightly blue-shifted was obtained in
a pulsed mode using Cr4+: Y1.5Lu1.5Al5O12 crystal [61]. Other crystals laser emission
such as Cr4+:Y2SiO5 (Cr:YOS) [13,57] or Cr4+:Ca2GeO4 [56] also demonstrated
laser action in the near-IR. The Cr:YOS was pumped longitudinally at 1064, 532,
and 840 nm and operated successfully at low temperatures (77–257 K) [57,62]. The
room temperature, quasi-CW operation was carried out by CW pumping at 1047 nm
using Nd:YLF laser or long pulse of Nd:YAG. The pumping conditions are
unoptimized both for CW and long pulse pumping, and therefore the laser is very
inefficient, with slope efficiency of E0.4% and bandwidth of 12 nm [13]. Room
temperature operation of Cr4+, Mg2+:YAG pumped at 1079 nm by a free-run long-
pulsed Nd:YAP laser operated at 10 Hz was reported by Kalisky et al. [63]. This laser
was tunable over a 1.4–1.5 mm spectral range, with a slope efficiency of 14% at
40 mJ/pulse output energy.
Folded resonator: A significant improvement in the CW Cr–forsterite laser
performance was obtained by using a V-shaped, astigmatically–compensated
configuration (or a three mirror-folded resonator) [52]. This configuration provided
more flexibility in the cavity length for further technological developments such as
mode locking and ultrafast applications, as well as for mode matching, to obtain
optimal laser performance. A very similar configuration was also employed to obtain
quasi-CW operation of Cr4+:YAG [59] or Cr4+:LuAG [24,64]. Fig. 5 describes a
typical experimental setup of a folded resonator used to pump Cr4+-doped crystals
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Y. Kalisky / Progress in Quantum Electronics 28 (2004) 249–303 271

Fig. 5. Experimental setup used for CW action of Cr4+:LuAG and YAG. L—focusing lens; EM—
entrance mirror for the pump beam; FM—folding cavity mirror; OC—output coupler; HR—cutoff filter
at 1064 nm; P – power meter.

such as various types of garnets and forsterite laser. Improved technique of heat
removal and lowering Cr4+ concentration (optimized absorption coefficient is
a ¼ 0:57 cm1 ) allowed the operation of Cr4+:forsterite laser at 15 1C with absorbed
power slope efficiency of E30% at 1.26 mm [65]. The folded mirror resonator
presents an extension in the range of applications of the Cr:forsterite or Cr4+:YAG
lasers both in basic research such as high repetition rate, mode-locked lasers and in
the use of such lasers for eye-safe ranging, remote sensing, and diagnostics. This laser
configuration was utilized later to produce femtosecond pulses.

4.3.2. Mode-locked ultrafast lasers


In the case where there is a need for both a long resonator and a small focused
beam waist inside the cavity, a folded resonator is usually used. In the case of intense
focusing inside the resonator, it is necessary to avoid damage to the crystal AR
coating; therefore, Brewster-cut laser crystals are commonly used. However,
insertion of Brewster angle inside the resonator introduces astigmatism which can
be compensated by the folding mirror [66].
One of the major applications of Cr4+-doped solids is the ability to generate
ultrafast femtosecond (fs) lasers, tunable in the near-IR. (The pulse duration is
measured at FWHM.) These lasers have potential applications in industry
(micromachining, high-precision drilling, laser ablation), in microscopic imaging
of surfaces, coherent tomography of biological tissues, and biomedical applications
such as multi-photon confocal microscopy. Several methods were employed to
generate picosecond (ps) and femtosecond (fs) pulses such as active mode locking in
Cr4+:YAG (26 ps-duration)[67], sub-100 fs pulses [68], passively or self-starting
mode locking (sub-100 fs in Cr4+:YAG [69], synchronously pumped mode locking
(pulses of 260 fs duration) [70], or regenerative initiation (48 and 120 fs for Cr4+-
doped forsterite and YAG, respectively) [71,72]. The ultrafast Cr-doped crystals
were employed in various oscillator and oscillator–amplifier configurations. In the
latter configuration, pulses of 135 fs with peak power of E1.5 GW were obtained.
Presently, the self-starting fs Cr4+ forsterite oscillator produced 17 nJ pulses of 40 fs
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pulses at 26.5 MHz repetition rate duration which is the highest energy obtained
from an oscillator [73]. Shorter pulse duration, of 25 fs, was obtained by using
passive mode-locking semiconductor saturable absorber with self-starting Kerr-lens
mode locking [74], or with an improved version of semiconductor saturable
absorption mirror (SESAM) which produced 22 fs pulses [75]. It is also possible to
generate fs pulses in the orange wavelength spectral regime (600–630 nm) by SHG,
using Cr:forsterite oscillator and BBO as intracavity frequency doubling crystal [76].
The all-solid-state laser produced pulses of 170 fs duration with 81 MHz repetition
rate. This laser has clear advantages over dye lasers such as compactness, stability,
high output power, and compatibility with the newly developed KLM forsterite
lasers. Other SHG results using Cr:forsterite laser with LBO or CDA doubling
crystals produced orange pulses of 130 fs pulse duration, or oscillator dye-
amplifier configuration, with energy of 0.6 mJ per pulse with pulse duration of 43 fs
at 630 nm [77].
Mode-locked fs Cr:forsterite with laser emission at 1.26 mm, coupled with non-
linear ZnGeP2 (ZGP), AgGaS2, HgGa2S4, or RbTiOAsO4 (RTA) crystals, can be
used also for the generation of near-IR fs (180–200 fs) OPO in the range of
2.5–12 mm. In the case of Cr:forsterite fs oscillator with ZGP as the non-linear
crystal, maximum single pass internal conversion of 2.5% was achieved, whereas in
the case with amplification stage, transform-limited E200 fs pulses were observed
with both AgGaS2 or HgGa2S4. For the latter material, 11% total internal
conversion efficiency was obtained [78–81].
The same phenomenon was found in Cr4+:YAG. Similar to Cr4+:forsterite,
Sennaroglu et al. [72] reported the operation of CW mode-locked fs Cr4+:YAG laser
with transform-limited pulse of 120 fs (FWHM) at 1.52 mm and with TEM00 output
power as high as 360 mW. The pulsewidth was reduced below 100 fs using self-mode-
locked Cr4+:YAG laser [82,83]. The laser reported by Ishida et al. [84] was a stable,
compact, all solid-state self-mode-locked Cr4+:YAG laser pumped by Nd:YVO4
operated at 1.5 mm. Further cavity optimization yielded pulsewidth of 43 fs for
Cr4+:YAF and 68 fs for Cr4+:forsterite [85].
Another method to obtain an ultrafast laser is to use a saturable absorber mirror
(SAM) structure for passive mode locking with pulsewidth of 120 fs at 1488 nm [86],
similar to the technique used for other solid-state lasers (see, for example Ref. [87]).
By optimizing the laser beam mode inside the gain medium and the laser cavity itself,
it was possible to obtain pulses of 55 fs (FWHM) and 1.2 GHz repetition rate at
1.52 mm [88]. A passively mode-locked (using SESAM) Cr4+:YAG laser, by direct
diode pumping of Cr4+:YAG at 1.06 mm or by Yb fiber was reported by Naumov et
al. [89]. The diode-pumped passively mode-locked Cr4+:YAG laser produced pulses
of 62 fs pulsewidth (FWHM) at average output of 15 mW. Ultrashort pulses (E30 fs)
were achieved with Yb-fiber pumping using a similar experimental setup.

4.4. Thermal effects in a laser system and resonator design

The study of thermal effects in a laser system is important for obtaining an


efficient and stable laser performance.
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Laser crystals have finite thermal conductivity. Due to this fact, accumulated heat
in the crystal during the pump process cannot be removed efficiently and thermal
build-up is generated in the laser crystal. Heat sources in a Cr4+-doped crystal laser
rod that is pumped at 1.06 mm result from several reasons:

1. Non-radiative processes, as a result of the coupling between the lasing and the
ground-state levels, or quenching and non-radiative energy transfer to other ions
or impurities in the host. (In reviewing thermal effects in Cr4+ system, we ignore
quenching or energy transfer processes as a heat source input.)
2. Stokes shift: the energy difference between the pumping and lasing photons
(quantum defect) is lost to the host as heat.

The fractional thermal loading in Cr4+ forsterite is about 35–40%. The thermal
load in the crystal affects the small signal absorption and the saturation absorption
coefficients due to the temperature dependence of the absorption coefficient
according to a ¼ a0 þ aðTÞ; where a0 is the loss coefficient due to scattering and
absorption by impurity ions and aðTÞ is the absorption coefficient due to thermally
populated sublevels. In crystals with high absorbance, the laser power performance
and the beam quality are degraded due to the high thermal load, high losses, and
radial changes in the refractive index due to temperature gradients. Efficient laser
operation with slope efficiency of E30% relative to the absorbed power was
achieved near room temperature (15 1C) using crystals with low Cr4+ concentration
and low absorption coefficients, in the range of a ¼ 0:5720:64 cm1 [65,90]. We
therefore see that the laser performance is a combination of the spectroscopy of the
active ion, and the physical parameters as well as the thermal properties of the host.
All these parameters determine the non-radiative rates and the thermal load on the
crystal, and will be discussed briefly below.

4.5. Effect of spectroscopy and physical parameters on laser performance

The Cr4+-doped crystalline laser is a vibronic, quasi-four-level system. Such a


system requires cooling in order to achieve population inversion and efficient laser
operation. The non-radiative coupling between the two states can be enhanced by
several vibrational frequencies in several electronic states (quadratic coupling) [26].
The electric states are mixed by phonons having promoting modes, while the
difference in the energy of electronic states is absorbed by accepting phonon modes.
The non-radiative decay rate, Wnr, is a function of the phonon occupation number,
the energy gap between two electronic states, and the angular frequency of the
promoting modes [26] as shown below
X
W nr ¼ np op ½np þ 1 GðO0  op Þ þ np GðO0 þ op Þ; (6)
p

Where np is a factor describing the mixing of electronic states, namely, promoting


interaction, op is the angular frequency of the promoting mode p, np is the
occupation number of the phonons with angular frequency op ; given by the
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Bose–Einstein statistics as np ¼ ½expð_op =kT  1 1 ; and GðO0 ; op Þ is a line shape


parameter which is a function of the energy gap, _O0 ; between two neighboring levels
at an equilibrium state, and of op : Therefore, the phonon modes that participate in
the non-radiative process contribute to the thermal load in the crystal, and as a
result, the fluorescence lifetime and intensity will decrease with the increase of
temperature—see Table 1 for more details, and also experimental results for
Cr4+:forsterite [90], Cr4+:LuAG [16], and Cr4+-doped garnets [14]. The above-
mentioned facts indicate clearly that the fluorescence quantum efficiency decreases
with the increase of temperature and that phonon assisted non-radiative processes
are dominant at elevated temperatures.
Thermal build-up in the laser rod is deleterious to the gain medium and to the laser
operation. For example, Carrig et al. [54] found that the Cr4+:forsterite output
power decreased significantly when the crystal temperature was varied from 77 to
300 K at several pumping wavelengths. For example, at a pumping wavelength of
1064 nm, the output power at 300 K decreased by 60% relative to the power at 77 K,
while the laser threshold doubled at 300 K relative to 77 K. Thermal load can be
reduced by reduction of the active ion concentration. It was found that the incident
threshold pump power was always lower for reduced Cr4+concentrations (samples
with absorption coefficients of a=0.57 and a=1.691.78 cm1, respectively). The
ratio of the threshold pump power for the high and low Cr4+ concentrations
increases with the increase of the crystal temperature. This provides evidence that at
high temperatures and hence at high thermal load, there is a significant reduction in
population inversion and an increase in the threshold pump power [65,90].
Petricevic et al. [53] observed E40% reduction in lasing efficiency of
Cr4+:forsterite upon switching the laser operation from quasi-CW to CW-pumping
mode. It was found that the Cr4+ forsterite laser efficiency and stability region
depend on the thermal lensing [91]. The mode matching ratio also changes with the
input pumping power and should be adjusted to compensate for internal focusing. In
a quasi-CW pumping of Cr4+:forsterite crystal, the laser efficiency reduced by 5%
only at maximum pumping power of 12 -W when the laser crystal was insufficiently
cooled. Without cooling the laser efficiency was reduced significantly even at low
pumping power level [92]. When the crystal temperature was changed while pumping
at a constant pumping energy, the lasing was completely quenched at crystal
temperature of 380 K. Optimization of Cr4+:forsterite laser system parameters such
as proper thermal management, mode matching, and optimization of the active ion
concentration to low absorption coefficient (a=0.570.64 cm1) improved the laser
performance significantly [65,90]. Room temperature (15 1C) operation of Cr4+:for-
sterite under optimized conditions as to the thermal load yielded absorbed power
slope efficiency of E30% at 1.26 mm emission wavelength, and tenability over the
spectral range 1198–1132 nm, with the output coupler of T ¼ 4:7% [93].
Prevention or reduction of the thermal build-up is necessary in order to suppress
thermal gradients which are the source for thermal effects in a laser crystal such as
thermal aberrations caused by thermal lensing and thermal induced birefringence,
thermal stresses, and photoelastic effects. In the case of birefringent media such as
Cr4+:forsterite, thermally induced anisotropy is small compared to the natural one,
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namely, Dn
0:02: Also, longitudinal laser modes are affected by lengthening of the
laser crystal.
To summarize, reduction of the thermal build-up in the laser crystal can be
achieved by efficient heat removal or proper thermal management, as follows:
1. Use of materials with high thermal conductivity. For example, the thermal
conductivity of YAG is k=10–13 W/mK vs. forsterite, k=5/WmK.
2. Thermal management: using efficient heat sink cooled by thermoelectric cooler,
and thin indium foil wrapping the crystal for good thermal contact between the
crystal and the heat sink.
3. Pumping at low duty cycles or pulsed mode to prevent thermal build-up.
4. Eliminating non-radiative processes, energy transfer, or unused absorption by
improving the crystal quality or by using low Cr4+ concentration aE0.5 to
0.64 cm1, as was suggested first by Ivanov et al. [94], and was elaborated later
by Sennaroglu et al. [90].
5. Reduction in the quantum defect (Stokes shift) by pumping closer to the emission
peak.

5. Passive Q-switching

5.1. Introduction

Q-switching is a method to generate laser pulses with short pulse duration and
high peak power. In this method, the fast giant pulse is generated by allowing the
pumping process to build up a population inversion and gain inside the laser cavity
without oscillations, which are larger than the normal values under free-running
operation.
This is done by altering the quality factor Q of the laser cavity to low values by
introducing losses inside the laser cavity for a pre-determined time duration. During
this period of time, there is no laser output due to the losses introduced inside the
cavity by the Q-switching element, thus allowing the storage of energy inside the gain
medium. As a result the population inversion in the gain medium is increased to
levels that are above the threshold achieved under normal pumping conditions.
When the Q value of the cavity is switched to high values, a short, high peak power
laser pulse is generated.
This technique is of practical importance in many areas such as industry,
medicine, military applications and basic scientific research. Q switching is carried
out either by active or passive methods. Among the active methods are electro-
optical, acousto-optical and mechanical devices. The active Q-switches are driven by
external driving sources such as Pockels cell voltage power supply, RF oscillator and
rotating mirror, coupled with polarizing optics, and are usually expensive and bulky.
Contrary to this, the passive Q-switch is a simple optical element which utilizes the
nonlinearity of the absorption at some photon flux. Since the switching is done by
the laser radiation, there is no need for external devices with high-voltage drivers and
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modulators or polarizers. Therefore, the system is compact, simple, inexpensive,


robust, easy to operate, with minimum or no optical elements inside the laser cavity.
When non-linear optical elements are employed, linearly polarized light is achieved
easily by using a tilted Brewster plate [95].
The main drawbacks of the system are the temporal and amplitude jitter and the
lower output relative to active devices due to inherent losses which prohibit full
saturation of the absorption line, therefore affecting the Q-switching efficiency. The
passive Q-switch operation is achieved by using organic or inorganic compounds
which have saturable absorption at the lasing wavelength. In this case the photon
build-up in the cavity is done in two steps:
1. The laser gain exceeds the cavity loss and the unsaturated absorption losses.
2. Build-up of photon density takes place inside the cavity to values large enough to
saturate the saturable absorber.

The passive Q-switching process is a competition between the saturation of the


saturable absorber and the gain media. When the saturable absorber saturates first, it
allows the growth in the rate of the photon number. However, if the gain medium
saturates first, no Q-switch pulse will be developed.

5.2. Saturation of Cr4+ doped crystals

A saturable absorber is a material that absorbs at the laser wavelength and has low
saturation intensity. It can be an organic dye solution Eastman (Kodak 19152 or
14015 dyes) or dye-impregnated thin film of cellulose acetate, color center (F 2 :LiF)
crystals, bulk semiconductors (InGaAsP film grown on an InP substrate), or
inorganic doped crystals such as Cr4+:YAG or other Cr4+-doped solids, mostly
used for Q-switching of the 1.06 mm emission of Nd:YAG laser. The organic dyes or
the color center crystals are photochemically unstable with thermal management
limitations, especially at high repetition rates. The color center crystal has a low
absorption coefficient at 1064 nm; therefore, bulky material is required to obtain Q-
switching. The Cr4+:YAG has excellent photophysical characteristics as well as
thermal, mechanical, and chemical properties, which make this material a reliable
and durable device, suitable for the saturable absorber at high photon fluence,
without chemical or photochemical degradation. The additional advantages of the
Cr4+-doped solid is its relatively large absorption cross-section and low saturation
fluence of around 1064 nm, which are attractive for passively Q-switching Nd-based
lasers, mainly Nd:YAG lasers.
Passive Q-switching is achieved by employing an element with saturable
absorption at the laser frequency inside the laser cavity. This means that the
material with absorption line at the laser frequency becomes transparent as the
photon fluence increases. We assume that we have a saturable absorber with an
energy-level scheme presented in Fig. 6. The process is associated with the saturation
of the absorption line, denoted by the 1-3 optical transition. The spontaneous
emission occurs via optical transitions from the metastable level 3 to the ground
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Fig. 6. Schematic energy-level diagram of a saturable absorber with ESA. The solid lines indicate optical
transitions and the dashed lines indicate non-radiative transitions. The inter-system crossing 2-3 and the
non-radiative relaxation 4-3 are much faster than the lifetime of the metastable state 3.

level 1. We also assume that it is possible to have excited state absorption from the
metasble level 3 to higher energy levels 4, and that the transitions 3-2 and 4-3 are
fast relative to the transition 3-1.
The saturable absorber has ground-state absorption and ESA cross-sections, sgs
and ses ; respectively. For a saturable absorber to be used as a passive Q-switch, few
conditions are required: the ground-state absorption at the laser wavelength is large
enough, the ESA is negligible or small, namely, sgs  ses ; the material has low
saturation intensity, and long upper level lifetime, ta is long to allow ground-state
depletion.
At high fluence there is a saturation of the optical transition as a result of the
ground-state bleaching, and this results in high transmission of the optical signal. In
this case the population inversion is built up inside the laser cavity due to cavity
losses caused mainly by ground-state absorption of the saturable absorber. The
passive Q-switching operation is controlled by the build-up of the laser photons
inside the cavity. When the gain and the total absorption losses, including those of
the saturable absorber, are equal, low-level oscillations are developed inside the
cavity. This oscillation starts to grow to values large enough to saturate
the absorption line of the saturable absorber, therefore opens it and allows
the development of an intense laser pulse. The growth rate of the cavity photon
number, n(t), is given by [96]:
!
2
dnðtÞ K 2a N a0 K g0 N g0

gg0 nðtÞ þ þ ½nðtÞ 2 þ    ; (7)
dt g2a gg0
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where gg0 is the initial growth rate of the cavity photon number before saturation,
N go ðtÞ and N a0 ðtÞ are the initial population differences of the gain medium and the
saturable absorber, respectively, Kg and Ka are the coupling coefficients for the gain
medium and the saturable absorber, respectively, and g2a is the decay rate (or
recovery rate) of the saturable absorber; g2a ¼ 1=ta ; where ta is the decay rate of the
excited state of the saturable absorber.
Let us assume a non-degenerate two-level system with population N1 and N2 for
the ground and excited states, respectively, with total population defined as
Nt=N1+N2, and transition frequency n0 : In the presence of external electro-
magnetic wave of intensity I n ðn
n0 Þ; there is a change in the relative population of
levels 1 and 2. For low values of I n ; we have that N1bN2, and the populations N1
and N2 are approximately at their thermal equilibrium state. For high values of I n ;
the population difference DN ¼ N 2 2N 1 becomes smaller and significantly different
from thermal equilibrium. In this case we define the system as saturated. The
population difference under steady state conditions is given by
DN 1
¼ ; (8)
Nt 1 þ I n =I s
where Is is the saturation intensity defined as
hn
Is ¼ ; (9)
2sa ta
hn is the laser photon energy, sa is the absorption cross-section of the transition, and
ta is the spontaneous lifetime of the first excited level. For the case of I s ¼ I n ðn ¼ n0 Þ;
we have DN ¼ N t =2; and therefore, Is is defined as the saturation intensity where the
population difference is half of the total population.
The absorption coefficient of the saturable absorber depends on the intensity
under steady-state conditions as well:
a0 a0
aðIÞ ¼ ¼ ; (10)
1 þ I n =I s 1 þ en =es
where a0 is the small signal absorption coefficient of the saturable absorber, Is is the
saturation intensity at which the small-signal absorption coefficient is reduced by one
half, and en and es are the incident and the saturated energy fluences, respectively.
The small-signal transmission of the absorber of thickness ‘s and ground state
density Nt, which is also the total concentration of the absorbing ion is given by
T 0 ¼ expða0 ‘s Þ ¼ expðN t sgs ‘s Þ: (11)
The current Cr4+-doped solids used as saturable absorbers are not fully bleached.
They have a residual absorption which is attributed to ESA therefore their
saturation transmission has a maximum value, Tmax. In order to evaluate the
ground-state absorption and ESA cross-sections, few assumptions are made:
I. We assume that since the 1E level is energetically close to 3T2, the singlet level
can also participate in the excited state absorption dynamics and there is a fast
inter-system crossing between the two electronic levels. As was noted, the Cr4+
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center can be located in at least four different sites [28], and hence the value of
the excited state absorption cross-section is averaged out over several initial
electronic states.
II. We assume that the ESA is the only absorption mechanism in the system and
that the lifetime of the first excited state 3T2 of Cr4 is much longer than the pulse
duration of the pumping laser. In this case we have a slow saturable absorber.
III. The non-radiative relaxation processes from any higher levels into the 3T2 level
are faster than the laser pulse duration. Therefore, during the pulse duration the
total population density is given by Nt=N0+N2 and at saturation we have
N0EN2, and hence we have the maximum concentration that corresponds to the
maximum transmission of the saturable absorber.

The ratio between the ground-state absorption and ESA cross-sections is given by
sgs lnðT 0 Þ
¼ : (12)
ses lnðT max Þ
The measured transmittance TE is a function of the input energy fluence and the
saturation fluence according to Frantz–Nodvik equation [97]:
eS
  
T FN ¼ ln 1 þ exp ev =es  1 T 0 ; (13)
ev
where TFN is the measured transmittance in the absence of the ESA, en is the input
incident energy fluence at frequency n, es is the saturation fluence, and T 0 is the
small-signal transmittance in the absence of ESA. There are two limiting cases for
the transmission of the saturable absorber: T FN ¼ T 0 for en oes and TFN=1 for
en 4es ; assuming that ses ¼ 0:
As was indicated before, the currently used saturable absorbers do not have
transmission of 100% at incident values above saturation, namely, en 4es : This
results from losses due to excited state absorption at the laser wavelength originating
from the metastable level to higher states. The process is illustrated in Fig. 7, where
transitions can occur from the metastable level (level 3) with lifetime ta to higher
electronic level denoted by 4 at the frequency of the laser transition. When the
transition 1-2 is saturated and the ground state (level) is already depleted, a
residual excited state absorption via 3-4 at the laser frequency transition will take
place.
This residual absorption is deleterious to the proper operation of the saturable
absorber, and thus the value of the ratio sgs =ses is a measure of the quality of the
saturable absorber, and a saturable absorber is a good candidate for Q-switching
when sgs 4ses : The ratio between the ground state absorption and ESA cross-
sections defines also the Figure of Merit (FOM) [98] of any saturable absorber:
FOM ¼ sgs =ses :
In the case of ESA, a modified Frantz–Nodvik equation was introduced by
Kalisky et al. [99]
es

T E ¼ ln 1 þ expðen =es Þ  1 T n0 tesa (14)
en
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Fig. 7. Energy-level diagram of a saturable absorber with ESA

where TE is the lossy transmittance, tesa is an empirical factor introduced to correct


for the excited state absorption. The small-signal transmission, To, corrected for
ESA is
T 0 ¼ T 0 tes (15)
and the high fluence saturation transmission, Tmax, is given by
T max ¼ tes : (16)
The best fit of the experimental results to the calculated transmission using
Eq. (14) yielded values of es, T0, and Tmax. See also Table 7 below for
more details.
In the low fluence regime, the transmittance in Eq. (14) can be approximated to
yield a linear dependence on the incident fluence
 
en T0
TE ffi T0 1 þ 1 : (17)
2es tesa
From the linear regression of the small-signal transmission data and equation [17], it
is possible to obtain the value of T0 and es as well. The values of To and es obtained
from Eqs. (14) and (17) are very similar, as can be expected.
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Table 7
Calculated physical parameters for Cr4+-doped garnets

Physical parameters YAG YSGG LuAG

Refraction index (n) 1.82 1.933 1.836


Fresnel loss (%) 16.2 19.2 16.6
Tmax (%) 90.7 90.6 95.6
T0 (%) 49.6 32.8 32.8
sgs =ses (at 1064 nm) 7.2 11.3 24.9
es (J/cm2) 0.068 0.045 0.018
seff (cm2) 2.76 1018 4.14 1018 1.02 1018
sgs (cm2) 3.2 1018 4.55 1018 1.1 1018
ses (cm2) 4.5 1019 4.0 1019 4.3 1020

The absorption cross-section was calculated from the energy fluence at saturation
assuming uniform transverse power distribution:
hn
es ¼ : (18)
sab
Therefore it is possible to calculate the absorption cross section according to Ref.
[18] by knowing the saturation fluence, using Eqs. (14) or (17). Since Cr4+ doped
garnets have excited state absorption, the calculated cross-section, sab, represents an
effective cross-section [99]
sab ¼ seff (19)
and the effective cross-section is defined as
seff ¼ sgs  ses ; (20)

where sgs and ses are the ground-state-absorption and ESA cross-sections can be
calculated with the help of Eq. (12). This method was used to calculate physical
parameters of various Cr4+-doped garnets including the ESA [99], and the results
are presented in Table 7 below.
Fig. 8 presents the transmission curves of Cr4+-doped YAG, YSGG, and LuAG
at 1064 nm as a function of the energy fluence, and the theoretical transmission as the
modified Frantz–Nodvik curves.
Fig. 9 displays the linear dependence of the small signal-transmission at 1064 nm
as a function of the low-energy fluence for the same garnets.
The temporal behavior of the 1064 nm transmission through Cr4+:YAG
and Cr4+:LuAG in the saturation range (2–4 J/cm2) is presented in Fig. 10,
and it indicates that saturation of the transmission occurs within 40 and 17 ns,
respectively. The effect of ESA on the 1064 nm saturated transmission is
also observed clearly from Fig. 10: in the case of Cr4+:LuAG, the maximum
saturated transmission has an average value of TmaxE100% within the laser
pulse, while for Cr4+:YAG, TmaxE90% within the duration of the 1064 nm
laser pulse.
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Fig. 8. Energy transmission accounted for Fresnel losses, as a function of the incident energy density for
1.06 mm laser pulse. The solid line denotes the modified Frantz–Nodvik equation (Eq. (14)) (taken from
Ref. [99]).

Fig. 9. Transmission of Cr4+-doped garnets at low-energy density. The solid lines are curve fitting using
Eq. (17) (taken from Ref. [99]).

Another analytical approximation to the solution of the Frantz–Nodvik equation


(Eq. (13)) in the presence of ESA for a slow saturable absorber is given by [100]

T FN  T 0
TE ¼ T0 þ ðT max  T 0 Þ; (21)
1  T0
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Fig. 10. Temporal evolution of 1.06 mm transmission through (a) Cr4+:LuAG, and (b) Cr4+:YAG. The
laser pulse intensity without saturable absorber is also presented in the figure taken from Ref. [99]).

where TFN is the solution to the Frantz–Nodvik equation, namely, the transmission
in the absence of ESA, and Tmax is the high fluence-saturated transmission limit. This
approximation was used to predict the saturation behavior of a saturable absorber
with T0=60% and Tmax=90% [100]. In the low fluence regime Eq. (21) can be
approximated as
 sgs 
TE ¼ T0 1 þ ðT max  T 0 Þ en (22)
2
or it can be represented by the exact solution to the Frantz–Nodvik equation,
namely, Eq. (13)- as follows:
 sgs  ses 
TE ¼ T0 1 þ ð1  T 0 Þen ; (23)
2
provided that ðsgs  ses Þen o1: From Eqs. (21) and (23) and from the saturation
curve of a saturable absorber, it is also possible to derive its physical parameters such
as ground-state absorption and ESA cross-sections or the pumping fluence at
saturation. Specifically, by using Eq. (23) with the assumption of transversely
Gaussian distribution of the 1064 nm transmitted beam, the physical parameters
extracted from the transmission saturation curves at 1064 nm for Cr4+:YAG and
Cr4+:GGG are summarized in Table 8 below. The results for Cr4+:LuAG [101] are
presented in Table 8 for comparison.
The saturation curve of a saturable absorber can be described also by an equation
which describes the energy fluence as a function of the position in an absorptive
medium, based on the fundamental photon transport equation. This equation,
derived by Avizonis and Grotbeck was modified to the case of a solid-state saturable
absorbers [22,102]:
 
dE ses sgs
¼ hnN 0 1  1  exp   N 0 ses E  aE ; (24)
dz sgs hn
where E is the energy fluence, z is the coordinate along the longitudinal direction of
the crystal, hn is the photon energy, Nt is the doping concentration, sgs and ses are
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Table 8
Calculated physical parameters for Cr4+:YAG, Cr4+:GGG , and Cr4+:LuAG [100,101]

Physical parameters Cr4+:YAG [100] Cr4+:GGG [100] Cr4+:LuAG [101] Cr4+:YAG [101]

sgs (cm2) (770.8) 1018 (5.870.5) 1018 (1.070.2) 1018 (2.070.4) 1018
ses (cm2) (270.3) 1018 (1.370.2) 1018 p3 1020 (2.070.4) 1019
sgs =ses at 1064 nm 3.5 E4.5 E30 10
Nt (cm3) (3.470.4) 1017 (7.1570.5) 1016 (2.570.2) 1018 (1.170.1) 1018

the ground and ESA cross-sections, respectively, and a represent non-saturable


losses. Curve fitting of the saturation data of Cr4+:YAG and Cr4+:LuAG with
Eq. (24) yielded values for the doping concentration and cross sections. The values
obtained numerically are also presented in Table 8 for comparison with data
obtained by analytical methods [100]. The cross-sections for Cr4+:LuAG that are
shown in Table 8 are in close agreement to the values that are presented in Table 7,
and which were obtained analytically by using Eqs. (12–20).

5.3. ESA spectra

A saturable absorber is useful for Q-switching when its ground-state absorption is


much greater than any ESA, or in other words, when sgs 4ses : Therefore, the
knowledge of ESA spectrum and wavelength-dependent cross-sections, particularly
in the near-IR is essential, for a proper Q-switch operation. ESA and stimulated
emission measurements on several Cr4+-doped garnets such as YAG, YSAG and
CaY2Mg3Ge3O12 (CAMGAR) indicate that both YAG and YSAG possess three
main ESA bands, the first one peaking at 750 nm, the second band in the spectral
range of 600–950 nm and the third band at 1150–1300 nm. The Cr4+:CAMGAR has
two absorption bands: one in 600–900 nm and the other in 1200–1700 nm, but no
stimulated emission in the near-IR was observed [103]. Other materials such as
Cr4+:Mg2SiO4, Cr4+:Y2SiO5 or Cr4+ doped crystals with Wurtzite-like structure
(Cr4+:LiAlO2 and Cr4+: LiGaO2), also show polarized ESA both in the UV–violet
bands (200–450 nm)—due to charge transfer transitions—as well as in 600–800 nm
and some ESA in 1100–2100 nm [21,104].
The ESA of Cr4+-doped YAG, GGG, YSGG is presented in Figs. 11–13 below
[100] and that of Cr4+:LuAG [101,105]– in Fig. 14.
From the ESA spectra of Cr4+-doped YAG, GGG, YSGG, and Cr4+:LuAG, the
useful spectral range for effective Q-switching was determined. For example,
Cr4+:YAG is not an appropriate Q-switch for the 710–800 nm spectral regime. On
the other hand, for l4820 nm; it is a saturable absorber since sgs 4ses : For Cr4+
:GGG and Cr4+:YSGG, and Cr4+:LuAG, these crystals can be used as saturable
absorbers above 840 nm and 790, and 750 nm, respectively, for example,
Cr4+:LuAG can be used as passive Q-switch in the 940 nm spectral region [106].
In the spectral range where ses 4sgs the Cr4+-doped materials act as ‘‘inverse
saturable absorbers’’, and are used to stabilize a CW laser output when inserted
inside the cavity [100].
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Fig. 11. Ground-state, excited-state and effective cross-section spectra in Cr4+:YAG taken from
Ref. [100]).

The stimulated emission cross-section of Cr4+ can be evaluated from the ESA
spectra of the doped samples. For the crystal of Cr4+:LuAG, the value of the
emission cross-section at 1400 nm was calculated from the ESA spectra assuming
that the ground-state and ESA cross-sections are known. The cross section value
found using this method, e.g. sem ¼ 2:8 1019 cm2 ; is in close agreement with the
stimulated emission cross-section of sem ¼ 2:7 1019 cm2 obtained from analysis of
laser experiments [24].

6. Passively Q-switched lasers

6.1. Lamp-pumped lasers

Quadrivalent Cr4+-doped hosts, in particular, Cr4+:YAG codoped with Ca2+ or


Mg2+ as charge compensators, are currently used as passive Q-switches in Nd:YAG,
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Fig. 12. Ground-state, excited-state and effective cross-section spectra in Cr4+:GGG taken from
Ref. [100]).

Nd:YVO4, and Yb:YAG lasers, as well as in microlasers. The reasons for this stem
from several reasons: they have a wide absorption band around 1 mm; with FOM
that is appropriate for passive Q-switched performance. The lifetime of the first
excited-state level of Cr4+ is relatively long enough to allow energy storage until
saturation of the optical transition occurs, and the saturation fluence of various
Cr4+-doped hosts is relatively low. Also, Cr4+-doped crystals, in particular garnets,
exhibit good thermal, mechanical, and optical properties which allow the extraction
of laser pulses having high peak power and high repetition rates and the
manufacturing of electro-optical devices with good quality. These systems, unlike
the ones with active Q-switching devices, are compact, inexpensive, simple, robust
and easily operated and aligned, and they do not require any external power
supply or polarizing optics. Cr4+-doped garnets are superior relative to other passive
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Fig. 13. Ground- state, excited-state and effective cross-section spectra in Cr4+:YSGG taken from
Ref. [100]).

Q-switches, such as organic Q-switching materials or inorganic color center crystals


due to their photochemical, thermal, and mechanical characteristics. Another
significant advantage of the system is the possibility of using Nd3+ or Yb3+:YAG-
codoped with Cr4+ to create monolithic, self-Q-switching operation, using laser
materials such as Nd, Cr:YAG, Yb, Cr:YAG, or Nd, Cr:GSGG [107–110], or
microchip lasers with diffusion-bonded elements[111–113]. This laser has a miniature
flat–flat monolithic cavity and is pumped with close-coupled unfocused diodes. This
arrangement offers even more simplicity and compactness as well as short pulse
durations and high output peak powers for various applications, using diode-
pumped systems [113]. Passive Q-switching using Cr4+-doped garnets in both lamp-
and diode-pumped configurations of Nd:YAG lasers was achieved by Andrauskas et
al. [114] by using several Cr4+, Ca2+-doped garnets. By using uncoated samples of
Cr4+: GSAG or Cr4+:GIGG (Gd3In2Ga3O12), in a simple experimental setup for
both lamp- and diode-pumped lasers, they obtained Q-switched pulses with pulse
widths (FWHM) in the range of 10–30 ns, with repetition rates of 5–30 Hz, and laser
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Fig. 14. ESA (a) and ground-state absorption spectra (b) in Cr4+:LuAG taken from Ref. [101]).

energies in the mJ order of magnitude. Klimov et al. [115] demonstrated the


Q-switching operation of Cr4+:YSGG in a simple plane–plane laser resonator. This
Q-switching device yielded multi-spikes having repetition rates up to 300 kHz and
pulsewidths as short as 100 ns (FWHM), depending on the resonator length. Similar
multi-spiking was obtained in passive Q-switching of pulsed Nd:YAG laser using
Cr4+:YAG as a saturable absorber [116]. Fig. 15 exhibits the oscilloscope traces of
output pulses from Nd:YAG laser operating both in free-running and Q-switched
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modes. A shortening in the Q-switched pulse duration (28 ns FWHM) relative to the
pulsewidth of a selected spike from the random spiking train(168 ns FWHM) was
observed upon Q-switching. It was concluded that the peak power in the Q-switched
pulse was about two orders of magnitude higher than in the free-running spike.
Fig. 16 presents a typical curve of output energy vs. input pumping energy of free-
running and passively Q-switched lasers. In this case, the passively Q-switched curve
shows an increase in threshold pumping and several steps along the curve where each
step reflects the appearance of additional spike. The flat ramps that form the steps
indicate the situation where the energy continues to pump the rod but is still
insufficient to induce bleaching and create more spikes. The steps become less
resolved at high pumping power where there are many spikes that overlap with each
other as a result of temporal jittering [95].
A similar multi-spiking was also observed in passively Q-switched Nd:YAG by
Cr4+:LuAG [101,105]. In the case of Cr4+:YAG, Miller et al. [117] used samples
with small Cr4+ concentration, in the range of E0.02 and E0.05 at%, with a range
of different thicknesses, and AR/AR coating on both sides. They studied the Q-
switching performance both in a lamp- and diode-pumped configurations of
Nd:YAG lasers. For the lamp-pumped Nd:YAG laser system they obtained TEM00
Q-switched pulse of 100 ns duration, 30 Hz repetition rate, and about 30% extraction
efficiency of Q-switched output energy relative to the free-running performance. The

Fig. 15. Oscilloscope traces of a passively Q-switched and a free-running Nd:YAG laser. (a) Q-switch
performance using Cr4+:YAG sample as a saturable absorber, 50 mV/div sensitivity. (b) Free-running
performance with random spiking. (c) Free-running performance using undoped YAG. (d) Waveform of
the pumping waveform. Sensitivity in traces b–d: 5 mV/div. Inset: Q-switched (curve e) and free-running
spiking (curve f) on a more detailed time resolved scale taken from Ref. [116]).
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Fig. 16. Output vs. input pumping energy of a Nd:YAG under free-running operation (a) and (b), and
passively Q-switched operation mode (c). Curve (b) was measured with undoped YAG as a Brewster plate
taken from Ref. [95]).

extraction efficiency increased to 40% by increasing the absorbance of the saturable


absorber. Theoretically, it was shown that by increasing the optical density of the
element, the energy extraction efficiency can have values of E75%, with pulsewidth
as short as 20 ns (FWHM). Experimentally it was found that the energy extraction
efficiency in the high-energy pumping range is 67%, and that the shortest pulsewidth
obtained under these conditions was 28 ns (FWHM) [116]. A comparative behavior
of Cr4+-doped YAG, YSGG, and LuAG as passive Q-switches of Nd:YAG laser
(under the same experimental conditions) presents interesting results. As expected,
the relaxation oscillation spiking of Nd:YAG emission in the free-running mode was
replaced by a single, giant pulse, with peak power which was 10 times bigger
compared to the free running, and with pulse duration (FWHM) of 52, 42 and 23 ns,
respectively. The above results of Cr4+:LuAG are very similar to those reported
elsewhere [101,105] which reported extraction efficiency of E35% for Cr4+:LuAG.
As an example, the performance of Nd:YAG laser under free-running and
Q-switching conditions using Cr4+:YSGG as saturable absorber is presented in
Fig. 17 [99].
The time between the trigger of the flashlamp and the appearance of the first Q
switched pulse is 6 ms for Cr4+:YAG, 15 ms for Cr4+:YSGG, and 18 ms for
Cr4+:LuAG. This time delay measures the energy storage capability of various
Cr4+-doped garnets. The shorter the time delay is, the smaller is the energy necessary
to saturate the saturable absorber and to obtain Q-switching. This observation is
consistent with the saturation curve results presented in Fig. 9. The broad absorption
band of Cr4+ in the near-IR allows for passive Q-switching of lasers such as
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Fig. 17. Oscilloscope traces of passively Q-switched and free-running signal of Nd:YAG laser using
Cr4+:YSGG as a saturable absorber. (a) Free-running performance with oscillation relaxation structure.
(b) Q-switched signal. (c): Q-switched pulse on an expanded time scale. The sensitivity of (a) is 20 mV/div,
of (b) and (c) 0.2 V/div taken from Ref. [99]).

Nd:YAP (lem ¼ 1079 nm) using (Cr4+, Mg2+):YAG as a saturable absorber [63], or
even dual Q-switching at 1.06 and 1.44 mm using the same element as a saturable
absorber [118].
Laser media can be pumped in pulsed or continuous (CW) modes. Similarly to the
case of pulsed lasers, the lasers based on CW operation can also be passively Q-
switched by Cr4+-doped hosts, yielding repetitive modulation at high frequencies.
Such systems are useful for applications where high repetition rates and high peak
power are required. The jitter in these systems, both temporally and as related to
energy, may be a limitation, and therefore the lasers are useful for applications where
timing is not required. Since the pump average power applied to a CW laser is low,
the inversion ratio, Ni/Nth and the peak power are also low. (Ni is the population
inversion just after the switching, Nth is the threshold inversion just after switching.)
At low repetition rates, f pga ; where f is the repetition rate and ga is the decay rate of
the first excited state of the saturable absorber, the laser produces Q-switched pulses
with an average power that is proportional to the repetition rate, and the pulse
energy is almost constant. At high repetition rates, f Xga ; the laser acts as a CW
source and its operation is limited by the decay rate. The average power flattens and
pulse energy decreases with the increase of the repetition rate. In the case of CW
Nd:YAG laser, the variation of lamp pumping power and the Cr4+:YAG optical
densities yielded repetition rates ranging between 2 and 29 kHz and pulses with
80–300 ns pulsewidth (FWHM), with temporal jitter of E715% and 75% in
amplitude [119].
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6.2. Diode-pumped systems

The advent of diode-pumped solid-state lasers (DPSSL), particularly diode-


pumped Nd:YAG and Nd:YVO4, has stimulated new opportunities for Cr4+-doped
solids as saturable absorbers have emerged. Particularly, the medium power, CW
diode-pumped solid-state lasers have been sought for various scientific, medical, and
military applications because they provide unique properties to these applications,
where compact, reliable, cost-effective, stable, and highly efficient sources are
required. Due to these advantages, there has been practical incentive to couple CW
diode-pumped solid-state lasers with passive Q-switches based on inorganic-doped
Cr4+ crystals, for operation of an all solid-state Nd:YAG laser. Since diode-pumped
lasers can be operated in two pumping modes, namely, transverse (or side pumping)
as well as end (or longitudinal pumping) modes, it is necessary to test the concept of
repetitive modulation applied to diode-pumped solid-state laser systems by using
both pumping geometries.
The first operation of a medium power, CW diode-pumped Nd:YAG passively
Q-switched laser was reported by Agnesi et al. [120]. The laser which was pumped by
a fiber-coupled diode array at 808 nm, produced 1.5-W average output power at
1064 nm at maximum pumping power, with pulses of 100 mJ, 36 ns pulsewidth
(FWHM), repetition frequency of 15 kHz, and beam quality of M 2 p1:5: They also
observed the dependence of the pulsewidth and modulation frequency on the pump
power: as the pumping power increased, the pulse duration decreased while the
modulation frequency increased. Further improvement in passively Q-switched
diode pumped Nd:YAG laser and preliminary results pertaining to Nd:YVO4 laser
operated under the same experimental conditions were reported by Agnesi et al.
[121]. For a CW and passively Q-switched DPSSL (Nd:YAG), pulse energy ofE200
mJ or average output power (E2 W) was reported later [121]. This was achieved by
an optimized resonator design, utilizing the saturable absorber crystal as an output
coupler, and adjustment of the mode area in the gain (Ag) and in the saturable
absorber (As) elements, such that Ag/Asb1. The high peak power, the excellent beam
quality generated by the laser, and the possibility to produce a linearly polarized
laser beam, allowed the coupling of non-linear elements such as KTP or LBO [121]
or PPLN [122] with these lasers for various applications.
Repetitive modulation of longitudinally pumping Nd:YAG and Nd:YVO4 lasers
yielded mean modulation frequencies of 12 and 60–100 kHz for YAG and YVO4,
respectively, under 7.3-W pumping power. Efficient operation was obtained by
optimizing the pump and cavity volume modes. At lower pumping power, in the
range of 5.5–6.2 W, the modulation frequencies of both Nd:YAG and Nd:YVO4
decreased to values of 7 and 18 kHz, respectively. This trend is similar to what
was reported by Agnesi et al. [121,122]. The pulsewidth (FWHM) produced by
the saturable absorber in Nd:YAG and Nd:YVO4 was E60 and E100 ns,
respectively [123].
For a CW, transversely diode-pumped Nd-doped crystal, a similar picture was
observed using Cr4+:GGG both as a saturable absorber and as a back (HR) mirror.
For Nd:YVO4 operation, the modulation frequency in the pumping level of 10–15 W
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varied between 225 and 410 kHz, respectively. For repetitively Q-switched Nd:YAG,
the mean modulation frequency varied with the pumping energy in the 10–50 kHz
frequency domain. The difference in the average modulation frequencies between
YAG and YVO4 is accounted for the short lifetime of the 4F3/2 lasing level of
Nd:YVO4 relative to Nd:YAG. The pulsewidth (FWHM) depends on the pumping
level. It decreased with the increase in the pumping power, from 400 ns at 10 W to
125 ns at 15 W [123]. Fig. 18 [123,124], presents the change in the Q-switched
pulsewidth as a function of the pumping power The experimental data are presented
together with the calculated results which are based on a dynamic model that takes
into account the rate equations for the population inversion density and the photon
density inside the resonator [124].
The average output power of the Q-switched operation as a function of the pump
power for both Nd:YAG and Nd:YVO4 is presented in Fig. 19. The slope efficiencies
of the CW Q-switched Nd:YAG is 25% and that for Nd:YVO4 is 18%, and the
conversion efficiencies of the Q-switched average power relative to the free-running
mode are E70% and E45%, respectively.

Fig. 18. Calculated and measured Q-switched laser pulse (HWHM) of the Nd:YVO4 laser as a function of
the pumping power. Inset: the calculated and measured temporal evolution of the Q-switched laser pulse at
15-W pumping power taken from Ref. [124]).
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As was mentioned before, the saturable absorber element can be attached to the
gain element by diffusion bonding, optical contact, or codoping of Cr4+ with Nd3+
in the same crystal. A comparative investigation between Cr,Nd:YAG (codoped
sample) and Nd:YAG/Cr4+:YAG (diffusion-bonded sample) has been conducted
[109]. The diode-pumped diffusion-bonded system provided maximum average
output power of 2.2 W with 42% slope efficiency and 53% conversion efficiency of
free running into Q-switched mode. The Cr,Nd:YAG-codoped sample produced
1.8 W of average output power, with 34% slope efficiency and 24% optical-to-
optical efficiency. Both Q-switched samples produced pulses in the kHz frequency
regime and pulsewidths (FWHM) in the range 11–20 ns, independent of the input
pumping power. Fig. 20 presents a linear plot of the average output power of the
diode-pumped, self-Q-switched Cr,Nd:YAG laser.
Besides the Nd:YAG laser crystal, there are other crystals that are attractive
candidates as compact, high-gain passively Q-switched DPSSL, and that have
potential to be effective diode-pumped microlasers. One example is the Nd:
KGd(WO4)2 (denoted also as KGW), with emission wavelength at 1068 nm [125].
Compared to Nd:YAG, it has broader and polarized absorption and emission
transition bandwidths, relatively low thermal lensing due to small values of dn/dT,
and high doping level, up to 10 at% in Nd:KGW compared to 1.1 at% in Nd:YAG.
This implies that Nd:KGW can be utilized as a compact, low average power
microlaser. The passive Q-switching of Nd:KGW was obtained by using several
samples of Cr4+:YAG and Cr4+:GGG as passive Q-switches, with small signal
transmission ranging from T0=89% to 97%. Both the Q-switched pulsewidth and
repetition frequency exhibited dependence on the absorbed pump power similarly to
Agnesi et al. [121]. The changes in the pulsewidth and modulation frequency and of

Fig. 19. Average laser output power of Q-switched Nd:YAG and Nd:YVO4 lasers as a function of the
pump power taken from Ref. [124].
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Fig. 20. Laser output average power and slope efficiency of 1.06 mm laser emission of the diode-pumped,
self-Q-switched laser vs. incident pump power at 808 nm of the CW diode taken from Ref. [109]).

Nd:KGW as a function of the pumping power for two types of saturable absorbers
are presented in Figs. 21 and 22, respectively.
The passive Q-switched Nd:KY(WO4)2 (Nd:KYW) performed poorly relative to
Nd:KGW due to overall crystal quality and effective Nd3+ concentration, which
resulted from the small ionic radius of Y3+ (1.015 Å) as compared to Gd3+ (1.06 Å)
and Nd3+ (1.12 Å) [126]. Passively Q-switching of Yb:YAG laser is another option
which allows us to develop and obtain a compact and efficient microlaser based on
Yb-doped laser. In the case of Yb:YAG that is Q-switched with Cr4+:YAG, the
modulated peak power was E10.4 kW, with pulse energy of E0.5 mJ/pulse, and
30% extraction efficiency relative to the free-running, and average output power of
E4.8 W. The dependence of the repetition frequency and pulsewidth on the pumping
power using Cr4+:YAG as a saturable absorber is presented in Fig. 23. Q-switched
operation with Cr4+:YAG out performs other saturable absorbers such as
Cr4+:LuAG or Cr4+:GSGG. The average output power using the latter garnets
was lower than using Cr4+:YAG. Both Cr4+:LuAG and Cr4+:GGG exhibited
modulation frequencies in the kHz frequency regime and pulsewidths in the range of
E25 ns and E16 ns for, respectively [127].
Scale-up of a Nd:YAG passively Q-switched laser was obtained by employing a
monolithic non-planar ring laser. This scheme yielded 800 mW average output
power, 70 mJ pulse energy of 3 ns pulse duration, and 30 kW peak power [128].
Recently, Tordella et al. [129] reported the operation of an all-fiber passively
Q-switched CW-pumped laser. This laser is an Nd3+-doped silica fiber which was
fusion spliced to a Cr4+-doped silica fiber—see Fig. 24 for the experimental setup
details. This all-fiber laser system had a core diameter smaller than 10 mm core
diameter. In the pumping power range of 25–50 mW, the pulse duration varied from
31 to 17 ns, while the repetition rate increased from 10 to 23 kHz.
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Fig. 21. The dependence of the Q-switched pulsewidth (FWHM) vs. absorbed pump power for Nd:KGW
laser for two saturable absorbers: (a) Cr4+:GGG, (b) AR coated Cr4+:YAG taken from Ref. [125]).

Fig. 22. The dependence of the modulation frequency on the absorbed pump power of Nd:KGW laser for
two saturate absorbers: (a) Cr4+:GGG, (b) AR-coated Cr4+:YAG taken from Ref. [125]).

7. Summary

This review provides an overview on the subject of Cr4+-doped solids and their
applications in laser physics, technology, and industry. The transition metal ions
have spectral properties which make them favorable candidates for active
lasing ions. The Cr4+-doped crystal has the unique characteristics of being both
saturable absorber for the 1.06 mm laser emission of Nd:YAG as well as being a
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Fig. 23. The repetition frequency and output pulsewidths versus pumping power of a passively Q-
switched, diode-pumped Yb:YAG/Cr4+:YAG laser taken from Ref. [127]).

Fig. 24. Experimental setup of Nd3+: Cr4+ doped silica fiber laser: M1 and M2 broadband mirrors with
reflectivities 499% and 90%, at the laser wavelength, respectively; Pp and Ps are the pump beam and
output laser power, respectively taken from Ref. [129]).

tunable mid-IR laser in the spectral range of E1.3 to E1.6 mm with significant
practical implications.
The basic spectroscopic concepts and particularly the spectral properties, the
structural characteristics, and the physical parameters of Cr4+-doped various solids
were discussed and analyzed. In particular, the effects of the non-radiative relaxation
from the first excited-state level on the laser performance and on the quantum
efficiency was critically reviewed, and possible proposed models were introduced.
Knowing the spectroscopic properties, the physical parameters, and the crystal
field effects on the position of the energy levels, we analyzed the use of various Cr4+-
doped solids such as forsterite and garnets as room temperature, tunable mid-IR
lasers in the spectral range 1.3–1.6 mm. We emphasized the crystal field and
coordination effects on the spectroscopy as well as on the laser performance of Cr4+-
doped solids, and further analyzed the thermal effects on Cr4+ laser performance
and its resonator design. The recent technological developments in mode-locked
ultrafast, femtosecond Cr4+:YAG and Cr4+:forsterite lasers have been also
reviewed with the context of their unique usefulness as ultrafast laser sources in
the eye-safe spectral region.
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In the last section we reviewed the role of Cr4+-doped garnets as saturable


absorbers in various Nd- and Yb-doped crystals. We explored the physics of the
saturation and extracted the relevant cross-sections necessary for saturation and
consequently, for Q-switching.
The passively Q-switched operation was discussed both in lamp and diode-
pumped systems, where modulated pulses in the kHz frequency range, with several
nanosecond pulsewidths (FWHM) were obtained. Currently systems based on
Nd3+- or Yb3+-doped solids, coupled with Cr4+-doped saturable absorbers are
optimized toward more efficient performance. These systems aim at producing high
peak power from compact monolithic microchip lasers toward applications in
industry (micromachining, drilling), medicine, instrumentation, and sensing. The
main advantage of Cr4+-based lasers, namely, the broad bandwidth emission in
the near-IR, is utilized to generate ultrafast pulses, ultrafast optical transmitters in
the eye-safe region, and ultrasensitive sensors for chemical compounds with
absorption bands in the mid-IR. [130].

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