Interpretation of the Emission Spectra

of Trivalent Chromium-Doped Garnet Crystals

Using Tanabe-Sugano Diagrams
Michael D. Seltzer
Chemistry Division, Research Department, Naval Air WarfareCenter Weapons Division, China Lake, CA 93555-6001
In this paper I provide an example of an application in The splitting of energy levels is a consequence of the re-
which Tanabe-Sugano diagrams (I, 2) are used to relate pulsive interaction between the d orbitals of the transition
the optical properties and performance of a material to its metal ion and the neighboring anions in the host crystal.
physical and chemical properties. Tanabe-Sugano dia- Due to their geometrical orientation in the octahedral
grams illustrate the effect of the strength of the octahedral field, some of the d orbitals experience a more direct, and
ligand field on the relative positions of the various energy correspondingly stronger, electrostatic repulsion than oth-
level components that arise as a result of the splitting of ers. Accordingly, these orbitals become raised in energy
the degenerate free-ion states of transition metals. The ap- and are labeled eg. Other orbitals, labeled tzg, experience a
plication of these diagrams can also be extended to the
spectra of transition metal ions found in solid-state matri-
ces where the predominant external force is the crystal
field. In crystalline materials such as garnets, transition
metal ions occupy sites with six anions as nearest-neigh-
bors, forming a coordination sphere characterized as a dis-
torted octahedron. Although the actual site symmetry is
lower than Oh in most cases, an octahedral approximation
is qualitatively sufficient for the present application in-
volving an analysis and interpretation of the emission
spectra of chromium-doped garnets.

Crystal-Field Splitting and TanabeSugano Diagrams

Figure 1 is a TanabeSugano diagram specifically repre-
senting the cr3+ion, which has three electrons in d orbitals.
This is one of a series of diagrams representing transition
metal ions with different dn configurations. In the Tanabe-
Sugano diagram, the abscissa (Dq)represents the increasing
crystal-field strength in equivalent wavenumher units. The
ordinate represents the energy separation between various
states and is also expressed in wavenumber units.
The term symbol for the degenerate ground state of a
free ion of d3 configuration is 4 ~ In. an octahedral field, the
degeneracy is lifted, and the 4~ state is split into a 4 ~ 2
ground state and two excited states: 4 ~ and4T,.
z Similarly,
each of the degenerate excited states of the free ion is split
into a number of components. The term symbols of the Figure 1. Energy diagram adapted fromTanabe and Sugano (I). The
free-ion states (Dq = 0) are shown on the left-hand side of diagram is specific to trivalent chromium and has been simplifiedrela-
the diagram, and the term symbols representing the re- tive to the eneralized Tanabe-Sugano diagram for d3transition met-
sults of crystal-field splitting are shown on the right. al ions (&, "', b7n4*).

886 Journal of Chemical Education

weaker repulsion as a result of less direct interaction with Non-radiative
the neighboring anions. relaxation

The Spectra
\
Energy
F i v e 1shows that the energy separation between the *TZ transfer
and Az levels is very sensitive to the magnitude ofDq. Popu-
lation of the 4 ~level
z involves electron occupation of both the
e, and tzr orbitals (see below). Thus. the enerev senaration
t&eeikis level and the 4 ~ ground
2 state is &&t indica- Laser
m
3 output
tion of the demee of electrostatic repulsion between the occu-
pied orbitalsand the neighboring &ions. This separation is g
assimed a value eauivalent to 10Du and can be assessed em- 2 W
piri&ly from abso&on spectra b4 measuring the cnergy of
the 'T~-"A?transnion. Convrrselv, thc Tunahc~5ueanndia-
gram also allows one to predict theiptical spectrum i f a tran- Cr3+Sensitizer ~ d Activator
~ +
sition metal ion in a particular environment given some
knowledge of the crystal-fieldstrength. Figure 2. Energy diagram illustrating the absorption of pump energy
The absorption and fluorescence spectra of transition by sensitizer ions, the transfer of energy to the activator ions, and the
metal ions are typically broad (50-100 n m full width at re-emission of energy as laser radiation.
half maximum) though the associated transitions occur be-
tween discrete electronic levels. This is especially true in
crystal hosts where vibration of the crystal lattice ions
about their equilibrium positions modulates the crystal
field exerted on the transition metal ions and dynamically
varies the separation between energy levels. This gives
rise to what is commonly called vibronic or phonon-broad-
ened spectra. Rare earth ions on the other hand. exhibit
relatively narrow band spectra (around 1nm full k d t h a t
half maximum) due to the absence of phonon broadening.
The f orbitals associated with rare earth ion spectra are
well-shielded and are therefore less subject to electrostatic
repulsion than are d orbitals. Accordingly, rare earth ions
-
also experience a more limited crystal-field sulittine than
do transition metal ions.

Chromium lons as Sensitizers in Laser Crystals

Crystals doped with rare earth ions or transition metal
ions, or both, are extremely useful as active media for solid-
state lasers (3).Agood example is necdymium-dopedyttrium
aluminum garnet (Nd:YAG),the workhorse of the solid-state
laser world. The chemical composition of YAGisY3A15012.h
undoped YAG crystal is not fluorescent. However, highly flu*
rescent ~d~~ ions substitute for a small fraction of the y3+
ions in YAG, thereby activating the material. Thus, the Nd3+
ions can be called activator ions. When a Nd:YAG crystal is
placed in a laser resonator and pumped or excited with an
external light source, the Nd3+ ions exhibit intense stimu-
lated emission at a wavelength of 1.064 pm.
Fluorescence Sensitizer
There has been considerable interest in impmving the effi-
ciency of the Nd:YAG laser by enhancing the absorption of light
energy from the pumping s o m , which is mually a xenon flash-
lamp. The problem with flashlamp pumping is that flashlamps
emit light over avery hmad spe&nm, whereas the Nd3+activa-
tor ions absorb DUD e n e m onlv -
" at s d c waveleneths. Con-
sequently, a la& &are o f & n p energy is wasted, &reby lim-
550 650 750 850 950
WAVELENGTH (nm)
Figure 3. Room temperature emission spectra of c?+-doped yttrium
aluminum garnet and c?+-doped gadolinium scandium gallium gar-
net. ~ d -laser pump absorption bands are also shown.
Use of Trivalent Chromium lons
Trivalent chromium ions in most crystals have strong,
broad absorption hands in the W and visible regions of
the spectrum. Chromium ions characteristically re-emit
absorbed energy as fluorescence in the red to near-IR re-
gion of the spectrum where Nd3+ions have several strong
absorption bands. Because chromium ions can substitute
readily for some of the aluminum ions in YAG during crys-
tal growth, they would appear to meet the requirements as
a sensitizer for ~ d ~However.
+ . initial a t t e m ~ t to
s use cr3+
as a sensitizer have proved disappointing due to unfavor-
able emission characteristics observed for cr3+in the YAG
host. Figure 3 shows that there is only minimal overlap
between the emission spectrum of cr3+ and the Nd3+ ah-
sorption bands in YAG.

i h the efficienwof the laser. One solution to this dilemma is
the~corporationbfa second species of fluorescentions into the
laser crvstal to serve as a fluorescencesensitizer forthe activator
ions. The ideal sensitizing ion is one that absorbs pump energy
over a bmad spectrum and then transfers the concentrated en-
ergy to the activator ions by reemitting it at wavelengthswhere
the activator ions absorb mast stmngly The energy diagram in
Figure 2 illustratesthe absorption of pump energy by sensitizer
ions, the transfer of energy to the activatorions, and the reemis-
sion of energy as laser radiation.
Interpreting the Emission Spectrum
We can interpret this emission spectrum in terms of the
YAG cmstal field and its effect on the relative ~ositionsof
the crJi. energy levels, a relationship clearly illustrated by
the Tanabe-Sueano diamam shown in Figure 1.The value
of Dq for C ~ : Y ~has
G been estimated to i e 1640 cm-I (4).
As shown in Figure 1, at this value of Dq the 'E level is
positioned somewhat lower in energy than the 4 ~ level. z
Even at room temperature, the two levels are not in ther-
mal equilibrium and all of the energy absorbed by the

Volume 72 Number 10 October 1995 887

broad chromium absorption bands is deposited in the
lower 'E level (5).The predominant emission from cr3+
ions in YAG a t room temperature is associated with weak,
spin-forbidden transitions between the ' E excited level
and the 4 ~ ground
2 state that do not coincide with Nd3+
absorption bands. As a consequence, energy transfer to
Nd3+is not efficient, and the potential benefits of cr3+ sen-
sitization are not realized. F i p e 1shows t h a t i h e separa-
tion in energy between the E level and the Az ground
state is relatively insensitive to variations i n the magni-
tude of Dq. Accordingly, the transitions between these lev-
els are not subject to extensive phonon broadening.
Spectral Differences between Cr:YAG a n d Cr:GSGG
The room-temperature emission spectrum of chromium-
d o ~ c deudnlinium scandium eallium earnet IC~:CSC;CI
shbwn k Figure 3. GSGG is Ydenticalalin structure to YAG
-
e x c e. ~ eadolinium
t ions r e ~ l a c evttrium ions, and scandium
and gallium ions rcplacr ulummum ions. The chemical cum-
onsition of GSGG is C ~ ? S ~ K ~ P~Kr ' ~ . ions
I ~ . substitute fnr
Lome of the scandium ions in GSG.As can be seen in Figure
3, the intense cr3+emission band effectively overlaps the
Nd3+absorption bands between 750 and 900 nm. l h what can
we attribute this dramatic shiR in the cr3+emission spec-
trum? Spectral differences between Cr:YAG and Cr:GSGG
can best be explained in terms of the crystal field with the
help of the Tanabe4ugano diagram. Figure 1indicates that
the magnitude of Dq determines the mutual proximity of the
4 ~ and z ' E levels, which can be of considerable influence on
the emission characteristics of cr3+.
Field Strength and Energy Differences
I n the garnets, the crystal field decreases a s the radii of
the cations and the associated lattice narameter increases.
Due to the incorporation of large caiions (sc3+ and ~ a ~ has
-
instead of A13+).GSGG bas a lareer lattice Darameter than
YAG and, thus, H wwkrr crystal field From the ahsorpt~on
sowtrum of'Cr:GSGG one can estlmatr the value of Do to
de 1479 cm-I (6).Figure 1shows that a t this fieJd strength,
the energy difference between the 4 ~ azn d E levels in
GSGG is considerably less than that in YAG. In fact, this
energy difference is sufficiently small in GSGG for these
levels to be in thermal equilibrium a t room temperature;
this favors the predominance of spin-allowed fluorescence
fmm the 4 ~ level.z Most importantly, the intense emission
originating from the 4~ level extends much further into
2
the near-IR than the E emission observed in Cr:YAG
though these levels are approximately equal in energy
Fluorescence a t Longer Wauelengths
The energy diagram in Figure 4 shows the vibronically mu-
nlrd enerw levels invol\.cd in Cr" ion emission and indicutes
ihat the g t t o m of the potential well for 4 ~ isz located a t a
greater interionic distance than the bottom of the potential
wells for4Az and'^. Population of the excited 4 ~level z occurs
-
when one of the three electrons in the t r i.~-l vdegenerate tzc
orbitals 1s pnlmoted into thc doubly degenerate e,. orbitals
twr Fia. 4). The stronr t~ltxtrostaticrepulsion of the i r c u ~ i r d
eg o r h a causes an I>crease in the interionic distanci be-
tween the cr3+ ion and the neighboring anions. he'^ level
and t h c ' ~ 2grnund state are associated w t h vlrctron occupa-
tion ol'thc less repulsivr 1x1 orbitals only w e Fig. 4,. lircause
emission originates from the bottom ofthe ex&d-state en-
ergy well, and the interionic distance does not change during
this process, emission from the lowest vibronic levels of the
4 ~ canz only proceed via transitions to the upper vibronic lev-
els of the 4~~ ground state as shown in Figure 4.
The notion that the interionic distance does not vary in
the time frame associated with emission of light is called
the Franck-Condon Principle (7).The transitions from the
888 Journal of Chemical Education
-
Interionic Distance
is
Figure 4. c?+ion energy diagram showing thatfluorescencefrom4 ~ 2
level has lower energy (longer wavelength) than fluorescence from
' E due to the increased interionic distance associate with the 4 ~ 2
state. Multiple arrows represent phonon-broadened emission. Also
shown are electron-orbitalconfigurations associated with the 4 ~ 2' E, ,
and 4 ~ energy
z levels.
bottom of the 4 ~ ezn e r w well to the upper vibronic levels
of the 4 ~ ground z state are longer &-wavelength than
those associated with emission from the bottom of the E '
to the lowest vibronic levels of the 4 ~ ground z state. In ad-
dition, the 4 ~ +24 ~ 2transitions are honon-broadened to
a much greater extent than are the 9E + 4 ~ ztransitions,
thereby supporting fluorescence a t longer wavelengths. As
aresult, optimum overlap with the pumping bands of Nd3+
is achieved thus enabling eff~cientenergy transfer be-
tween cr3+ ions and Nd3+ions. Not surprisin ly, cr3+ions
are extremely effective as sensitizers for Nd & ions . in the
GSGG host, and efficient operation of a Cr,Nd:GSGG laser
' been successfully demonstrated (8). However, despite
the efficiencv advantape obtained bv incornoratine cr3+
ions a s senskizers in &,N~:GSGG, ksensiiized N ~ Y A G
continues to Dredominate over Cr.Nd:GSGG for most ao-
plications due to the superior optical and thermal proper-
ties of YAG relative to GSGG.
Summaw
The preceding discussions of thc cmission spectr:1 nf t n -
valcnt chromium ions in YAG and in GSGG emohasize thr
value of Tanabe-Sugano diagrams for makingLqualitative
comparisons of the crystal-field environments in different
hosts. The slight difference in crystal field between the
YAG and GSGG hosts, due to differences in the radii of the
constituent cations, has a profound effect on the channel-
in of absorbed energy, the emission characteristics of
Cr5 +Ions,
. and their utility a s sensitizers for a Nd3+laser.
The Tanabe-Sugano diagram clearly illustrates that it is
the crystal-field-dependent energy separation between
various s t a t e s t h a t determines the emission charac-
teristics of transition metal ions in a particular host.
Acknowledgment
The author would like to thank Daniel C. Harris for the
valuable discussions, interest, and enthusiasm that facili-
tated the preparation of this manuscript.
Literature Cited
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1975;p 368.
3. Milonni, P. W.; Eberly, J. H. Losrs: Wiley: Nelr York, 1988; p 310.
4. Morrison, C.A.;Gmber. J.B.; Hills, M. E. Chem. Phys. 1981,154,437447.
5. Struve. B.: Huber, G. Appl. Phys B 1985,36,19%201.
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1988.37.8564-8574,
7 . Herzberg. G.Sprcfm ofDlolomle Moleules; Van Noatrand: New York, 1950;p 194.
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