1302 IEEE JOURNAL
OF QUANTUM
laser parameters such a &-switching can be achieved by the
applied gate-voltage less than 5 V.
REFERENCES
P. -T. Ho, L. A. Glasser, E. P. Ippen, and H. A. Haus, “Picosecond
pulse generation with a cwGaAlAslaser diode,” AppZ. Phys.
Lett., vol. 33, pp. 241-242, Aug. 1978.
T. C.Damen and M. A. Duguay, “Optoelectronic regenerative
pulser,” EZectron. Lett., vol. 16, pp. 166-167, Feb. 1980.
T. Kobayashi, A. Yoshikawa, Y. Aoki, and T. Sueta, “Generation
of picosecond optical pulses bysemiconductor laser,” Tech. Group
Opto-Quantum Electron., IECE Japan, vol. OQE80-12, pp. 17-
24, May 1980.
I. Ury, S. Margalit, M. Yust, and A. Yariv, “Monolithic integra-
tion of an injection laser and a metal semiconductor field effect
transistor,” Appl. Phys. Lett., vol. 34, pp. 430-431, Apr. 1979.
T. Fukuzawa, M. Nakamura, M. Hirao, T. Kuroda, and J. Umeda,
“Monolithic integration of a GaAlAs injection laser with a
Schottky-gate field effect transistor,” Appl.Phys.Lett., vol. [12] M. Danielson, “A theoretical analysis for gigabit/second pulse
36, pp. 181-183, Feb. 1980.
D. Wilt, N. Bar-Chaim, S. Margalit, I. Ury, M. Yust, and A. Yariv,
Papers
Tunable Alexandrite Lasers
JOHN C. WALLING, OTIS G. PETERSON, HANS P. JENSSEN, ROBERT C. MORRIS
AND E. WAYNE O’DELL
(Invited Paper)
Abstruct-Wavelength tunable laser operation has been obtained from
the solid-state crystal alexandrite (BeA1204:Cr3*) over the continuous
range from 701 to 818 nm. The tunable emission was observed at room
temperature and above in a homogeneously broadened, vibronic, four-
level mode of laser action. In this mode the laser gain cross section
increases from 7 X cm2 at 300 K to 2 X a n 2 at 475 K,
Manuscript received April 30,1979; revised August 15,1980.
J. C. Walling, R. C. Morris, and E. W. O’Dell are with the Corporate
Research Center, Allied Chemical Corporation, Morristown, NJ 07960.
0. G . Peterson was with the Corporate Research Center, Allied
Chemical Corporation, Morristown, NJ 07960. He is now with the
Applied Photochemistry Division,LosAlamos Scientific Laboratory,
Los Alamos, NM 87545.
H. P. Jenssen is with the Center for Materials Scienceand Engineering,
Massachusetts Institute of Technology, Cambridge, MA 02139.
0018-9197/80/1200-1302$00.75 0 1980 IEEE
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ELECTRONICS,
NO.
QE-16,
VOL. 12, DECEMBER 1980
“Low threshold Be implanted (GaAl)As laser on semi-insulating
substrate,” IEEE J. Quantum Electron., vol. QE-16, pp. 390-391,
Apr. 1980.
[7]T. Tsukada and C. L. Tang, “Q-switching of semiconductor
lasers,” IEEE J. Quantum Electron.,vol. QE-13, pp. 37-43, Feb.
1977.
[8] T. Kajimura, K. Saito, N. Shige, and R. Ito, “Leaky-mode buried-
heterostructure GaAlAs injection lasers,” Appl. Phys. Lett., vol.
30, pp. 590-591, June 1977.
[9] W. T. Tsang and R.A. Logan, “Lateral-current confinement in a
GaAs planar stripe-geometry and channeled substrate buried DH
laser using reverse-biased p-n junctions,” J. Appl. Phys., vol. 49,
pp. 2629-2638, May 1978.
[ l o ] Y. Suematsu and M. Yamada, “Oscillation-modes and mode-
control in semiconductor lasers with stripe-geometry,” Trans.
IECE Japan, vol. 57-C, pp. 434-440, Nov. 1974.
[ 111 P. M. Boers, M. Danielson, and M. T. Vlaardingerbroek, “Dynamic
behaviour of semiconductor lasers,” Electron. Lett., vol. 11, pp.
206-208, May 1975.
code modulation of semiconductor lasers,’’ IEEE J. Quantum
Electron., vol. QE-12, pp. 657-660, Nov. 1976.
which results in improved laser performance at elevated temperatures.
Efficient 2.5 percent, low-threshold (10 J) operation has been obtained
with xenon-flashlamp excitation of the 6 mm diameter X 76 mm length
laser rods. Output pulses of greater than 5 J and average power outputs
of 35 W have been demonstrated, limited by the available power supply.
The emission is strongIy polarized E ( l b , with a gain that is 10 times that
in the alternate polarization.
The 262 ps, room-temperature fluorescence lifetime permits effective
energy storage and @switched operation. Tunable Q-switched pulses as
large as 500 mJ have been obtained with pulsewidths ranging between
33 and 200 ns depending on the laser gain.
Laser action has also been demonstrated on the high-gain (3 X
cm2 emission cross section) R line at 680.4 nm and is also polarized
Ellb. This three-level mode is analogous to the lasing in ruby except
that the stimulated emission cross section in alexandrite is ten times
larger than for ruby.
WALLING et al.: TUNABLE ALEXANDRITE LASERS 1303

INTRODUCTION characteristics, physical properties of the host crystal, and

LEXANDRITE [I] , chromium-dopedchrysoberyl, is spectroscopicproperties Of the doped crystal* The follo*g
A the third material after ruby ~ 2 1and Cr :YAG [31
in which the Cr3+ ion has been reported to lase [4] - [6] . In
sections will show both that high quality crystals ofalexandrite
can be produced and that the physical properties of these are
as good as or better than most other laser crystals. Because
alexandrite, however, the laser action occurs not only on the
of the very different and unique nature of the spectroscopic
R-line, as in the former two materials, but also in the vibronic
properties of alexandrite, efforts have beenmade to relate
sideband where the lasing is four-level and is broadly tunable.
these to the laser properties. Even though there are no other
Similar performance has also been reported in othersolid-state
laser materials directly commensurate with alexandrite, com-
laser materials [7] such as Ni :MgF2 [8] , Co2+:MgFzand
parison of the performancewith that of otherwell-known
Co2+:ZnF2 [9], and V2+:MgF2 [lo] . Alexandrite is the first,
lasers is difficult to avoid. The main feature ofthe alexandrite
however, to operate at room temperature and with improved
laser is its tunability. The theory of tunable phonon-terminated
performance with increasing temperatures up to about400 K.
lasers (vibronic lasers) was developed by McCumber [22] and
The full complement of alexandrite laser capabilities is ex-
is used asa basis for analysis of the alexandrite laser properties.
tensive and Suggests that this material may become important
Specifically, an effective stimulated emission cross section is
over a wide .range of applications. For example, the material
~ . ... .
defined that can be used for direct comparison of alexandrite
1) c& be continuously tuned from 700 to 818 nm,2) can be
withwell-known laser crystals and glasses. Thepeak cross
Q-switched, 3) has a low threshold and high slope efficiency
section in the tunable region of the alexandrite laser is on the
roughly comparable to Nd :YAG, 4) is mechanically strong
orderof
cm2 at roomtemperature
and increases with
and chemically stable, 5 ) has a high average power capability
temperature.
based on a thermal conductivity between that of YAG and
The fluorescent lifetime of the alexandrite emission is also
sapphire, 6) actually performs better with increasing tempera-
ture, and7) can be grown by amodified Czochralski technique.comparable to that of other laser crystals so that energy stor-
age forQ-switchedoperation is accordingly possible. The
Alexandrite, like ruby, is a naturally found gem for which
early spectroscopic data can be found [l 11- [14] . Laser op-
tunable wavelengthregioncovered byalexandritehas pre-
viously been covered only by dye lasers. However, dye lasers
erationoftheR-line in alexandrite was first suggested by
are characterizedby highemissioncross sections andshort
Farrell and Fang [15] whoproduced fluxgrown material
anddid detailed structural analysis of it. Growthof large fluorescent lifetimes which prevent Q-switched operation.
single crystals by the Czochralski method made possible the In addition to the four-level tunablemodeofoperation,
alexandrite also lases on one of the R-lines in a manner di-
first lasing of alexandrite in 1974 [16] . It was subsequently
rectly analogous to that of ruby [23], [24] . These no-phonon
discovered in 1977 (Jenssen and Walling) that lasipg occurs in
the dbronic sideband as well as the expected strong R-line fluorescent lines are narrow and occur at the exact equivalent
emission. of the energy difference between the initial and final purely
vibr&ic lasers derive their gain from transitions between electronic states of the ion. Because the terminal level of these
coupled vibrational and electronic states, where there is a R-line fluorescence transitions is the ground state, the associ-
changein both the electronic and vibrational quantum num- ated laser action is three-level and exhibits a characteristically
bers. In other words, phonons are either emitted or absorbed high threshold. However, the peak 680.4 nmR-line stimulated
concurrent with theelectronic transition. emission cross section is 3 X 10-19cm2 at room temperature,
Vibronic
room-temperature laser operation had previously which is ten times higher than the Cross
not been observed in any transition metal ion doped crystal. section in ruby. This large emission cross section may be used
Weber and varitimOs [I71 reported the first, thou& unsuc- to an advantage in certain applications; for example, it will
cessful, attempt to cr3+ v i b r o i c d y lase in y 4 0 3 .
permit single .pass extraction of the stored energy as required
Nelson and Sturge [I81 speculated on the possibility of vi- in high-magni'fication resonators [251
bronic lasing inruby as early as 1965. Moulton,Mooradian,PROPERTIES OF THE CHRYSOBERYL HOST
and Reed [19] have recently revived the MgF2 :Ni2+ vibronic Chrysoberyl, a member of the olivine family of crystals, has
laser by CW YAG:Nd3+ laser pumping. These authors report a unit cell with four formula units BeA1204 in an orthorhom-
37 percent power conversion efficiency yet find that cryogenic bic structure of space group Pnma [l ] , [26] . The unit cell
temperatures are required aspreviously reported for pulsed dimensions are a = 0.9404 nm, b =.0.5476 nm, and = 0.4425
flashlamp-pumpedlasingthis
in material. nm the
in terminology of the Pnma space group [27]. Two
Room-temperature phononassisted laser operation has been crystallographically inequivalent M 3 octahedrally coordinated +

observed inHo3+:BaY2F8 [20l and Ho3+:LiYF4 [211; sites exist; onewithmirror C, andonewithinversion Ci site
however,these are tunableonly over a smallregion and are symmetry. It is on these sites that Cr3+ is substituted.The
in nature different from the transition metal ion lasers. The total density of octahedral sites (A3+sites) is 3.509 X
transitions in these crystals are vibronic innature and are ~ m - ~ .
greatly amplified by nearlyresonantelectronic transitions. Thephysical properties ofchrysoberyl relevant toits appli-
The suitability of a crystal as a laser gain medium depends cation as an optically pumped laser host material are summa-
.onmany factors. Thesecanbe divided into crystal growth rized in Table I. The relatively highstrengthandthermal
'

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1304 IEEE JOURNAL O F QUANTUM ELECTRONICS, VOL. QE-16, NO. 12, DECEMBER 1980

TABLE I TABLE I1
PHYSICAL
PROPERTIES
OF BeAlzO4 REFRACTIVE
INDEXES
FOR BeA1204

MeltingPoint T 1870OC
(nm) n
a 1
I
"b "c

250) 1.8175 1.8231 1.8127

Density 3.69g/cm3 275) 1.8056 1.7960
1.7994
300) 1.7931 1.7838
1.7870
V i c k e r sH a r d n e s sH V ( 2 0 0 q load) 2 0 0 0 kg/mm2 350) 1.7705 1.7765 1.7678
400) 1.7603 1.7661 1.7579
450) 1.7534 1.7592 1.7512
T h e r m a lC o n d ~ c t i v i t y ( ~ * ) 0 . 2 3 W/cm-K* 500) 1.7486 1.7544 1.7466

T h e r mE
a lx p a n s i o' 3n 9 ) IIa - S X ~ O - ~ ~ C - ~ 600) 1.7478 1.7401
1.7422
700) 1.7436 1.7361
1.7381
N e a r room t e m p e r a t u r e 11 b - 6 ~ 1 0 - ~ 800 1 1.7352 1.7406 1.7331
IIc - ?x~O-~
900) 1.7328 1.7383 1.7309
1000) 1.7362 1.7289
1.7309
Y o u n q sM o d u l u s 0.469 x lo1' Pa** 1200) 1.7272 1.7326 1.7252
1400) 1.7240 1.7290 1.7218
B r e a k i n gS t r e s s 4.57 - 9.48 x Pa*** 1600
1800)
1.7206 1.7255
1.7224
1.7186
1.7149
1.7170
2000) 1.7183 1.7105
1.7131
N o n l i n e a rr e f r a c t i o ni n d e x 2.0 % 0.3 x m2/W**** 2200) 1.7137 1.7059
1.7089
2400) 1.7090 1.7006
1.7041
coefficient, '30) 2600 1.7036 1.6953
1.6991

T h e r m a cl o n d u c t i v i t y of a l e x a n d r i t e a t 1 a t . % Cr3+ is
r o u g h l y1 0 % less.

** B a s e do nu l t r a s o n i cs p e e do fs o u n dm e a s u r e m e n t s at
A l l i e dC h e m i c a lC o r p o r a t i o n by M i c h a e lD u t o i t ,u n p u b l i s h e d .

*** B a s e do np r e l i m i n a r yr e s u l t so f a 3 - p o i n tb e n d i n g test
p e r f o r m e d a t A l l i e dC h e m i c a lC o r p o r a t i o n .T h ev a r i a t i o n
i s t h er e s u l to ft h ec o n d i t i o n of t h es a m p l es u r f a c e .
* * * * T h i sv a l u e is e q u i v a l e n t to a n o n l i n e a rr e f r a c t i v ei n d e x ,n 2 ,
e x p r e s s eGi nda u s s i au nn i t s of 0 . 8 3 x esu.

conductivity of this host, combined with the moderate and

relatively isotropic thermal expansion coefficients, allow it
to withstand high-energy optical pumping, both pulsed and
CW, withoutfracture.The absorbed power loading, Pa per 500 1000 1500 2000 2500
Wavelength [ nm t
unit rod length L , that a laser rod can withstandwithout
Fig. 1. Refractive index of chrysoberyl versus wavelength: a, b, and c
fracture is given by the expression [28] refer t o the polarization of the electric vector E with respect to the
8nKumax(1 - V)
crystal axes.
Pa/L=
&G-
tion although this effect may reflect material quality rather
where Kis thethermal conductivity, umaxis the tensile strength, than anintrinsic property.
v is Poisson's ratio, CY is the thermal expansion coefficient , and
E is Young's modulus. By using typical values for these param- CRYSTAL GROWTHAND QUALITY
eters for the materials ruby, alexandrite, andYAG, the resulting The growth of large, high optical quality alexandrite crystals
heat loading at fracture is 1000,600, and 120 W/cm, respec- has been achieved by the Czochralski process. Iridium cru-
tively. The thermal conductivity of alexandrite is approxi- cibles, zirconia ceramic furnaces, and Nz-O2 atmospheres are
mately one-half that of sapphire but twice that reported for used. The best optical quality cIjrstals obtained to date have
YAG. been [OOl] oriented blades measuring about 1 cm X 2 cm in
Because of the orthorhombic symmetry of alexandrite, the cross section and 10 to 20cm in length with Cr3+ substitutions
crystal is optically biaxial with the principal axes of the index of up to 0.3 atm percent (of A 1 3 + sites). Crystals of relatively
ellipsoid along the crystallographic axes. The refractive in- good optical quality have been produced that contain up to
dexes were measured by the method of Bond [29] for the 0.4 atm percent Cr3+ and measure 5 cm in diameter by 5 cm
wavelength region 0.25-2.5 pm (see Table I1 and Fig. 1). long.
The nonlinear refractive index coefficient y which governs Optical defects which have been identified in these crystals
self-focusing at extreme power levels has been found to be and which have now been largely eliminated orcontrolled
2 f 0.3 X mz/W [30] which is lower than in either include iridium inclusions, dielectric inclusions (voids), and
sapphire or YAG. refractive index inhomogeneities. We haveobserved inser-
Preliminary studies of thesurface damage threshold,in which tion losses as low as 0.003 cm-' as determined from laser
-
0.05atm percentCr3+rubyand 0.08 atmpercent Cr3+ performance bythemethodof Findlay and Clay [31] in a
alexandrite were irradiated with focused 750 nmradiation, 0.12 atm percent Cr3+ rod measuring 6.35 mm X 76.2 mm.
have shown that alexandrite is at least as resistant to optical This same rod exhibited a totalwavefront distortion (Twyman-
damage asis ruby.Furthermore,the damage threshold in Green, 632.8 nm) of 2-3 fringes. Other rods of this size have
alexandrite appears to vary inversely with the Cr3+concentra- exhibited wavefront distortions ofless than one fringe.

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WALLING et al.: TUNABLE ALEXANDRITE LASERS 1305

SPECTROSCOPY OF ALEXANDRITE 1
The spectroscopic features of Cr3+ in alexandrite are quali-
tatively similar to those of octahedrally coordinated Cr3+ in
otheroxidehosts,including A 1 2 0 3 [2] and YA103 [17], in
that they all have the two, well defined 4A f, 2E R-lines and
the broad-band T , T absorptionbands.Thestrengthand
relative position of these transitions vary from host to host
however. In general, if the Cr3+ site possesses inversion sym-
metry, parity forbids electric dipole transitions between
states of the d3 configuration. As a consequence, a Cr3* ion
that resides on an inversion site,such as in YA103, hasa
weak magnetic-dipole no-phonon transition. Phonon assisted
transitions or vibronicstend also to be weaker inthis case than 1 2 000 13 000 11000 15 000 16000
Wave Numher(cm-')
when the Cr3+ ion is in a noninversion symmetry site such as
in A 1 2 0 3 . (For example, the fluorescence lifetime of Cr3+ in Fig. 2. Alexandrite Cr3+-fluorescencespectra at 300 K: the fluorescence
intensity is the average intensity in photons per second per unit wave-
YA103 at 4 K is 54 ms [17] , compared to 3.7 ms for Cr3+ in number interval per unit solid angle about any direction in the plane
A12°3 [181 *) perpendicular to the specified polarization direction. [In the text,f*
Alexandrite, on the other hand,has both inversion andnon- is defined per unit energy rather than wavenumber interval. In order
to convert to the text definition, the values of this curve must be mul-
inversion (mirror) sites present for Cr3+. At a low temperature, tiplied by (kc)-' .] In this normalization, it is assumed that the emis-
it is possible to excite selectively the R l-lineemission for each sion is entirely electric dipole. SV and ASV refer to theR 1 line single
of the two sites. With pulsed excitation, the fluorescence life- phonon Stokes and anti-Stokes nbronics, respectively; T1, T2,and
T3 are the members of the 2T1 -+4A2 transition. Excitation by 1p s
time for the two sites was measured to be 1.32 and -60 ms, laser pulses at 597 nm. Sample contains 1.5 X 1019 Cr3+ ions/cm3.
respectively, for the mirror and inversion sites at 4 K. The
stronglyabsorbingand fluorescing mirror site dominatesin
alexandrite fluorescence to the point that at room tempera-
turethe inversion-site ,spectral features are completely ob-
scured. The inversion-site no-phonon lines (or R-lines) fall
at 689.3 and 695.0 nm at 77 K. Because inversion-site Cr3+
ions play only a minor role in the alexandrite laser, except
perhaps at higher Cr3+concentrationsthan are currently
being employed, a discussion of the inversion-site spectros-
copy will not bepresented at this time,
The alexandrite fluorescence spectra at 300 K are shown
in Fig. 2.Thefluorescenceinone polarization, Ellb, is an
order of magnitude stronger than the fluorescence in the other
two polarizations and establishes the polarization of vibronic
laser emission. The room-temperature absorption spectra are
shown in Fig. 3 for all three polarizations and are the same as
that reported by other workers [ 131, [ 141. It is seen that the Wavelength (nm)
absorption effectively blankets the entire visible region of the Fig. 3. Alexandrite absorption spectra: the absorption coefficient is
spectrum. naperian. A Cary spectrophotometer Model 118CX was used (reso-
lution 2.0 nm) except for the R-line region which was resolved with a
The features of the spectroscopic data can be identified in 1m Czerny-Turner spectrometer.
reference to the theory of Tanabe and Sugano [32] and the
extensiveCr3+literature [33] . The electronic energy level 25
T, (VtbratlonalBand)
structureofthe alexandrite mirror-site Cr3+ion so derived
appears in Fig. 4. The broad levels are the strong vibrational
sidebands of the 4A2 +- 4T2 and 4A2 + 4T1 transitions. The
energy and degeneracy of these levels are given in Table 111.
Higherlevels exist but are omitted for simplicity. The R1,
and R z m lines (where the m refers to the mirror site) each
appear at precisely the same wavelength, 680.4 and 678.5 n m ,
respectively, in both absorption and fluorescence at room tem-
perature. These lines are the no-phonon transitions between
the 'E-orbital doublet and the 4A2-orbitalsinglet ground level.
Vibrational sideband fluorescence associated with these tran-
sitions appears in Fig. 2 as superstructure upon a broad back-
Fig. 4. Energy level diagram of Cr3+in chrysoberyl; broad bands are the
ground fluorescence. Stokes sidebands of 4Az -+ e T z , 4T1) transitions as indicated. The
The l i e s associated withno-phonon 'T1 4A2 transi- ff vibronic transitions associated with lasing are not indicated.

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1306 IEEE JOURNAL OF QUANTUM ELECTRONICS, VOL. QE-16, NO. 12, DECEMBER 1980

TABLE I11
ENERGY
OF ELECTRONIC LEVELS INVOLVED GAIN
IN VIBRONIC

Transition Transition L e v e lo c c u p a t i o n
Designation Wavelength Ener y probability
Spin ( w i t hg r o u n d ( i n a i r ) nm .*-1 of e x c i t e di o n
M u l t i p lDe te g e n e r a c y level) 300 K 375 K 300 K 375 K 300 K 375 K,
23 2 6 8618. 50 . 4 71041 61748 0 . 4 60 0. 500 0 6
2 6 7697. 38 . 3 71447 71244 0 . 3 80 2. 410 1 5

655.3 656.2 15 264 15 243

2T1 2
2 3 649.3 650.2t 15 405 15 384t
0.0336
0.0171
0.0472
0.0267
2
4 645.2 646.1t 15 503 15 482t 0.0107 0.0180

4 ~ 2 4 647.2t 648.7t 1455 51t5 420t 0.0269 0.0462

4 638.lt 639.6t 1657 51t5 640t 0.0094 0.0191
4 604.2t 605.5t 1565 51t6 520t 0.0001 0.0005

4 ~ 2 4 0.0 0.0 0.0 0.0

E* - - 682.7 680.3 67150413

t E x t r a p o l a t e d estimates

I I I I
tions are indicated in Fig. 2 , labeled TI , T 2 ,and T3 for the
2.00 t i
655.7, 649.3, and 645.2 nm lines, respectively (at room tem-
..._.....'
... . . .
perature). No fluorescencesidebandstructure clearly asso-
1.00 -
ciated with the 'T1 tf 4A2 transition has so far been identi-
fied. The dominant no-phonon line in Ellb of the 4T2 * 4A2
transition Ti is not resolved at room temperature but has been 0.50 - ..... Data
- Theory using 2 level
identified from low temperature data where it appears in both model
-
emission andabsorption.The Tk and Ti 4A2 transitions ff
E

have not been unambiguouslyidentified. The reason for thisis

that these transitions fall at wavelengths in absorption where I
\ i
I
vibronic lines of comparable intensity and width also occur
and because the T; and Ti levels are too high above the meta-
stable level to beseen influorescence at temperatureslow
enough for good resolution. Table I11gives energies for these
two transitions which are the best estimate that can be made TEMPERATURE lK)

from the spectroscopic data at the present time. In particular,
the energies of Ti and T J are subject to interpretive error in
the identification of spectral features. The 590 nm absorption
band (see Fig. 3) is the vibrational sideband component of the
4A2 -+ 4T2 transitions. The counterpart of this band in fluo-
rescence, Stokes shifted to a nearly symmetrical position on
the long wavelength side, is identified with the broad back-
ground fluorescence of Fig. 2. This identification is substan-
tiated by low temperature fluorescence data where the broad
background fluorescence is not present. This fluorescence is
responsible forthebulkofthetunablevibronic laser gain.
Because eachexcited active ionoperatesindependentlyand
provides equivalent gain at alI operating wavelengths, thelaser
gain is homogeneously broadened.
The large reduction in the Ella and Ellc vibronic emission
can be understood by reference to the absorption data (see
Fig. 2) where the 4A2 tf 4T2 vibronicbands are shifted to
higher energies for Ella and Ellc compared to Ejlb. This
shift implies that the transition from 4A2 to a higher energy
member of the 4T2 triplet, presumably T i , is dominantin
Ella and Ellc. The reduced vibronic emission in these polari-
zations is partlythe resu.ltof aweakervibronictransition
strength, as seen in the relative amplitude of the lower energy
band in Fig. 2, and partly becauseof the lower probability for
Fig. 5. Intrinsic fluorescence lifetime of Cr3+ in chrysoberyl: lifetime is
inferred from the integrated decay half-time; accuracy is +3 percent;
excitation was achieved with 597 nm laser radiation;Cr3* concentra-
tion is estimated to be <0.005 atm * percent.
occupation of Ti ,in the excited ion, due to the higher energy
of T i .
The lifetime of alexandrite mirror-site Cr3+ ions as a func-
tion of temperature (see Fig. 5) was obtained from a sample
-
with less than 0.005 atm percent Cr3+ by exciting (with a
dye laser tuned to 590 nm) a smillvolume of material. There-
fore, this lifetime shouldaccuratelyrepresent the value for
isolated ions. The rise in lifetime with increasing temperature
between 4 and 70 K is caused by thermal excitation in excited
ions from the lower zE to the longer lifetime upper 2E level.
This longer lifetime is anticipated from the relative strengths
of R, and R z in Fig. 6 . The reduction in thefluorescent life-
time with temperaturesgreater than 70 K is due to thethermal
excitation of the higher lying triplet levels. Analysis of the
oscillator strength of the 4A2+ 4A2 transition yields a value
of approximately 10 ps for the 4T2 intrinsic lifetime. The ' T I
levels have an arbitrarily long intrinsic lifetime by comparison,
based on theobservedlow oscillator strengths of the 2T1cf 4A2
transitions in both absorption and emission. Relatively weak

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WALLING e t al.: TUNABLE ALEXANDRITE LASERS 1307

I
N TABLE IV
-i5 SECTIONS
CROSS
ABSORPTION
&LINE
MIRROR-SITE AT 300 K
.-.
-
0

s
i-
1.0-
~ l l a E Ilb E I1 c
m
R1 Peak (cm21 9.4 x 1.46 x 1 0 - l ~ 3 . 4 x 10-21
e
0 Integrated (cm) 1.2 x 2.65 x 10-l' 4.7 x
c
i-
E Peak R2 (cm2) 2.1 x 5.2 x 3.1 x
UI
a Integrated (cm) 2.6 x 5.2 x 3.8 x 1O-l'
a

682 683
*The E 1 1 a spectra show a significant dependence on Hthe
vector
Wavelength(nm) orientation.
for
are
These
data H I I b.

Fig. 6. Alexandritemirror-site Cr3+ R-lineabsorptioncross section:

instrumental resolution is0.02 nm. The crosssection is evaluated from
data on that 2.2 x 1019 Cr3+ ions/cm3 of
which 53 percent are assumed to be on mirror sites. The absolute ac-
curacy of the E 11 a spectra is about 25 Percent; the E 11 b and E 11 C
data are accurate to within 15 percent. The Ella data depend on H
vector
orientation, in case
this Hllb.
zT1 ,+4~~ transitions to 4T2 .++ 4 ~
are~ also
ported for Cr :YA103 [171 and ruby [ 181 .
menthe cr3+concentration is increased, fifetime mea-
surementbecomescomplicatedby radiative trapping
stretches the observed lifetime. The lifetime isalso expected
to increase with concentration because of inversion-site trap-
ping: theexcitation transfer betweenmirror-andinversion-site
metastable levelsis facilitated by the proximity of mirror- to
inversion-site cr3+ ions. The inversion-site metastable level
is lower than that of the mirror-site and the radiative lifetime
is longer. These sites, therefore, serve as excitation traps with
an activation energy that corresponds to approximately 100 K,
as determined from selective excitation measurements. At still
higher concentrations in excess of 1 atm *percent Cr3+,pairs,
triplets, andhigherorder clusters appear in concentrations
sufficient to alter significantly the spectroscopic properties of
the crystal.
In order to compute the absorption cross section from the
absorbance data, it is necessary to ascertain not only the total
Cr3+ ion concentration but also the mirror- to inversion-site
Cr3+ occupancy ratio. For Cr3+ concentrations ranging from
20 to 50 percent by weight in flux growncrystals, the site par-
titioning has been reported to be 0.74 in favor of the mirror
site [34]. No publisheddata exist forCr3+concentrations
of a fraction of 1 percent in Czochralski grown alexandrite
crystals however. Nelson andSturge [18] employed the
Ladenburg formula, which relates integrated absorption cross
section to lifetime by means of the Einstein detailed balance
relations between absorption, stimulated emission, and fluo-
rescence, to evaluate the radiative lifetime of ' E in ruby and
obtained 10 percentagreementwith the measured lifetime.
We have employed the same technique in alexandrite at 77 K
where the quantum yield is expected to be 100 percent, and
have obtained -53 percentoccupancy ofavailable Cr3+ on
the mirror site foraCzochralskisamplewhichcontained
*
0.083 0.002 atm * percent Cr3+. This result is in significant
conflict with the 0.74 figure reported above. Work is currently
underway to resolve this discrepancy.The data reported in
this paper reflect the use of 0.53 for the occupancy ratio.
With the site distribution coefficient forCr3+ tentatively
established, the absorptioncross sections can be obtained from
absorbancedata provided the absorbancecan be unambigu-
ously attributed to one site or the other. the absorbance due
to theR , fines can be accurately identified and these dataare
given in Fig. 6 and
Table IV. TheR-line absorbanceFig.of 6,
which indicates that the Ellb component of R1, is strongly
) re-
dominant,doesnotincludethe 10 percentbackgroundcom-
ponent since the source of this absorbance has not been posi-
tively identified. The emissioncross section for each of the
alexandrite R-lines is twice the corresponding absorption cross
section based On the 'pin degeneracies Of the and 4 A 2
states. The room-temperature stimulated emission cross section
is, therefore, approximately 2.9 x cm2 which is about
lo times that Of ruby and that Of YAG:Nd3+ [28].
Theabsorption spectra shownin Fig. 3 are believed to arise
mostly from absorption due to the mirror sites because of the
parity consideration discussed earlier. However, this question
has not been resolved by experiment as yet. Therefore, the
ordinate in Fig. 3 has not been converted into cross-section
units. Under the assumption that the absorption by the in-
version site is insignificant, the absorption cross section for
the 590 nm peak with Ellb is 2.6 X lo-'' cm2 ,based on the
53 percent chromium occupancy of the mirror site computed
from measurements.
THEORY OF VIBRONIC LASEROPERATION
The principle theoretical work expressly devotedto vibronic
(phononterminated) laser operation is by McCumber [22]
and is again based on the Einstein detailed balance relations.
In the alexandrite case, a special adaptation of the McCumber
theory may be made. Multiple,well-separated upper electronic
levels contribute to the vibronic laser gain in alexandrite. The
lower electronic level 4A2 is a fourfold multiplet that is un-
resolved at room temperature. Involved in the vibronic tran-
sition, therefore, are a set of upper electronic states j and a
set of lower states i, the latter of which are essentially degen-
erate in energy. The i index runs from 1-4 and the j index
runs from 1-22 in order to span the ' E , 'TI , and 4T2 multi-
plets (see Table 111).
The laser gain per unit length g h ( f t , E ) , for radiation with
energy E , unit wave vector E , and polarization A, is gven in
the McCumber theory by

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1308 JOURNAL
IEEE
occupy the specific state (similarly for Ni), pji is the chemical
potential difference between the lower and the upper states,
and hpji is the net free energy required for a no-phonon exci-
tation from the ith to the jth state, n(E, E ) is the index of
refraction, k is Boltzmann's constant, and T is temperature.
The function f,(fi, E)ji is the rate that photons of polariza-
tion X are emitted in a unit solid angle about k^, per unit en-
ergy about E, as a result of an electronic state change from j
to i. Both vibronic andno-phonon transitions are included
in this function. In this analysis, the assumption is made that
h p ji = Eji, the no-phonon transition energy. This assumption
is not a requirement for the theoretical analysis but is required
in order to use the theory to interpret the experimental results.
The accuracy of this assumption is expected to be high in the
alexandrite case. However, the required detailed analysis
will be deferred to a subsequent work. The transition rate
f,(ff, E)ji is related to the stimulated cross section o,& E)ii:
In the event that the jth states are in quasi-thermodynamic
equilibrium with one anotherand the ground states areall
degenerate, it is possible to derive a simpler expression for
g k . Under these assumptions, the population of the jth state
is given by
N* exp (-Ejg/kT)
Ni =
Z j exp (-EjglkT) .
Here, N * is thetotalconcentration of excited-stateions
and i = g for all j (based on the assumption of ground-state
degeneracy).
The assumption that the 4A2 multiplet is degenerate is not
strictly true. However, because the 4A2 energy splitting in the
mirror site Cr3+ is onIy 0.54 cm-' , the assumption is opera-
tionally accurate. The assumption ofthermodynamic equi-
librium has been verified for ruby [35] where the nonradiative
relaxation rate between the 4T2 and ' E states was found to be
on the order of 1013 s-'.
By carrying outthe summations indicated in (2) and by
letting N be the total ion concentration, the gain assumes the
simplified form
, ) = [N* - (N - N * ) exp [(E- E*)/kT]] . a:!($, E).
g k ( f fE
Inthisequation, o z ~ ( $ , E )is the effective emission cross
section
E * is an effective no-phonon level
exp (-Ejg/kT)- In y
where y is the ground-state degeneracy (in this case y = 4), and
finally,
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OF QUANTUM
ELECTRONICS, VOL.NO.
QE-16, 12, DECEMBER 1980
where the right-hand side represents thesummation of the
fluorescence rate between individual electronic levels (and the
associated individual vibronic sidebands) weighted according
to the Boltzmann occupation probability function. f z ( $ , E )
is therefore the total emission rate.
The measured fluorescence spectrum is proportional to
fz(fi7 E ) and theproportionalityfactor canbe determined
from the radiative lifetime r by the relation
(9)
where E' is perpendicular to the X component of the electric
vector. In this calculation, 100 percent quantum yield ( Q Y )
is assumed. This expression, as written, is valid for pure elec-
tric dipole emission, which we haveobserved to be strongly
dominant in the alexandrite room-temperature vibronic spec-
trum. A precise analysis would also include the magnetic
dipole emission. Magnetic dipole emission has been observed
in the Ella and Ellc polarizations where the shape of the
fluorescence spectra does depend moderately on the orienta-
tionofthe magnetic vector of the emission. However, the
emission strength in these polarizations is already down by an
order of magnitude from Ell b emission which shows no sig-
nificant change in shape with magnetic vector orientation.
For these reasons and to simplify the analysis, the assumption
of pure electric dipole emission is made. It is important to
note that f:(k, E) is defined per unit energy interval rather
than per unit wavenumber interval as is the case in Fig. 2.
By performing the computation indicated in (6), using the
data for R,, Ell b (see Fig. 2) divided by the fractional occu-
pancy of R 1 , from Table II170.5006, one obtains the peak
R , , emissioncross section of 2.3 X cm2. This value
compares fairly well with 2.9 X cm2computed earlier
fromtheroom-temperatureabsorption cross-section data
(oe = 20,). It is likely that a good part of the difference is
caused by self-absorption of the R line in fluorescence which
reduces its relative intensity. The Ellc R 2 , line isweak by
comparison and is not as much affected by self absorption in
fluorescence. For this line, the peak absorption cross section,
when computed from the fluorescence and absorptiondata,
respectively, is 6.3 X lo-'' cm2and 6.4 X lo-'' cm2. We
conclude that these results are equal within the estimated
10 percent experimental error. Because these absorption
(5) cross-section data arederived fromtheCr3+ site selectivity
fraction, evaluated at 77 K, again under the 100 percent QY
assumption, the agreement between thetwo emission cross-
section computations implies thatthe QY does not change
significantly between 77 and 300 K. This factfurthersup-
ports the 100 percent QY assumption.
The function E" depends on temperature and has the value
of 14 701 cm-' (680.4 nm in air) at 300 K and 14 657.5 cm-'
(7) (682.4 nm in air) at 375 K,computed from thevalues in Table
111. In the context of the vibronic laser model, the function
E* is the effective no-phonon level. However, in a more gen-
eral interpretation, valid for three-level operation as well, E*
provides the coefficient that expresses the degeneracies and
occupancy ratios among levels. For example, in ruby or
alexandrite at 4 K, only the lower ' E level with a degeneracy
WALLING et ai.: TUNABLE ALEXANDRITE LASERS 1309

6.6psLMrne
-. lnttial Level 1 4 1 MULTIPLETI
~

--(Lasing Transltion)

5k oo'-y--- 50 ' ' '

too 150 200
z Temperature('C)

Fig. 7. Temperature dependence of the effective-emissioncross section

[defiied by (6)] : the pointsindicatecalculationsperformed on
experimentally
measuredspectra. Solid lines arestraight line
Wavelength (nm)
approximations. 700800 750 650

Wavelength (nm)
750 700 650

.e
4 001

ti
J 0.001

0.0001
i
13000 14000 15000

Wave Number(cm.1)
Fig. 10. Alexandrite laser gain computed from (4): p'is the excitation
level N*/N. Solid lines are for 25" C; dashed lines are for 75"C.

Wave Number (cm-l)

The increase in effective emission cross section and, hence,
the laser gain with temperature, is caused by a thermally in-
Fig. 8. Effective stimulatedcross section versustemperatureand
wavelength. duced increase in the occupation probability of the 4T2levels
compared to that of lower lying metastable 2E levels. Since
of two is occupiedin the excited ion. Because the ground these upper states provide the major contribution to the vi-
leveldegeneracyis four, the threshold for three-level lasing bronic laser gain, a strong, positive temperature dependence
occurs when onlyone-third of the ions are excited. The of gainoccurs.
parameter E* accounts for this phenomenon more generally Onesimple model which illustrates this phenomenon is
as a function of temperature, with 4T2and 2T1 occupancy shown in Fig. 9. This model has been simplified t o the point
considered as well. that only the essential factors that are needed to demonstrate
The above relations allowthe laser gain tobecomputed the temperature dependent gain are given. The terminal level
from the measured values of fluorescence lifetime, quantum refers to a vibronic state in which the vibrational component
yield, and electronic energy levels. It is not necessary, there- has been increased as a result of the transition; this increase
fore, to know how much eachelectronic transition contributes represents adisplacementfromthermodynamicequilibrium
to vibronic lasing or the number of vibrational quanta emitted in thelattice. Thisdisplacementthen relaxes withatime
in order to calculate the laser gain. (It should be pointed out constant that is subnanosecond [ 2 2 ] , thus reestablishing the
that the expression E * is very insensitive to the energies of Ti ground level. A close fittothe lifetime dataof Fig. 5 is
and T; which are in question, and, in fact,if Ti were to have achieved with this model where the energy gap between the
the same value as Ti (a change of 880 cm-I), then E* would initial and storage level is 800 cm-' and the initial andstorage
differ only by about 2 cm-l .) The effective emissioncross lifetimes are 6.6 ,xs and 1.54 ms, respectively. It is interesting
section in the-vibronic.modeis presented in Figs. 7 and 8 as to compare these parameterswith the 10 ps calculated life-
a function of temperature. This cross section has been com- time of 4T2and the energy gap between the respective lowest
puted by use of (8) from the lifetime data (seeFig. 5) and member of the 4T2 and 2E multiplets which is 754 cm-' at
from fluorescence data, analogous t o that in Fig. 2, obtained 300 K.
-
from a 0.1 atm percent Cr3* sample. The error in the emis- The intrinsic laser gain [see ( 5 ) ] has been plotted in Fig. 10
sion cross sectionfor this particular set of data may beas for several values of p+ = N * / ! . Excluded from this computa-
much as 10 percent because of the influence of the radiation tion are losses attributed to sources other than ground-state
trapping. The temperature dependence of the effective emis- vibronicabsorption,such as excited-stateabsorptionand
sion cross section is explicitly presented in Fig. 7 fortwo scattering losseswhich may be present. An increase in the
wavelengths 750 and 780 nm over the range of 300 to 500 K. operating temperature causes the free-running (untuned) laser

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1310 IEEEJOURNAL OF QUANTUMELECTRONICS, VOL. QE-16, NO. 12, DECEMBER 1980

Time (rs)
Fig. 12. Waveform of electric current being deliveredto flashlamp.

Fig. 11. Laser system schematic.

wavelength, which occurs at the gain peak, to shift to the red

as Fig. 10 illustrates. There are three contributions to the red
shift. One is the increased optical phononpopulation with
temperature which reduces the effective population inversion
at the shorter wavelength; this is manifest in the explicit tem-
perature dependence of (5). A second contribution is the shift
of the no-phononlines with temperature andthe enhancement
Lamp Input Enerqy IJ)
of the long wavelength vibronics. Finally, a third contribution
is the reduction with temperature of the required excitation Fig. 13. Laserperformanceversusoutputcouplingforrod B (6.3
mm X 76 mm, 0.12 atm . percentCr3+):theoutput mirror reflec-
level required to reach threshold that is the result of the fact tivity and slopeefficiency are shown. Flashdurationis 250 ps.
thatthe laser gain has increased. The consequence of this Temperature is 22°C.
reduction in the threshold excitation level is the increased
ground-stateconcentrationand associated increased ground- pedances. The maximum energy discharge during a pulse of a
state absorption which shifts the laser gain curve to the red. specific width was flashlamp limited.For almost all of the
This latter kinetic effect, as wellas the no-phonon line red alexandrite laser experiments, a PFN witha capacitance of
shift, is accounted for in the function E *. 250 pF, maximum energy storage of 500 J, and FWHM dis-
The cross section for excited-stateabsorptionsubtracts charge time of 200 p s was used. The current waveform is dis-
from the stimulated emission cross section. Thus, if the ab- played in Fig. 12. The circuit parameters were chosen to en-
sorption cross section equals or exceeds the emission cross sure that the discharge was slightly underdamped so that the
section, no gain can occur regardless of the excitation level. SCR would be turned off by the reverse current. The pulse
It is necessary, therefore, to determine the excited-state ab- repetition rate of the laser was limited by the 1.5 kW average-
sorption cross section in order to computethe laser gain power capability of the high voltage power supply.
correctly. This cross section can be inferred from the laser The laser rods used in this study were cored parallel to the
performance characteristics. boule axis from c-axis boules. Data are presented from two
rods with differing Cr3+ concentrations; 0.043 atm . percent
for rod A and 0.12 atm * percent for rod B. Rod A and rod B
VIBRONIC LASEROPERATION
displayed, respectively, 2 and 4 fringes on a Twyman-Green
The data on the laser operation of alexandrite were obtained interferometer. The rods were both 6.35 mm in diameter and
by using a flashlamp excitation apparatus. This apparatus is a had lengths of 76 mm (rod A ) and 96 mm (rod B). The ex-
direct adaptation of ruby laser technology with the added so- cited length of the rod was 70 mm in each case.
phistication ofa birefringent tuning element (see Fig. l l). The laser resonator employed in the measurements was ap-
The optical pumping cavity was a singlesilver plated ellipse proximately 30 cm in length and the mirrors were aligned par-
which focused the 6 mm ID by 76 mm long flashlamp onto the allel to theuncoated laser rod ends to minimize reflection
6.35 mm diameter by 76 mm long laser rod. To enhance the losses. A typical resonator was composed of one flat and one
focusing and simultaneously cool the components, the laser 4 m radius mirror.
head was filled with flowing cooling water. Even though the In the initial measurements, the Pockels cell and the bire-
closed cycle cooling water was doubly distilled and deionized, fringent filter were not present in the laser resonator. Under
the reflector required continued maintenance and repolishing. these conditions, the laser emission occurred over a 5 nm wave-
The flashlamp was excited with amultielement pulse forming length range centered around 750 nm. The performance with
network (PFN) with a maximum working voltage of 2 kV which respect to output mirror transmission is shown in Fig. 13 for
was limited by the high voltage, high-current SCR (Westing- rod B. The curvature in these performance curves indicates the
house T96H2208K3) used to switch theexcitation circuit. presence of nonuniform pumping such that only a small volume
The capacitance of thePFN could be varied from 100 to 500 pF. of the rod is lasing initially. As expected for a four-level laser,
The width of the current pulse could be set at values between thethreshold increases with output coupling. However, the
50 and 900 ps by appropriate choice of the PFN segment im- lower slope efficiency for the 85 percent mirror with respect

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WALLING et al.: TUNABLE ALEXANDRITE LASERS
1.0 , I
'.'} Rod A
0.8
0.7
0.4
0.3
0.2
0.1
0.0
0 20 40 60 80 100 120 140
Input Energy (J)
Fig. 14. Laserperformanceversustemperature for rod A (6 mm X
76 mm, 0.043 atm . percent Cr+3). At 73, 5 5 , and 22"C, the slope
efficiency is 0.86, 0.66, and 0.50 percent, respectively. Mirror reflec-
tivity is 93 percent. Flash duration is 200 ps.
o.61ROdB-------l
0.0 L suggest that a substantial improvement in performance with
0
Lamplnput Energy(J)
Fig. 15. Rod B (0.12 atm percent Cr33 performanceversustempera-
ture: the slope efficiency at 64°C is 1.5 percent;flashduration is
200 Ids.
to that for the 93 percent mirror is within measurement error
and is not significant. Also as expected, thelaser performance
improves with increasing temperature. As illustrated in Figs.
14 and 15, a decrease in threshold with increasing temperature
is evident. The decrease in the threshold is expected from the
higher gain at elevated temperature. The increase in slope effi-
ciency with temperature shown for rodA in Pig. 14 is not en-
tirely expected from theory and maybe due t o artifacts of the
experiment. However, part of the effect may be explained by
the fact that in the lower concentration material a significant
fraction of the active ions must be excited t o achieve laser
threshold. Thisrequirementreduces theconcentration of
ground-state ions available to absorb the excitation radiation.
A reduction inthe laser threshold dueto a temperature increase
will result in a higher ground-state occupancyat threshold and,
thereby, theabsorption by the rod and theslope efficiencywill
be improved. The thermal dependence of the slope efficiency
for rod B would be less from this effect because of its higher
concentration. The results for rod B in this respect are more
in keepingwith theoretical expectations.And, infact,the
slope efficiency for rod B remains within 5 percentof 1.4
percent value.
This 1.4 percent slope efficiency should be compared with
the value of 0.51 percent for ruby, 1.7 percent for YAG:Nd,
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1311
I 1
73oc.
/ i
".
0 20 40 60 00 100
Temperature ("C)
Fig. 16. Temperature dependence of output energy and threshoid for
rod B (0.12 atm * percent Cr3+): input energy is 50 J (data are de-
rived from Fig. 15).
160 180 200 and 2.75 percent for LazBe205 :Nd all found in systems com-
parable to the one used to test alexandrite [ 3 6 ] . It should be
noted that the 64°C data, if extrapolated past thelimit of the
energy detector, wouldsurpass 1 percent absolute efficiency at
approximately 0.6 J of output energy.
The substantially lower threshold of rod B , a factor of three
improved over rod A , can be accounted for by the improved
pump radiation absorption which is roughly proportional to
theCr3+concentration. These results strongly suggest that
substantial improvement in performance can be obtained with
further increase in Cr concentration.
The nearly linear improvement in performance with temper-
ature was achieved without reoptimization of output coupling
or flash duration for each temperatureabove 17°C. These data
temperature will continue well beyond the 8OoC limit of the
test apparatus.
Tests were made on the high fepetition-rate performanceof
rod A . At the maximum power available from the high voltage
supply, 1.5 kW, an average power of 7 W was obtained at7 Hz,
corresponding to an overall efficiency of 0.46 percent.
Tuning of the alexandrite laser was accomplished by using
either a Brewster prism or a three-element birefringent filter at
the Brewsterangle. In principle, wavelengthtuningcanbe
achieved with any of the many schemes used to tune dyelasers.
The birefringent filter and prism tuning elements were chosen
because of their high damage resistance which is particularly
important for the alexandrite laser application because of the
energy storage capabilities and resulting high peak power out-
put. Also, the low insertion losses of these tuning devices are
attractive in light of the low alexandrite laser gain. With the
birefringent filter, a linewidth less than 0.1 nm could be easily
achieved at moderate power levels. The center frequency was
highly reproduciblefrom pulse to pulse. Continuous tuning
withthe birefringent filter extended,atbest,from701 to
796 nm; more -typical results are depicted in Fig. 17. Tuning
with a prism could be extended beyond800 nm to an ultimate
limit of 818 nm, but the bandwidthwas substantially broader
and the laser exhibited inferior pulse t o pulse stability. The
tuning limit of the birefringent filter was determined by the
onset of two frequency operation, which occurred when a sec-
ondary transmission peak ofthe filter appeared nearthe center
of the laser gain curve. This frequency range and its temper-
ature dependence are currently under study. At low chromium
1312 IEEE JOURNAL OF QUANTUM ELECTRONICS, VOL. QE-16, NO. 1 2 , DECEMBER 1980

0 1 " ' " " " '

700 750 800 Input Energy (J)
Wavelength (nrn)
Fig. 18. Q-switchedR-lineperformance-rod A (0.042 atm . percent
Fig. 17. Wavelengthdependence of threshold: solidcurves are for Cr3+), flash duration is 200 ps.
rod A and dashed curves are for rod B ; tuning is accomplished by a
three element birefringent fidter.
mium ion are responsible forthe three-level laser actionin
concentration,theshorter wavelengths are favored. The re- both materials. The ground 4A2 multiplet is fourfold spin de-
sults imply that tuning below 701 nm is achievable particularly generate and the ' E multiplet is twofold degenerate so that
at reduced temperature. This conclusion can be inferred from the population in the E state, which serves as the initial laser
Fig. 10 where the peak gain shifts to shorter wavelengths with level, need only be one-half the population in the ground or
higher p'. A higher p' is normally required in the low concen- terminal laser level. The excited states of the chromium ions
tration material in order to overcome a given loss. This phe- are near enough in energy so that at room temperature the pop-
nomenon accounts for the premature branch-over of the bire- ulation of these states, determined by the Boltzmann partition
fringent filter to a longer wavelength mode, foreshortening the function, is comparable. The distribution of levels for alexan-
tuning range that appears in Fig. 17 for rod B and also for rod drite is presented in Table I11 for 300 and 375 K. By a straight-
A at the higher temperatures. It is anticipated that the tuning forward calculation, it can be shown that three-level laser ac-
range of the birefringent tuner can be extended with further tion in alexandrite has a thresholdwhere 50 percent of theions
design optimifation. are excited and 25percent are in the lower ' E level (consistent
The 8 18 nm long wavelength limit could not be significantly with the fact that E* has, by accident, the same energy as R1
extended by increasing either the excitation level or the Sam- at 300 K). For ruby, the corresponding fractions are 48 and
ple temperature. The abrupt increase in laser threshold around 26 percent, the difference between ruby and alexandrite being
818 nm can not be attributed either to the decrease in emission due to minor differences in the energy-level spacings induced
cross section (which is too gradual) or to any resonator param- by the different hosts.
eters. The sudden change could be due to the onset of a dom- The R-line lasing was observed only on rod A and perfor-
inance of the excited-state absorption cross section over the mance with three output couplings is shown in Fig. 18. Rod B
effective emission cross section just beyond 818 nm. If this is was slightly longer so that a 2 cm portion could not be pumped.
the case, then laser emission can not beextended much beyond The absorption of this unexcited region at the R-line wave-
this wavelength. length effectively limited the laser action to the vibronic mode
The qualitative laser-threshold behavior evident in Fig. 17 independent .of theotheroperating conditions. In rod A ,
follows thetheoreticaltrends displayed in Fig. 10. The ex- however, a 70 percent Routput mirror introduced enough
perimentally determined minima in the threshold curves shift loss to cause the population inversion to reach approximately
to the red for increases in both the ion concentration and the 50 percentprior to the onset of lasing. At these inversion levels,
temperature. This shift is consistent with the gain calculations the high gain of the R-line forces the emission to be at 680.4 nm
of Fig. 10. Also, it is evident from Fig. 10 that an inversion ofeven without any explicit wavelength tuning elements in the
approximately 2 percent would be required to produce, in rod cavity. The gain in theR-line was sufficiently high so that
B , a laser gain sufficient to overcome the insertion-loss of lasing occurred when the output mirror consisted of the un-
0.003 cm-l measured for that rod. The maximum gain for coated face of the laser rod. 400 mJ could be achieved in long-
this inversion occurs at a Wavelength very near to the room- pulse R-line operation with rodA , but the slope efficiency was
temperature minimum laser-threshold wavelength, 750nm, only approximately 0.15 percent. This relatively low value
shown in Fig. 17. The 2 percent inversion is also consistent may be attributed to the low optical absorption of the l o w
with very approximate estimates of this quantity that can be concentration rod.
made by comparing the 750 nm threshold energy with that It is expected that the optimum Cr3' concentration forR-line
which is required to achieve R-line laser action. lasing in alexandrite will be determined by the same considera-
tions that establish optimum performance in ruby, with the
R-LINE LASEROPERATION added consideration that vibronic lasing must be prevented.
The alexandrite laser will lase in both three- and four-level The efficiency of R-line lasing in optimized systems is expected
modes. In the three-level mode, the operation is analogous to to be comparable to that of ruby butwill remain substantially
lasing in ruby. Identical states and transitions within the chro- less than the ultimate efficiency to be achieved in the alexan-

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WALLING et al.: TUNABLE ALEXANDRITE LASERS 1313

Input Energy(J)

Fig. 19. Comparative performance of alexandrite and ruby in the same apparatus with optimized output coupling. The
total Cr concentrationsand slope efficiencies are:(a)alexandrite rod B, 4.2 X loi9 ions/cm3, 1.5 atmpercent; '(b)
alexandrite rod A , 1.5 X 1019 ions/cm3, 0.50 atm * percent; (c) ruby 1.6 X 1019 ions/cm3, 0.57 atm percent. In the+

alexandrite case,only 53 percent of the Cr ions are on the active mirror sites.

drite vibronic mode. Also, in complete analogy with ruby, the have been obtained. For example, as much as 7 J per pulse at
R-line laser operation will improve at a reduced temperature a 5 Hz repetition rate for a total ofW has
35 been obtained from
based on the reduced thermal broadening of the R-line, the a 6.35 mm by 7.6 cm rod orientated along thee-axis that con-
increased storage time which facilitates pumping, the increased tained 0.36 atm * percent Cr3+. The overall efficiency for this
thermal conductivity, and the reduction in vibronic laser gain. operation was 2.5 percent. This operation was long pulse at a
240 (us FWHM flashlampduration,untuned,andnon-Q-
@SWITCHEDOPERATION switched. Furthermore, CW operation has been obtained from
Because of strong gain polarization it was not necessary to a 3 mm by 6.4 cm e-axis rod with 0.27 atm *percent Cr3+ .[37]
introduce a polarizer in conjunction with the Pockels cell in This performance was achieved bv means of a dual elliptical
order to achieve Q-switch operation as long as pumping was silver plated cavity that incorporated two mercury capillary
kept below twice the.normal-mode threshold energy. The use lamps with 2 mm bores powered by60 Hz ac-current supplies
of the birefringent tuner in conjunction with Q-switch opera- such that each lampwas driven 90" out of phasewith the other.
tion further extends the pumping limit because the birefringent In a single lamp elliptical cavity, again withanac-powered
tuner provides the polarizing function aswell.Successfulsi- mercury lamp, a maximum of 6 W was obtained at wavelength
a
multaneous Q-switching and birefringent filter tuning have near 750 nm.
been achieved and will be reported subsequently.
Free-running(untuned) Q-switch tests were performed on DISCUSSION AND SUMMARY
both rods A and B. The pulse duration for rod A ranged be- There are several notable characteristics of the alexandrite
tween 120 and 200 ns depending on the excitation level. For laser: the fluorescence is emittedinone polarization which
rod B, the pulse duration was significantly shorter and ranged provides amaximumtunablegain-bandwidthproductfora
from 120 down to less than 70 ns. For R-line operation (rod minimum cost in storage time; the storage time is itself long
A only), the Q-switch pulse duration was less than 20 ns, the enough to permit practical flashlamp excitation; the emission
instrumental limit. Double pulsing that consisted of an R-line cross section is high enough to permit adequate energy extrac-
<20 ns pulse followed by a 200 ns vibronic mode pulse could tion at power levels which the high damage threshold can tol-
also be achieved under Q-switched operation with rodA [23] . erate and yet low enough to permit large energy storage; the
The Q-switched laser performance to date has been hampered materialoperatesmore efficiently at elevatedtemperature
byexceptional loss associated withimproper antireflection which reduces cooling requirements;the tunablegain is homo-
coatings and internal loss of the Pockels cell itself. A more geneously broadened;and thehostphysicalpropertiesand
thorough analysis of the Q-switched laser performance will be growth characteristics are excellent for laser applications.
reported subsequently. However, rod B has produced a maxi- It is obvious from what has been described that optimumper-
mum of 230 mJ Q-switched laser output under 15 percent formance in all phases of operation can not be expected from
output couplingandwith notuning element.Recent tests one material of one Cr concentration or one laser geometry.
using 6.3 mm diameter rods 7.6 cm long with 0.3 atm * percent Moreover, much of the diversity inherent in this laser remains
Cr3+ have yielded in excess of 500 mJ per pulse in less than to be explored. Nevertheless, the performance achieved to
33 ns pulses at repetition rates above 5 Hz. date is comparable or superior to laser materials well developed
in the field. A case in point is the direct comparisons with
OTHERTESTS ruby, the most widelyused high power red laser source, shown
This paper has discussed laser performance and the theoryof in Fig. 19. The ruby rod contained 1.6 X lo" ions/cm3 and
operation for alexandrite. In presenting the data,it was chosen was of high laser quality. The same rod size and laser system
to use results from two rods that, when combined, best illus- were used in this comparison, onlythe mirrors were optimized.
trate the several operating modes and the nature of the lasing Of course, it is expected that the threshold in ruby would be
action. Other interesting but less welldocumented results much higher because ruby is a three-level laser; still the superior

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1314 JOURNAL
IEEE
slope efficiency of alexandrite as well as its tunability is dra-
matic in comparison. The high slope efficiency andlow thresh-
old characteristic ofYAG:Ndandthe neodymium doped
glasses may be achieved in alexandrite with proper system
optimization. Furthermore, the 100 nm tuning range of alex-
andrite is comparable to the broadesttuning-range organic dyes.
In conclusion, alexandrite is a broadly tunable laser material
that does not require cryogenics, nor does it continuously de-
grade in use or from extended storage. The alexandrite laser
relies on well established laser technology and provides the
most practical, efficient, and powerful tunable source in the
700-800 nm range discovered to date.
ACKNOWLEDGMENT
The authors wish to acknowledge the work of J. D. Witt and
B. D. Forman who provided the alexandrite absorbance data
obtained on the Cary spectrophotometer, and to thank M. J.
Weber for clarification of the dominant source of the vibronic
emission, and especially to thank M. A. Gilleo for his con-
tinued support and interest in this work. In addition, the au-
thors are indebted to M. L. Shand for his careful check of the
mathematical modeling and datareductions which hasin-
creased the accuracy of this work.
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OF QUANTUM
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IEEE JOURNAL O F QUANTUM ELECTRONICS, VOL. QE-16, NO. 12, DECEMBER 1980 1315

Otis G. Peterson, for a photograph and biography, see p. 120 of the Robert C. Morris, for a photograph and biography, see p. 121 of the
February 1980 issue of this JOURNAL. February 1980 issue of this JOURNAL.

Oscillator Performance and Energy Extraction from a

KrF Laser Pumped by a High-Intensity Relativistic
Electron Beam
JAMES K. RICE, GARY C. TISONE, AND EDWARD L. PATTERSON, MEMBER, IEEE

(Invited Paper)

Abstmct-A laser cell with 2 1 of excitation volume was used to study
the electron-beam pumped KIF laser system at excitation rates of 1.8-
7.0 MW/cm3. The system was optimized as an oscillator for various
mixtures of Ar, Kr, and F2 at total pressures of 1000 and 2500 torr.
The resulting optimum conditions gave an intrinsic efficiency (laser
energy out/electron-beam energy deposited) of 12 percent for the 1000
torr total pressure mixture with an output energy of 11 J/1. An effi-
ciency of 10 percent with an output of 40 J/1 was obtained for the
2500 torr mixture. The system was then used as an amplifier t o mea-
sure the extracted power as a function of input power for the two
mixtures. The small-signal gain go, the nonsaturable absorption a, and
the saturationintensity I, were determined for the two mixtures.
Analysis of the data gave go = 16-18 percent/cm, a! = 0.75-1.25 per-
cent/cm, and Z, = 2 MW/cm2 for the 1000 torr mixture andgo = 17-19
percent/cm, a! = 1.0-1.5 percent/cm, and Z , = 9 MW/cm2 for the 2500
torr mix.
Manuscript received July 14, 1980. This work was supported by the
U.S. Department of Energy.
The authors are with Sandia National Laboratories, Albuquerque, NM
87185.
I. INTRODUCTION
T HE electron-beam pumped KrF system at 248 nm is a
short wavelength high-power, efficient laser which has
received muchattention in recent years [l]. Most ofthe
previous work concentrated on determining the kinetic pro-
cesses relevant to this laser system and ondemonstrating
efficient long-pulse laser operation for pump intensities near
0.1 MW/cm3. Early work with high-intensity electron-beam
excitationatpumprates above 1 MW/cm3 showed lowered
efficiency, presumably the result of unfavorable kinetic pro-
cesses or opticalmateriallimitations associated with high
pumpand laser power. However, as understanding of this
laser system increased and as plans to scale this system to high
energies developed, it became evident thatthis high-power
regime should be reexamined for some of the advantages it
offers to laser-system scaling, such as increased specific power
and lowered total volume.

0018-9197/80/1200-1315$00.75 0 1980 IEEE

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