Laser Physics II

PH482/582 2E PH482/582-2E (Mirov) Color Center Lasers C l C t L Lectures 4-5 Spring 2009
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OUTLOOK
1. Types of color centers in ionic crystals and principles of operation 2. Crystal hosts for active elements of color center lasers 3. Color center formation in ionic crystals 3a. Additive coloration 3b. Electrolytic coloration 3c. Color center formation in alkali halide crystals under ionizing irradiation alkali-halide LiF:F2- active element optimization LiF:F2+ active element optimization 4. Major spectroscopic characteristics of color centers 5. 5 CW and quasi-CW color center l d i CW l t laser operation (T 77K) ti (T=77K) 6. Pico and femtosecond quasi-CW color center laser operation (T=77K) 7. Room temperature CCL operation 7a. CW and quasi-CW q 7b. High peak power room temperature CCL operation in mode-locked regime 7c. High energy and power color center lasers 7d. 7d Color center energy and power amplifier 7e. Narrowline tunable color center lasers
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8. Practical applications

Major Literature
1. "Room temperature tunable color center p lasers", T.T.Basiev, S.B.Mirov, Laser Science & Technology book Ser., 16, 1-160, V.S.Letokhov, C.V.Shank, Y.R.Shen, H.Walter, V S Letokhov C V Shank Y R Shen H Walter Eds., Gordon and Breach Science Publ./Harwood Acad. Publ. (1994). ( ) 2. T.T. Basiev, P.G. Zverev, and S.B. Mirov. Color Center Lasers, Handbook of Laser Technology and A li ti T h l d Applications. I tit t of Institute f Physics publishing. Eds. C.E.Webb and J C Jo es, J.D.C.Jones, B1.8, 1-23, (2003). 8, 3, ( 003)
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1. Types of Color Centers

In general, the major crystals where laser active CCs can be developed are pure and i d impurity-doped fl id and chlorides of Li N K and Rb alkali it d d fluorides d hl id f Li, Na, K, d lk li metals [i], [ii], [iii], [iv], as well as CaF2 and SrF2[v]. Laser oscillation has also been reported using CCs in Al2O3[vi],[vii], diamond[viii], MgF2[ix], and the compound fluorides KMgF3 [x] and YLiF4 [xi]. In the primal state these crystals are optically transparent Under irradiation with high-energy electrons neutrons transparent. high energy electrons, neutrons, -rays, X-rays, or hard UV, or calcination in alkali metal vapor (additive coloration), anionic vacancies appear in the crystal lattice and serve to localize free electrons. The absorption bands of these (F) centers (vacancy + electron) give a typical coloring to the crystals.
[i] Yu. L. Gusev, S. I. Marennikov, V. P. Chebotaev, Bull. Acad. Sci. USSR, Phys. Ser., 44, 15 (1980). [ii] I.A.Parfianovich, V.M.Khulugurov, B.D.Lobanov, and N.T.Maksimova, Luminescence and stimulated emission of color centers in LiF, Bull. Acad. Sci. USSR, Phys. Ser., 43, 20-27 (1979). [ ] [iii] W. Gellermann J. Phys. Chem. Solids, 52, 249 (1991). y , , ( ) [iv] L.F.Mollenauer, Color Center Lasers, in Tunable Lasers, L.F.Mollenauer and J.C. White (Eds.), Vol. 59, pp. 225-277, Berlin, New York: Springer Verlag (1987). [v] V. A. Archandelskaya and P. P. Feofilov, Sov. J. Quantum Electron., 7, 657 (1980). [vi] E.F.Martynovich, V.I.Baryshnikov, V.A.Grigorov, Visible lasing of Al2O3 color center crystals at room p , p , , ( ) temperature, Opt. Commun., 53, 257-258 (1985). [vii] A.P.Voytovich, V.A.Grinkevich, V.S.Kalinov, S.A.Mikhnov, Spectroscopic and oscillation characteristics of color center sapphire crystals in the range of 1.0 m, Kvant.Electron., 15, 318-320 (1988); Sov. J. Quantum Electron. (1988). [viii] S.C.Rand, L.G.DeShazer, Visible color-center laser in diamond, Opt.Lett., 10, 481-483 (1985). [ ] [ix] A.P.Shkadarevich, A.P.Yarmolkevich, New laser media on color center compound fluoride, , , p , Inst.Phys.AN BSSR, Minsk, USSR, preprint 24 (1985). [x] G.Horsch, H.J.Paus, A new color center on the basis of lead-doped KMgF3, Opt. Commun., 60, 69-73 (1986). 3 [xi] T.T.Basiev, F.A.Vakhidov, S.B.Mirov, Radiational transformations in a new LiYF4 laser crystal with color centers, Kratkie Soobsheniya po Fizike, 7, 3-5 (1988); Sov. Phys.Lebedev Inst.Rep., 7, 1-5 (1988).

1. Structure of the simplest color centers in LiF crystals

F F2

e-

e-

e-

F2+

F2-

eeee--electron
4 Li+-- ions

e-

F-- ions

Anion Vacancy

1. Ionic configurations of other simple F type color centers

FA(I) centers in the ground and excited states t t

FB(I) centers ( ) ce e s in the ground and excited states

FA(II) centers in the ground and excited states

FB(II) centers in the ground and excited states

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1. Models of (a) F2 CCs in alkali-halide crystals; (b) (F2)A CC i alkali-earth fl CCs in lk li th fluorides id

1. Two possible arrangements of four F centers to form N centers. These arrays are either a tetrahedron or a parallelogram

1. Principles of CCL operations

E

E2

3
E1

1. Pump radiation i absorbed i th wide 1 P di ti is b b d in the id band of the electric-dipole electronvibrational transition 12. , 2. In a time on the order of 10-12-10-13 s, radiationless relaxation to the minimum of potential curve of the excited electronic state, 23 occurs, p y accompanied by a mutual rearrangement of the neighbouring ions and by phonon emission. 3. Then a radiative electron- vibrational transition (34) occurs with a probability of A =107-108 s-1, followed by 4. another rapid vibrational relaxation (41) to the potential curve minimum of the ground electronic state with resetting of the spatial ion configuration. Disregarding the details, one may consider this scheme as the f id thi h th four l levels l laser scheme of oscillation.
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1. Principles of CCL operations

The principles of CCL operation can be accounted for using th F k i the FrankCondon configuration diagram, diagram which describes the optical properties of an electron system interacting with molecular or lattice vibrations: in particular, the optical transition of CCs.

1. Two different groups of CCC. a) operating at RT; b) operating at T<77K ) ti t RT ti t

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1. Major Defects Classification

Edge Dislocations Screw Dislocations LINE IMPERFECTIONS

DEFECTS
Point Defects

Laser active optical centers

Cation Vacancies

Impurity Cation Cr3+; Ti3+ 3+ E 3+ Nd3 ;Er3 Ho3+ Anion OHO2-

Impurity-Vacancy Dipoles Cation-Vacancy FA; FB; (F2+)A; Me F M M +-F; Me++-F2-; F Zcenters : F-Me++VcAnion-Vacancy O--Va+

Intrinsic defects f Anion Vacancies Electron centers (Color Centers) Hole Trapping Centers

Simple F

F2; F2

+;

Aggregate F2-; F3; F3+; F3-; F4 11

2. Main physicochemical, mechanical and optical characteristics of the most promising crystal hosts with CCs
Crystal

(g/cm ( / 3)
2.64 2.79 2.17 2.50 1.99 2.75 3.13 2.76 2 76 3.18 3.18 4.24 3.974 3.515 4.55 2.539 2 539

d
o

H (kg/mm2) 99-102 60 15.2-18.2 7.2-9.3 6-7 5 576 120-163 144 2100 8820 1350 -

LiF NaF NaCl KF KCl KBr KI RbCl MgF2 CaF2 SrF2 Al2O3 Diamond Y3Al5O12 ED 2 ED-2 glass

( A) 4.03 4.62 5.64 5.35 6.29 6.60 7.07 6.58 6 58 a=4.64 c=3.06 5.46 5.79 a=4.76 c=13.0 3.57 12.0 -

Solubility (g/100g H2O) 0.12 4.2 36.0 94.9 37.4 70.9 144.0 94.2 94 2 0.0076 0.0016 <0.1 0 0 0 -

Tm (K) 1121 1270 1074 1130 1049 1007 959 717 1,536 1,676 1,190 2,313 3,770 2,223 582

K (W/mK) 14.2 9.2 6.4 6.0 4.8 2.1 21 c 30 c 9.7 35.0 900.0 13.0 1.4 14

RT* (W/m) 43-143 470 10,000 790 140

dn/dT x 105 (K-1) -2.9 -1.8 -3.7 -3.3 -3.2 -4.5 11.2 5.8 -1.05 1.3 0.97 0.4 1.05 0.3 03

Ithr x 10-12 (W/m2) 3600 1400 200 700 500 200 1000 >1000 1900 12000 2000

1.387 1.321 1.53 1.48 1.54 1.64 n0=1.373 ne=1.385 1.429 n0=1.765 ne=1.757 2.40 1.815 1.56 1 56

Transparancy range at =1cm-1 level 0.11-6.6 0.16-11.2 0.17-18.0 0.2-15.0 0.18-23.0 0.21-28.0 0.3-35.0 0.1-7.0 0.13-9.4 0.1-9.0 0.18-.5.1 0.24-2.7 0.21-5.3 -

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3. Methods of Color Center Formation

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3a. Formation of F centers by Additive Coloration ( ) (AD)

AC involves bringing the crystal in equilibrium with a bath of alkali vapor. The F-centers are formed at the crystal surfaces and fill up the body of the crystal through diffusion Assume that No diffusion. equilibrium density of F centers; N- the metal vapor density Usually No=N, where =2-3 for alkali-halides. At the beginning of coloration the F centers are concentrated at the crystal surfaces For a thin slab the behavior at later times surfaces. slab, (t>D) is
x l

4 t x N ( x, t ) = N o 1 sin exp l D
l2 D = 2 D
T D (T ) = D0 exp 0 T

Where D-diffusion constant; D-diffusion time

For KCl: T0=14,400K; D0=1.22x102cm2/s For T=600C; D=8x10-6cm2/s T=600 C; For l=2 mm; D=8.4 min and t=30 min for practically uniform coloration 14

3b. Electrolytic coloration

r. q. p.

a. b. c.

o. n. m. l.

d.

e.

k.

f.

j. j

g. g

i.

h.

a. Thermal insulation cap b. Quartz tube c. Crystal sample (ZnSe) thickness = 4.0mm d. Chromium (Cr) foil thickness = 1.0mm e. Electrode stage f. Adjustment spring assembly g. Ceramic base h. Cathode connection i. Anode connection j. Gas inlet port k. Threaded assembly rod l. Thermal insulation wrapping m. Anode plate nut n. Inert/evacuated atmosphere o. Gas exhaust port p. Cover plate and stand bracket q. Cover plate nut r. Steel support stand and base
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3c. Color center formation in alkali-halide crystals under ionizing irradiation

The formation of aggregate color centers in alkali-halide crystals under ionizing radiation is a complicated process involving emergence, separation, and recombination of primary Frenkel defects, association into aggregate F2, (F2)A, F2+, (F2+)A, F2-, F3, F3+, F3- and other color centers and recharging of color centers by electrons and band holes The defect formation may run fast or holes. slow. Decomposition of self-localized excitons into primary radiational defects and recharging of color centers are relatively fast processes (10-12 -10-7 s). Slow processes run either due to spatial diffusion of the defects and their associates or due to diffusion of associates, self-localized holes (resulting in color centers recharging). All the above processes determine the efficiency of formation of any type of color centers. These processes depend upon the temperature of irradiation and storage of the crystal, impurity t t f i di ti d t f th t l i it composition of the initial material, ionizing radiation dose power and irradiation dose.

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3c. Color center formation in alkali-halide crystals under ionizing irradiation y g

Separated electrons and holes, free and self-localized excitons are generated in alkali-halide crystals under ionizing irradiation. Selflocalized excitons decompose with the emergence of pairs of Fcenters and interstitial halogen atoms (H) A fast recharging of these (H). pairs under flux of electrons gives rise to actually simultaneous formation of the anion vacancies Va+ and interstitial halogen ions Ia

e so F + H

(1)

e so Va+ + I a (2) The mechanisms of formation of aggregate centers through migration of anion vacancies are mainly going through the following route: charged F2+ centers first appear, and then capture electrons to produce neutral F2 centers

Va+ + F F2+
F2+ + e F2

(3) (4)
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3c. Color center formation in alkali-halide crystals under ionizing irradiation

Simultaneously with a fast process of electron capture F2+ centers may capture, take part in a slow temperature-dependent migration process. Colliding with the F, F2+ and F2- CCs, they form more complex CCs - F3+, F4+ , and F4 , respectively: (5) F+ + F F+

F2+ + F2 F4+
F2+ + F2 F4

(6)

(7) whose further aggregation leads to the appearance of colloid particles in the crystal. The processes of F2 CCs formation by scheme (3.4) are competing with the processes of their ionization due to a fast capture of free electrons:

F2 + e F2
or holes

(8) (9) (10)

F2 + h F2+
or due to diffusion processes involving mobile anion vacancies

Va+ + F2 F3+
and self-localized holes

F2 + Vk F2+

(11)

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3c. LiF:F2- active element optimization

The LiF:F2- crystals combining unique modulation, thermal, and operational characteristics, are now widely used as active media in tunable lasers and as nonlinear elements with saturable absorption for neodymium laser Q, q y preparation switches. However, available techniques of such laser crystals p p fail to produce optically dense, high-contrast media required for a series of applications. Usually, the value of active absorption at the working wavelength does not exceed 0.4-0.6 cm-1 at a contrast (ratio of the active absorption coefficient to the loss coefficient at =1.06 m) of 10-20. Under the action of quanta commonly used for producing LiF:F2- laser crystals -quanta crystals, + CCs emerging by reaction (3) may be involved in three processes: the F2 a) fast process of electron capture to produce F2 CCs (reaction 4) and F2CCs (reaction 8); b) slow diffusion processes of aggregation of the type 5, 6, 7; c) dissociation on the F center and anion vacancy F2+ F + Va+. , ; ) y The rates of the processes and final concentration of CCs depend on the impurity composition of the initial material, irradiation dose, power, and crystal temperature. Varying the ratio of these parameters, one can essentially influence the processes of F2- CC formation in LiF. When we optimized the procedure of LiF crystal treatment under ionizing irradiation so, that the processes 3, 4 were efficient and 5-7 negligible, 57 maximum active absorption of F2- CCs at the wavelength 1.064 m exceed 1.5 cm-1 at a contrast as high as 20 40.

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3c. Optically Dense Electron Irradiated LiF:F2crystals t l

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3c. LiF(F2F2+) crystals optimization

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3c. Efficient, RT Stable LiF:F2+** Crystals

Formation Of The F ti Th Thermostabilized F2+** Active Color Centers
e so F + H ; eso Va+ + I a ; Va+ + F F2+ ; F2+ + e F2

F2+ + F F3+

F2+ + F2 F4+

F2+ + F2 F4

Va+ + F2 F3+

1. LiF crystals doped with LiOH, Li2O y p and MgF2 can be grown by any method which assures good optical quality o o e s F + H ; es Va+ + I a 2. Crystals are subjected to 2( 2( OH ) O2 + e + Va+ + H io , irradiation, irradiation X -ray or electron ray 2( OH ) + Va+ + e O Va+ + O + H io , irradiation with a dose of 2.5x103 1.5x104 Q/kg at a temperature lower than TV -- temperature of Va+ mobility in LiF crystals. y y Va+ + F F2+ 3. Crystals are heated up to TO-V <T< TF and stored in the refrigerator for O Va+ + F F2+ O a period up to one month (TF Me 2+ Vc + F Me + Vc + Va+ Vc ; Va+Vc + F F2+Vc corresponds to mobility of F2+CC and TO-V to O--VA+ dipoles dipoles. 4. Crystals may be reirradiated at the FVa+ temperature T< TV with a dose of 25-250 Q/kg and then subjected to the procedure described in 3. p O Va+ + F F2+ O ; Va+Vc + F F2+Vc ; F2+ + O + e F2+ O 5. Crystals heated up to RT and are stored for a period of some F2+ + F F3+ low efficiency scince NF is small months.

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3c 3c. Efficient, RT Stab e LiF:F2+** Crystals c e t, Stable C ysta s

Photostability Of Active CC As Well As Other CC That May Be Ionized By The Powerful Pump Laser Excitation 1. The technology of LiF should provide a highest possible concentration of the active CC. The pump radiation will be p p predominantly absorbed by the photostable F2+ like centers. 2. Pump radiation from one hand should match the absorption band of F2+** color, and from another, should color another be longer than the threshold wavelength determining the process of two step ionization of the neutral F2 centers ( (590 nm) ) 3. the wavelength of the pump radiation shouldnt match the absorption bands of the parasitic aggregate CC (500-600 nm) that may occur in the crystal and result in decreasing of the efficiency of lasing efficienc
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3c. Novel LiF:F2+** Crystals

(U.S. Patent No. 5,796,762 (U S P t t N 5 796 762 )
10

80000 70000 532 nm Excitation 633 nm Excitation

A Absorption Coefficient, cm-1 m

Intensity, arb. units

F 2 C e n te r
6

60000 50000 40000 30000 20000 10000

F 2 **
2

F 2 **-lik e

0 10 8 6 4
14

0 600 700 800 900 1000 1100 1200 1300

F re q u e n c y, H z (x 1 0

Wavelength, nm

40000

30000

New F 2 **-like Center (measured at 24 K) F 2 ** Center (measured at 13 K)

+

Intensity, arb. units

20000

10000

0 700 800 900 1000 1100 1200 1300 1400

W avelength, nm

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3c. Proposed model of F2+** stabilized CC in LiF

Four defect configurations with different symmetries are possible for closest (110) neighboring positions of the F center vacancy site (labeled 1 to 4) with respect to the charge compensating vacancy
F2+**
RT 1)O Va+ + F F2+O

Li+ O-Li+ FLi+ Va+

Va+

2)OH O + H io
RT O + e + Va+ O Va+ RT O Va+ + F F2+O

eLi+ VcF2

2(OH ) O2 + e + Va+ + 2 H io 2(OH ) + Va+ + e O Va+ + O + H io H io + e H i

Li+ FLi+ F-

3) F2+ + O + e Rt F2+O
RT 4) Mg + +Vc + F Mg + + Va+Vc RT Va+Vc + F F2+Vc

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3c. Key Advantages of the Optically Dense Color Center Active Media C l C t A ti M di
The key d Th k advantages of the optically d f h i ll dense active media are the i di h high efficiency of the pump energy conversion into the output generation and an opportunity for further miniaturization of the laser devices on their basis. The aforesaid advantageous are undeniably true and for the ionic color center crystals. H t d f th i i l t t l However, hi h highconcentrated color center crystals exhibit some new special features. g g y g light to light efficiency increasing color center crystal photostability may be essentially improved it is possible to reach high gain coefficients and laser threshold conditions on the colored layers with a thickness of about 0.01 1m such a thi colored fil h thin l d films of di l t i crystals are f dielectric t l semicanductor in character. This fact provides a theoretical reason enough to develop principally new lasers based on the dielectric crystals with an electrical pumping
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3c 3c. LiF:F2 ultimately high co ce t ated media u t ate y g concentrated ed a

e 150 keV I= 20 A d=90 microns k=1000 cm-1 LiF
A highly-concentrated (k = 400 cm-1) LiF:F2 crystal with a 90 m thickness of coloration was developed under low energy electron irradiation. This enables the threshold of generation of the LiF:F2 crystals to be significantly decreased to such a low level of pump radiation ( 3 J), that the probability of the F2 color centers two step photoionization started to be negligible.

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3c 3c. LiF:F2 ultimately high co ce t ated media u t ate y g concentrated ed a

X rays 1.06 YAG:Nd LiF E=1J t=4 ns f=10Hz k=1500 cm 1 cm-1 d=4 microns

A new method of radiational coloring of the LiF crystals with quanta of soft X-ray radiation, generated with the use of a laser (1.06 m) plasma source. The absorption coefficient in the F2 band was about 1500 cm-1, thickness of coloration - 4 m.
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4. Major spectroscopic characteristics of color centers

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4. Luminescence bands of (a) FA(II) and FB(II) centers; (b) F2+ centers, and (c) FA(Tl) centers in alkali-halides at 77K t

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4. Absorption (solid lines) and luminescence (dashed lines) bands of CCs in Al2O3crystal at 4.2 and 300 K, respectively. Numbers near the bands are wavelengths of zero p phonon lines

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5. CW and quasi-CW color center laser operation (T=77K) p ( )

The pump density of several kWcm-2 is needed to reach p p y the threshold of CCL oscillation. This is easily achieved for pulsed pumping by a flash lamp emitting few tens of j joules during a millisecond p g pulse. In this case the lasing g volume of color center crystal can be as large as 1 cm-3 or even more. In order to get the same pump densities for cw laser pumping with power of 0.1-10 W, one have to use strong focusing of the pump radiation and put the CCL crystal at the focal point or cavity waist of 0 1-1 mm in diameter 0.1 1 diameter. The crystal length is limited by the confocal parameter of focused beam and usually does not exceed 1 cm (typically it is a few mm) mm).
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5. CW and quasi-CW color center laser operation (T=77K)

The most popular optical scheme used now for cw CCL operation i th ti is the Kogelnik scheme with a Brewster cut active element and with Vshape or Z-shape folded cavity to compensate spherical lens or mirror astigmatism.[i] astigmatism [i]

t [i] H. W. Kogelnik, E. P. sin tan = 1 f Ippen, A. Dienes, and C. (n 2 1)(n 2 + 1) 2 V. Shank, IEEE J. of The beam waist diameter W0 and confocal length b can be Quantum Electron., QE- found from the formulas 8, 373 (1972). b f f2 W0 = f t b= = 2l2 l2 l f
2 2

n4

33

5 Cavities of CW CCL 5. Ca t es o C CC

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5. CW and quasi-CW color center laser operation (T=77K) ti (T 77K)

There are two sets of the most popular regimes p p g of operation in cw mode. 1. The first one is the narrow line (single frequency) broadly tunable CCL oscillation f f ) b dl bl ill i for visible and IR spectroscopy, analytical application, application and fundamental metrology metrology. 2. The second is the mode-locked pico- and femtosecond pulse operation regime for time resolved transient spectroscopy, high peak power nonlinear conversion, and fast telecommunication systems systems.
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5. CW and quasi-CW color center laser ope at o ( operation (T=77K) )

Single-mode, single-frequency operation of a KCl:Li FA(II) CCL under krypton ion laser pumping at 647 nm with linewidth less than 260 KHz and tunability in 2.5-2.9 m spectral range 2529 realized with the pair of birefringent plates and an intracavity solid etalon was obtained in Ref. [[i]]. By the active frequency stabilization, linewidth as low as 2 KHz was realized later in [ii] [ii]. To obtain a single mode operation and to improve linewidth and wavelength stability, the ring cavity operation can be also applied [iii], [iv]. Typical output power of FA(II) CCL varies from tens to hundreds milliwatts in 2.3 - 3.5 mm spectral region

150 O Output Pow mW wer, KCl:Li+ 100 RbCl:Li+ 50

0
[i] R. Beigang, G. Liftin, and H. Welling Opt. Commun. 22, 269 (1977). [ii] Ch. Breant, T. Baer, D. Nesbitt, and J. L. Hall in Laser Spectroscopy VI (Edited by H. P. Weber and W. Luthy) p.138, Springer, Berlin (1983). [iii] T F. Johnston and W. Proffitt IEEE J. Quantum T. F J h t d W P ffitt J Q t Electron., QE-16, 483 (1980). [iv] C. R. Pollock and D. A. Jennings Appl. Physics, B28, 308 (1982).

2.5 25

3.0 30 W avelength, m

3.5 35

Tuning curves of KCl:Li+ and RbCl:Li+ FA(II) CCL

36

5. CW and quasi-CW color center laser operation (T=77K) ti (T 77K)

With the Kr laser pump source, LiF:F2+, CCL operation p p p with a very high slope efficiency of 60%, close to the physical limit (output to pump photon energy ratio) 70%, was obtained. A wide tuning range 0.841.04 m was g g covered with the cw output power up to 1.1 W in pure cw regime and under synchronous picosecond pumping 6. , g ps pump In the last case, 25 times shortening from 100 p p p to 4 ps CCL output was demonstrated [i]. [i] L F Mollenauer Color Center Lasers in Tunable [i]. L.F.Mollenauer, Lasers, Lasers, L.F.Mollenauer and J.C. White (Eds.), Vol. 59, pp. 225-277, Berlin, New York: Springer Verlag (1987).
37

5. CW and quasi-CW color center laser operation (T=77K) ti (T 77K)

One of the main problems of the LiF(F2+) CCL is fast p ( optical bleaching due to orientational diffusion of F2+ CCs. The maximum cw lasing output (2.7 W) was recorded in the KF(F2+) CCL under 1.064 m Nd3+:YAG ( pumping with the tuning range of 1.221.5 m. [i] In the case of (F2+)A color center, the KCL:Li crystal showed a very good performance: Pout=400 mW under Pout 400 1.32 m cw Nd laser pumping and Eout=2.3 mJ under 1.41 m pulsed pumping with the tuning range from 2 to 2.5 m. 2 5 m [i] [i] K. R. German, in Handbook of Solid State Lasers (Edited by P. K. Cheo, Chap. 5, Marcel Dekker, New York (1989) (1989).
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5. CW and quasi-CW color center laser operation (T=77K) ti (T 77K)

The operation of (F2+)H color centers in NaCl crystals doped by OH ions looks very promising. For the first time it was reported in [i]. Output power as high as 3.05 W at the slope efficiency of 33% was reported in [ii] under 9W pumping at 1.064 m and 200 mW collinear auxiliary light of 514 nm. A very wide tuning range, 1.41.92 m, important for telecommunication study and test with output up to 1.3 W was obtained in [iii] at 6 W 1.064 m laser pumping and only 2 mW of 1 064 532 nm collinear auxiliary light. This laser can also easily operate in the mode-locked regime with picosecond pulses as short as 5 ps.

[i] F. Rong, Y. Yang, and F. Luty Cryst. Latt. Def. Amorph Mater. 18, 1, (1989). [ii] R. Beigang, J. J. Wynne, Opt. Lett. 6, 295 (1981). [iii] J F Pinto, E St tt J. F. Pi t E. Stratton, and C. R P ll k O t Lett., 10 384 (1985). d C R. Pollock, Opt. L tt 10, (1985)
39

5. CW and quasi-CW color center laser operation (T=77K) ti (T 77K)

A stable cw laser operation without using the auxiliary li h ih i h ili light was also obtained with the help of FA(Tl) color centers in KCl:Tl+, KBr:Tl+, and KF:Tl+ crystals. The first of these crystals provides about 1.4 W output at the maximum of the tuning t i curve with t ith tunability bilit from 1.4 to 1.6 m at the absorbed pump power ~ 3.5 W p p of 1.064 m Nd:YAG pump laser). [i]
1.0

P in=6.8 W P abs.=2.8 W

T=22%

T=22%

P in=5 W P abs.=1.7 W

0.20

o u tp u t p o w e r , W

0.8 0.15 0.6 0.10 0.4 04

0.2

T=8%

T=5%

0.05

[i] W. Gellermann J. Phys. Chem. Solids, 52, 249 (1991).

0.0
1.4 1.5 1.6 1.7

0.00

Tuning curves of FA(Tl) color center laser in KCl:Tl+ (solid lines) and KBr:Tl+ (dashed lines) pumped by Nd:YAG laser radiation (1.064 mm).
40

6. Pico and femtosecond quasi-CW color ce te ase operation (T=77K) center laser ope at o ( )
One of the most interesting and important regimes of CCL operation is the mode locked regime , when many longitudinal modes of a mode-locked broadband laser radiate with coordinated phase. According to the Fourier transformation, this multifrequency cw laser operation leads to a short pulse high peak power quasi-CW lasing with the pulse-topulse temporal interval equaling to the laser cavity round trip time and pulse duration being inversely proportional to the number of longitudinal mode operating in mode-locking regime. All types of the mode-locking techniques developed for dye lasers are applicable f d li bl for developing mode-locked CCL C l center l i d l k d CCL. Color t mode-locked operation is quite similar to the dye laser mode-locking regime with the only one distinction: the excited state lifetime of CC is about CC=15-1500 ns and is usually larger than the laser cavity round t i ti d trip time, tcavity=610ns, while for the d 6 10 hil f th dyes it i smaller is ll (dye=35ns).

41

6. Pico and femtosecond quasi-CW color ce te ase operation (T=77K) center laser ope at o ( )
One of the most popular and effective techniques for realization of pico- and femtosecond lasing is synchronous pumping, when the pump laser modelocking regime is transferred to CCL. In this case, the cavity round trip times g g , y p of both pump and CCLs should be synchronized and the synchronized CCL gain modulation results in pulsed CCL lasing and pulse shortening to duration much shorter than the pump pulse duration. Expression for the pulse width [i] shows that it should be proportional to the pump and CCL cavities mismatch parameters and i d ii i h d inversely proportional l i l to the logarithmic gain loss product . This means that the shortest pulse duration of CCL can be realized at the highest gain, pump energy, and power. When using 90 ps pulsed krypton laser synch pumping the LiF:F2+ CCL pulses had duration of 2 3 ps in synch-pumping, 2-3 linear cavities and 0.7 ps in ring cavities.[ii] Similar results were obtained in linear cavities of KF(F2+), NaCl(F2+), and KCL:FA(Tl+) lasers under Nd:YAG synch-pumping and for KCl:Li(FA) and RbCl:Li(FA) CCL under modelocked argon laser pumping) pumping). [i] Z. A. Yasa, Optics Lett., 8, 277 (1983). [ii] N. Langford, K. Smith, and W. Sibbett, Opt. Commun., 64, 274 (1987).
42

6. Pico and femtosecond quasi-CW color ce te ase operation (T=77K) center laser ope at o ( )
In the passive mode-locking regime with a dye saturable absorber, pulse duration of 180 fs was achieved in a LiF:F2+ CCL ring cavity at the lasing bandwidth of about 60 cm-1.[i] Using a multiple quantum well saturable absorber, a NaCl(F2+) CCL demonstrates 260 fs pulse operation with 50 cm-1 bandwidth.[ii] By d B developing new additive pulse mode-locking t h i l i dditi l d l ki technique f pulse for l shortening, 127 fs pulse duration instead of 23 ps from KCl:Tl CCL was realized.[iii] In a similar regime 50fs pulses have been generated by so-called soliton laser on KCL:Tl at 1.5 m. [iv] [i] N. Langford, K. Smith, and W. Sibbett, Opt. Lett., 12, 903 (1987). [ii] M. N. Islam, E. R. Sundermann, I. Bar-Joseph, N. Sauer, T. Y. Chang, Appl Phys Lett 54, Chang Appl. Phys. Lett. 54 1203 (1989) (1989). [iii] J. Mark, L. Y. Liu, K. L. Hall, H. A. Haus, and E. P. Ippen, Opt. Lett. 14, 48 (1989). [iv] L. F. Mollenauer, and R. H. Stolen, Opt. Lett., 9, 13 (1984).
43

7. Room temperature CCL operation 7a. CW and quasi-CW

Room temperature tunable CCLs color center lasers have special importance in comparison with dye and cryogenic CCLs due to their compactness, simplicity and easy to use both for laboratory and field conditions. Lithium fluoride with F2- CCs is one of the most reliable active media for room temperature tunable operation. During last two d D i l tt decades only several papers were d di t d t th d l l dedicated to the study of CW and quasi-cw laser operation on LiF:F2- crystals at T=300 K 3,[i],[ii] Most of them used neodymium solid state lasers as a pumping source. [i] T. T. Basiev, Yu. L. Gusev, S. V. Kruzhalov, S. B. Mirov, V. Ya. Petrunkin, Sov. J. Quantum Electron., 12 (1988). [i] W Gellermann, A Muller D Wandt S. Wilk, F Luty J Appl W. Gellermann A. Muller, D. Wandt, S Wilk F. Luty, J. Appl. Phys. 61, 1297 (1987).

44

7. Room temperature CCL operation 7a. CW and quasi-CW

For the first time, pure cw LiF:F2- lasing has been attained using the crystals with kabs=1.3 cm-1 at a pump wavelength of 1 064 mm and low 1.064 losses (KL = 0.01cm-1) in the lasing region of 1.1-1.2 m [i]. A ring cavity with 1 m base and astigmatism compensation incorporated two p p p plane mirrors (2 and 3) with 99.7% and 99% reflectance in the lasing region and two 100% reflectance spherical mirrors (1) with the curvature radius of 10cm. For a pump power of 3 W the lasing W, output power was 60 mW. These results were further improved: the maximum output CW power of LiF:F2laser exceeded 100 mW at a pump p p power of 5 W. The LiF:F2- active element preserved all its properties after a 30 h performance.
[i] T T. Basiev, Yu. L. Gusev, S. V. Kruzhalov, S T. T Basiev Yu L Gusev S V Kruzhalov S. B. Mirov, V. Ya. Petrunkin, Sov. J. Quantum Electron., 12, (1988).

L iF :F
2

Typical cavity for CW or Quasi CW Quasi-CW ring color center laser

45

7. Room temperature CCL operation 7a. 7 CW and quasi-CW d i CW

The first results on frequency tuning and picosecond generation at room temperature of CW LiF:F2 laser were obtained under synchronous pumping with a continuous train of picosecond pulses of CW-pumped Nd3+:YAG laser. The use of a ring cavity and Lyo filter as a dispersive element provided lasing over 1.1-1.2 m spectral region LiF:F2 oscillation under Nd3+:YAG laser region. synchronous pumping provided picosecond pulses with duration of 10 ps and 7 ns axial interval for continuous train of pulses [i] [i] T T Basiev, Yu. L. Gusev, S. V. Kruzhalov, S B. Mirov, V. Ya. T. T. B i Y L G S V K h l S. B Mi V Y Petrunkin, Abst. Rep. XIII Inter. Conf. Coherent Nonlinear Opt., Minsk, USSR, Part 2, 256 (1988).

46

7. Room temperature CCL operation 7a. 7 CW and quasi-CW d i CW

50 40 Efficiency % y,

2
30 20 10 0 1.05

1.10

1.15

1.20

1.25

1.30

Wavelength, m

Tuning curves of quasi cw oscillation of LiF:F2- CCL quasi-cw pumped by Nd3+:YAG (1) and Nd3+:YLF (2) lasers.
47

7b. High peak power room temperature CCL operation in pico and femtosecond regime. ti i i df t d i Since middle 70th there were a lot of studies on picosecond operation of F2+; F2+ O-; F2- and F3color centers in LiF and NaF crystals at room temperature. temperature Synchronous pumping by the train of picosecond pulses of ruby, Nd:YAG or Nd:glass lasers was used as the most effective g scheme of CCL pulse shortening. Fast CC gain switching (modulation) leads to the effective CCL pulse shortening depending on degree of pump power exceeding threshold, number of pulses and length of the train.
48

7b. High peak power room temperature CCL operation in pico and femtosecond regime. ti i i df t d i
Experimental setup of E i t l t f picosecond LiF:F2- CCL. (1, 2, 3) end, spherical and y ,( ) cavity mirrors, (4) active element (LiF:F2- crystal), (5) prism compensator of the group velocity dispersion, (6) aperture, aperture (7) Lyo filter (8) filter, streak camera, (9) -PC. Babushkin A V, Basiev T T, Vorob ev S, Vorob'ev N S Mirov S B B, Prokhorov A M, Serdyuchenko Yu N, Shchelev M Ya., Sov. J. Quantum Electron. 16, 1492 (1986).
49

1 7 6

9
= 1 .0 5 5 m = 1 .1 0 - 1 .2 2 m

7b. High peak power room temperature CCL operation in pico and femtosecond regime. ti i i df t d i
A precise matching of resonator's lengths gave rise to LiF:F2 femtosecond oscillation with a pulse duration of less then 500 fs at fs, a full train duration of 300-400 ns and a train energy of 250 mJ [i]. The durations of the subpicosecond pulses were measured directly on the screen of the t k th streak camera (2) with a resolution of ith l ti f 0.6-0.7 ps as well as with an autocorrelator which provided an average pulse duration in the LiF:F2- train of less than 0.5 ps. A conservative estimation of the th peak power for 0.5 ps output pulses k f 05 t t l gives a minimum power of 10 MW, which greatly (by 3-4 orders) exceeds the standard peak power generated by ordinary quasi-CW dye and CC lasers.
[i] Babushkin A V, Basiev T T, Vorob'ev N S, Mirov S B, Prokhorov A M, Serdyuchenko Yu N, Shchelev M Ya., Sov. J. Quantum Electron. 16, 1492 (1986).

-2

-1

Delay AK, ps

Auto correlation curve of a pulse duration 50 of synchronously pumped LiF:F2-

7c. High energy and power color center lasers c g e e gy a d po e co o ce te ase s

Success in the growth of big size and good quality alkali-halide optical crystals and in the development of homogeneous high contrast coloration homogeneous, technique gives rise to a unique opportunity to design a large scale high power lasers and amplifiers based on CCCs. Developing a large scale homogeneously colored LiF:F2 CC active crystals with a size up to 4080200 mm3 with 4 large polished faces allowed utilization of a huge (700 J in 120 ns pulse duration) pump energy from a multistage Nd-glass laser system. In a two pass pumping scheme with the 5 J/cm2 pump energy density a transversely directed lasing of F2- CCs was realized in the nonselective 300 mm long Fabri-Perot cavity with 50% output coupling. U d th t t li Under these conditions we were able t reach th record diti bl to h the d output energy of 100 J and peak power of 1 GW at 1.12 - 1.16 m and 100 ns pulse duration.[i] [i] T T. Basiev, S V D l h k B V E h T. T B i S.V. Dolzhenko, B. V. Ershov, S B K t S. B. Kravtsov, S B Mi S. B. Mirov, V. A. Spiridonov, and V. B. Fedorov, Bull. Acad. Sci. USSR, 52, 164 (1988).

51

7c. High energy and power color center lasers

For smaller (404020 mm3) LiF:F2 crystal in transversal LiF and ( y Nd:glass coupled cavity arrangement the Nd laser pump to CCL output conversion efficiency was increased up to 80 % with the CCL output energy of 8 J at 1.15 m [i]. [i] T. T. Basiev, S.V. Dolzhenko, B. V. Ershov, S. B. Kravtsov, S. B. Mirov, V. A. Spiridonov, and V. B. Fedorov, Bull. Acad. Sci. USSR, 52 52, 164 (1988).

7c. Dependence of LiF:F2- Laser Output Energy on Mirror (R4) Reflectivity for Different LiF Crystal Optical Densities, y y p , Measured in a Transverse-Oriented Coupled Cavity Scheme

Li Laser Outpyt Ene iF O ergy for Dif fferent LiF Optcal Densities, F D J

7 6 5 4 3 2 1 0 0 20 40 60 80 100 E out for LiF Optical Density 1.15 E out for LiF Optical Density 0.7 E out for LiF Optical Density 0.45

LiF Laser Output Mirror Reflectivity (R4), %

53

7c. Dependence of LiF:F2- Laser Output Energy on Mirror (R4) Reflectivity for Different LiF Crystal Optical Densities, y y p , Measured in a Longitudinal Coupled Cavity Scheme

54

7d. Color center energy and power amplifier

In many cases it is necessary and convenient to amplify a weak laser radiation with special spectral spatial or temporal properties to a high spectral, energy or peak power values. The four-level energy diagram describing electronic-vibrational transitions of CCs together with a considerable Stokes shift and quasi-homogeneous nature of their wide absorption and , g q y g fluorescence bands, , as well as a high quantum efficiency and a large amplification cross section are very favorable factors for tackling this amplification task. CCC can be effectively used in master oscillator power amplifier (MOPA) schemes or for pico- and femtosecond pulse amplification in near IR spectral region. High Hi h emission cross section ( em = 7 10 17 cm2) and lif ti i i ti ( 710-17 d lifetime (t = 100 ns) of ) f - CCs allows to predict a high amplification gain and efficiency of LiF:F F2 2 amplifier. Comparing to dye solutions the concentration of F2- CCs in LiF crystal is rather low. Due to this the longitudinally pumped amplifier scheme is preferable for good spatial overlapping of the pump and probe radiation in the bulk CCC with 4080 mm length

55

7d. Color center energy and power amplifier

Energy dependencies of amplification gain and output energy of LiF:F2single-pass CCL amplifier with 40 mJ pump pulse.
16 14 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 05 0.0 1.2

12 10 8 6 4 2 0 0.0

0.2

0.4

0.6

0.8

1.0

Probe energy, mJ energy

56

Am mplified ou utput ene ergy, mJ

Amplifica ation Gain G n,

7d. Energy dependencies of amplification gain and output energy of LiF:F2- two-pass amplifier two pass with 40 mJ pump pulse.
50 40 30 20 10 0 0.0 10 8 6 4 2 0 2.5

0.5

1.0

1.5

2.0

Probe energy mJ energy,

57

Amp plified ou utput ene ergy, mJ J

60

12

A Amplifica ation Ga G ain,

7d. LiF:F2+ Color center energy and power amplifier lifi

The feasibility of amplification of broadband radiation of diode lasers and LEDs with the aid of LiF:F2+ CCCs was demonstrated in [i] Single pass [i]. Single-pass amplifier configuration was used. The active centres were excited by the second harmonic (532 nm) of a multimode pulsed Nd3+:YAG laser emitting pulses of 10 ns duration. A GaAs laser diode generated 85 ns radiation p pulses with linear p polarization at the wavelength 900 nm ( g (close to the + CCs) with the spectral width maximum of the fluorescence spectrum of F2 was about 55 cm-1. In this experiment a single-pass gain G=5 in the short crystal (l = 0.8 cm) and gain G=20 in the long crystal (l = 2 cm) was reached with the pump pulse energy 1 mJ. N saturation of th gain relative t th energy of th l J No t ti f the i l ti to the f the amplified radiation from the laser diode was observed. The optical gain was constant when the pump energy was in the range 0.1-1 mJ and the energy of the amplified IR radiation was 0.4-33 nJ. [i] Basiev T T, Mirov S B, Ter-Mikirtychev V V Proc. SPIE Int. Soc. Opt. Eng. 1839 227 (1992).

58

7e. Narrowline tunable color center lasers

The main advantage of CCL is the p g possibility to obtain a y coherent radiation tunable over a wide near IR spectral range. Rough selection of the oscillating wavelength can y g pp p be made by choosing appropriate color center active medium. In the nondispersive cavity the oscillation occurs at the wavelengths near the maximum of g p fluorescence curve. The width of the oscillating spectra can be up to several hundreds of cm-1. Tunable radiation of CCLs in dispersive cavities is obtained when prisms, diffraction gratings, Fabri Perrot etalons, Lyo filters and g g , , y other wavelength selective elements are utilized.

59

7e. A Schematic diagram of the commercial tu ab e color center ase s tunable co o ce te lasers MALSAN-201 S 0 (bottom) and MALSAN-203 (top)
"MALSAN-203" LiF(F ->F+ 2 2 LiF:F 2 1.06 0.53

0.82 -1.1 1.08 1 26 1 08 -1.26 0.53 LiF(F ->F+ 2 2 NaF LiF:F 2 1.06 KDP CDA 0.82 - 1.1 1.1 1.34 1 1 - 1 34 1.08 - 1.25 "MALSAN-201" YAG:Nd

60

7e. Dependencies of the efficiency of MALSAN laser on the wavelength of tunable radiation: 1. the active medium is LiF:F2- - fourth harmonic; 2. LiF(F2 F2+) - second harmonic; 3. LiF:F2- - third harmonic; 4. ( LiF:F2+*(Mg); 5. LiF(F2 F2+); 6. LiF:F2- ; 7. NaF:F2+*; 8,9. LiF:F2- first and second Stokes components, respectively

20 18 8 16

1 2 3 4 5 6 7 8 9

EFFICIEN NCY, %

14 12 10 8 6 4 2 0 0 0.2

0.4

0.6

0.8

1.2

1.4

1.6

WAVELENGTH, microns
61

7e. The dependence of the conversion efficiency of the LiF:F2- laser crystal in the non selective cavity versus y y the reflectivity of the output mirror.
60

EFFICI IENCY, %

55

50

45

40 10 20 30 40

OUTPUT MIRROR REFLECTIVITY, %

62

7e. Dependence of the LiF:F2- laser efficiency on the wavelength of tunable radiation: 1,2-for a grazing incidence schemes, 1. - two gratings, 2. - one grating and a mirror as an end reflector for its ti 2 ti d i d fl t f it first order diffraction; 3,4 in a scheme of the MALSAN laser, 3.-for the usual pump source and active element; 4. - for the optimized one. one
40 30 25 20 15 10 5 0 3 2 1 1.05 1.085 1.12 1.155 1.19 1.225 1.26

WAVELENGTH, microns

EFFICI IENCY, %

35

63

Alexandrite laser pumped LiF:F2- laser

64

Summary
For the first time t our k F th fi t ti to knowledge LiF F2l d LiF:F lasing in 1-1.3 m spectral region was realized under 740 795 nm alexandrite l li d d 740-795 l d it laser pumping. Experimental data on LiF:F2lasing are reported and peculiarities of l i t d d li iti f mechanism of F2- excitation via F3- centers are studied. t di d

65

MOTIVATION
1. Broadening of LiF F2- C l C t 1 B d i f LiF:F Color Center t i tuning range. 2. 2 Development solid state system continuously tunable in 0.2-1.3 m spectral range.

66

Shortcoming of the LiF:F2- lasing under 1.064 1 064 m excitation it ti

E

N1 2*
E2
N2 = (12( p )I p +12(g )I g )N t

(( 21(g ) +12(g ))I g + ( 21( p ) +12( p ))I p + 21 N2

2 B12* 1/ B2*1 2 1
E1

Ig 1 = t cav I g (2lN 2 ( 21 ( g ) + 12 ( g )) t 2lN 12 ( g ) act pass ))

1 1*

N1 2
Q
67

Effective F2- Color Center Cross Section

8

1=965 nm 965
6 eff ,* 10-17 cm2 m

4=1064 nm 1064 5=1079 nm

N 2sat = N

ab ( p ) ab ( p ) + em ( p )

2=1029 nm 3=1047 nm
2

excitation e c o nm 950-980 1.047 1 047 1.064

N2sat/N0 ~0.97 0.43 0 43 0.26

3 4

2
5

0 1.0 1.1 1.2 1.3

Wavelength, nm

eff em

em ( os ) ab ( p ) em ( p ) ab ( osp ) = ab ( p ) + em ( p )

68

Comparison of main spectroscopic properties of LiF:F2-, LiF:F3- , LiF:F2+ and Ti S Ti-S laser media

Media LiF:F2LiF:F3LiF:F2+ TiS pp Sapphire

ab nm

ab nm

em nm 1130 920 906 760

em nm 180 170 185 175

em cm2 6*10-17 2*10-17 1.5*10-16 2.7*10-19

ns 55 10 20 3150

% 60 10 20 80

Damage J/cm2 10 10 10 10

K /mK 14.2 14.2 14.2 35

960 157 800 150 600 140 480 100

69

Structure of Color Centers in LiF crystals y

F2- center

F3- center

-Li+

-F-

-Vacancy

e -Electron 70

Idea of the lasing mechanism of the LiF:F2- crystal under alexandrite l l d it laser pumping i

Absorption and Emission spectra of F2Color Center C l C t

F3-+h793 F3-* F3-*F3-+h920 * F2-+h920 F2-* F2-*F2-+h100-1300

700 800 900 1000 1100

Wavelength, nm

1200

1300

Absorption and Emission spectra of F3Color Center

700 800 900 1000 1100 1200 1300

Wavelength, nm

71

Absorption spectrum of the LiF active medium

Absorption, cm-1

5 4 3 2 1 0 600 700 800

D=108 rad

F 2F3

900 1000 1100 1200 1300

Wavelength, nm

72

LiF:F2- Dispersive Cavity

Prism Mirror Pump Grating

LiF:F2-

Mirror

73

Experimental Results pe e ta esu ts

10

L Laser Efficiency

8 6 4 2 0 1.00

LiF:F2- tuning Curve under 793 nm Alexandrite laser pumping

1.05

1.10

1.15

1.20

1.25

1.30

Wavelength, nm

1.0 0.8 0.6 0.4 0.2 0.0 00 1.0

2 1

Normalized Tuning Curves of LiF:F2Color Center Laser under different pumping wavelength 1-=1064nm YAG:Nd3+ laser 2-=1047nm YLF:Nd3+ laser 3-=793nm Alexandrite laser
74

1.1

1.2

1.3

W avelength, nm

Photostability o LiF:F2- Laser otostab ty of ase

Spectral Dependence of Photoionization Probability P b bili (W) of F2- and F3- C l Centers f d Color C in LiF at RT
100

F2F3-

W, arb. un n.

80 60 40 20 0 320 340 360 380 400 420

Alexandrite Laser two photon/ two step excitation

wavelength,nm

310-390nm 620-780nm 310-380nm 310 380nm 620-760nm

F3-

F2- 75

The kinetics of F3- color center destruction under 740 nm excitation it ti

0.7 0.6
37.7 MW/cm2 25.7 MW/cm2 15.6 MW/cm2

K (c -1) cm

0.5 0.4 0.3 0.2 0.1 0.0 0 50

Rate of F3- concentration change

100 150 200
2

time (seconds)

F3-+2 h740 F3-*+ h740 F3+ e

-1 -1 K/dt (cm s )

1
0.8 0.7 0.6

0.4

K ~ I 2 t

0.2

10

20

30

40

50

2 Intensity @ 740 nm (MW/cm )76

LiF:F2- Oscillation Efficiency Decay under different pumping wavelength

Oscilla ation De ecay

1.0 0.8 08 0.6 0.4 04 0.2 0.0 00 0

pump=793 nm pump=760 nm pump=750 nm

10 20 30 40 50 60

Time, min

77

Conclusion
For the first time to our knowledge a direct alexandrite laser pumping of LiF:F2- laser was realized Tunable oscillation of LiF:F2- laser in 1-1.3 m spectral range with maximum efficiency 10% was achieved two-step mechanism of photoionization of F3- Color Center d =740 C t under 740 nm excitation was demonstrated it ti d t t d experimentally. Stable Oscillation of LiF:F2- laser at RT under =793 nm 793 excitation was predicted and shown experimentally

78

All-Solid-State System Based On Alexandrite - LiF:F2+** Laser For Deep UV (196 nm) And Mid-IR (4000 nm) Spectral Ranges B. Boczar, R. Frost, B. Pryor,
S.B.Mirov, V.V.Fedorov
Dept. of Physics, University of Alabama at Birmingham, Birmingham AL 35294 Tel: (205) 934-8088; Fax: (20 ) 934-8042 l (20 ) 934-8088 (205) 934-8042; E-mail: mirov@uab.edu

I. Rousseva
Light Age, Inc Two Riverview Drive, Somerset, NJ 08873 Tel: (732) 563-0600;Fax: (732) 563-1571; 563563E-mail: lightage@aol com lightage@aol.com

A.Yu. Dergachev A Yu
Q-Peak, Inc., 135 South Road, Bedford, MA 01730 E-mail: dergachev@qpeak.com
Motivation 2.Introduction 3. Room Temperature Stable LiF:F2+** Lasers Optical properties of LiF:F2+** crystals, g p y (>400 ultrabroadband tuning capability ( nm)? nonselective cavity, dispersive cavity, operational characteristics 4. Alexandrite-CCL System Design, y g , Frequency up-conversion (CLBO); Downconversion (LiNbO3 Ag3AsS3) 5. Conclusions
1.

OUTLINE

Highlights of Current Findings

We present a novel all solid-state laser system that exploits the best features of th hi h gain, d lik LiF F2+** f the high i dye-like LiF:F + medium and the high energy storage alexandrite laser. It is ideal for efficient deep UV (196 204 nm =23%) and (196-204 nm, mid-IR (2.2-5.5 m, =10%) lasing.
79 2002 OSA Annual Meeting and Exhibit/LS-XVIII

Motivation
Pulsed Laser sources with deep UV (below 200 nm) and mid IR (3-5 m) output radiation have attracted significant attention for use in integrated circuit processing, medicine, molecular spectroscopy, spectroscopy and remote sensing sensing. CCL with frequency up- and down conversion are very attractive candidates: easy to scale up, high efficiency (tens of %), wide amplification band (hundreds of nm) high wavelength stability nm), stability, extremely narrow oscillation spectral width, achievable virtually without power loss, low threshold, high gain, short oscillation built-up time, and absence of temporal delay between pump and output pulses. t t l Our goal was to demonstrate that Alexandrite - LiF:F2+** CCL combination exploits the best features of both the high gain, dye-like dye like CCL and the high energy storage alexandrite laser and is a promising drive source for a number of efficient nonlinear processes, including harmonic, sum-frequency and difference-frequency generation that offers simple and economical way to achieve widely tunable narrow-linewidth performance in the UV-middle IR spectral range.

80

Novel LiF:F2+** Crystals

(U.S. Patent No. 5,796,762 (U S P t t N 5 796 762 )
10

80000 70000 532 nm Excitation 633 nm Excitation

A Absorption Coefficient, cm-1 m

Intensity, arb. units

F 2 C e n te r
6

60000 50000 40000 30000 20000 10000

F 2 **
2

F 2 **-lik e

0 10 8 6 4
14

0 600 700 800 900 1000 1100 1200 1300

F re q u e n c y, H z (x 1 0

Wavelength, nm

40000

30000

New F 2 **-like Center (measured at 24 K) F 2 ** Center (measured at 13 K)

+

Intensity, arb. units

20000

10000

0 700 800 900 1000 1100 1200 1300 1400

W avelength, nm

81

Major physicochemical and mechanical properties of LiF crystal t l

Parameters Tm, melting point (oC) Solubility, (g/100g H2O) H, Knupp hardness (kg/mm2) Value 870 0.14 99 Parameters E, Youngs modulus (kg/mm2); Value 8820 0.28 1.2-4.0

, Poissons coefficient
S, compression (tension) or bending t b di strength (k / th (kg/mm2)

d, lattice constant (A);

4.03 2.64 14.2

R, thermal shock parameter (W/m) n, refractive index n2, nonlinear index (1022 m2/V2)

43-143 1.38 2.7

, density (g/cm3);
K, coefficient of thermal conductivity (W/m oC)

, coefficient of linear ffi i t f li

expansion (10-6/ oC) Transparency region (m)

32.0 32 0

dn/dT, temperature derivative d /dT t t d i ti refractive index ( 10-5/ oC)

-1.2 12

0.1-7.0

82

Input/output dependence for LiF:F2+** laser at 300 K with nonselective resonator under pumping with:
(1) pump=740 nm (real=31%; diff.=28%) nm, (2) pump=683 nm, (real=53%; diff.=58%; quant.=81%) (3) is linear fit. 100 1 2 80 3
Output energ per puls mJ gy se, 60 40 20 0 0 50 100 150 200 Input enegy per pulse, mJ 250
83

Alexandrite laser pumped tunable LiF:F LiF F2+** l laser

25 Energy per pulse, mJ m

Mirror M3 HR at 0 8 m0.8

20 15 10 5 0 800 900 1000 1100 W avelength, nm 1200 1 2

LiF:F2+** Mirror M1 HR at 0.8 m1.2m

Grating 1200 gr/mm

Pump P
Telescope

40

=1cm-1
30

Intensi ity

Mirror M3 HR at 0.8 mReflective Conner

20

=0.26 cm-1

10

300

350

400

450

500

pixel

84

Fundamental, SHG, THG, and SFG conversion efficiency with respect to alexandrite laser pump energy as a function of wavelength for LiF:F2+** laser
Efficien relative to Alexand ncy drite Beam,% %
14 12 10 8 6 4 2 0

1 2 3 3 4
pump

200

400

600

800

1000

1200

1400

Wavelength, nm

85

Typical temporal shapes and delays p p between the pump and the LiF:F2+** oscillating pulses
2.0 1.8 1.6

t1+t2

t3

Sign arb.un nal, n.

1.4 14 1.2 1.0 0.8 0.6 0.4 0.2 0.0 550 600 650 700 750 800 850

time, ns ,
86

Optical arrangement for sum frequency generation of deep UV radiation deep-UV

P2 800-1200 nm M6 P1 G T2 M3 P3

M1

Alexandrite Laser
M4 780-720 nm NC12 LiF:F2+** M5 260-240 nm T1

NC13 NC3 DP1

M2 PR1 PR2

DP2

800 00 800-1200 nm

196-205 nm

196-205 nm

87

Theoretically calculated angular tuning curves in CLBO crystal for different wavelengths of the pump radiation 240 nm, 243 nm, and 246 nm versus the SFG spectral output
SFG Phase matching for CLBO. Alexandrite laser radiation (3w) is mixed (type 1, ooe interaction) with the tunable radiation of alexandrite laser pumped LiF:F2+** laser
100 90 80 Phase matching Angle, degrees 70 3w=0.240 60 50 40 30 20 10 0 0.192 3w=0.243

3w=0.246

0.193

0.194

0.195

0.196

0.197

0.198

0.199

0.2

0.20

SFG Wavelength, microns

88

Deep UV Frequency Upconversion in CLBO

233.66nm(701nm/3)+1110 nm=193 nm (900)
22 20 18 16

245 nm+1035 nm (=900)

247 nm+1030 nm (=850)

Efficie ency, P/P3

14 12 10 8 6 4 2 0 195 196

248 nm+1035 nm (=820)

243 nm+1049 nm (=900) 247 nm+1110 nm (=730)

241 nm+1061 nm (=900)

197 198 199

247 nm+1173 nm (=690)

201 202 203 204 205

200

Wavelength, nm
89

FREQUENCY DOWNCONVERSION (40-60 ns pump pulse duration)

Glan Prism (5) M2 Digital Oscilloscope Polarization Rotator (4) M2 3:1 (12) HR M6 Input mirror (M7) LiF:F2+** (8) Beam comp. 5:1 (12) Beamsplitter (M1) 80/20 or 90/10 M11 M10 ooe interaction e (3) k M27 Beamcombiner M3 M11 k Alexandrite Laser E=80 mJ at 3=740nm =60 ns; f=10 Hz

Beam exp. Slit

Joulemeter J4-10 Ge Filter (16)

Grating (9)

1=2.2-5 m
M15

LiNbO3 M15

Beam compressor 5:1 ( ) p (12)

o (1)

o (2)

Ge filter-Spectrograph-InSb

90

Experimental and theoretical DFG quantum efficiency versus DFG wavelength for LiNbO3 (Li/Nb=1) nonlinear crystal. Power density of alexandrite laser was about 3 MW/cm2. Power density of LiF:F2+ laser was not constant. It varied from 6MW/cm2 for 3m DFG output to 0.3 MW/cm2 for spectral regions around 2.2 and 5 m.
40 35 30 IR (m ic ro n ) v s Q . E ff(T h ) IR (m ic ro n ) v s Q .E ff(E x p )

Effic ciency (%)

25 20 15 10 5 0 2 3 4 5 6

D F G W a v e le n g th , 1 ,( m )

91

The external phase matching angle for Ag3AsS3. Inset: DFG wavelengths as a function of LiF:F2+** wavelengths at a pump wavelength, 3 of 736.7 nm
A g 3A s S
3

DFG

7 3 6 .6 9 n m p u m p
(D F G ) v s (F
+ 2

) a t 3 (p u m p ) = 7 3 6 .6 9 n m

20
DFG Wavelength, (m)

10 8 6 4 2 0
T h e o r e tic a l E x p e r im e n ta l

E External phase matc ching angle (degrees)

-2 0

0 .7

0 .8

0 .9

2 ( m )

1 .0

1 .1
(F
2

1 .2
)

1 .3

1 .4

-4 0

T h e o r e tic a l A n g le E x p e r im e n ta l A n g le -6 0

-8 0 0 .7 0 .8 0 .9 1 .0 1 .1 1 .2 1 .3 1 .4

2 ( m )

(F

+ 2

92

FREQUENCY DOWNCONVERSION 500-600 ns pump pulse duration obtainable with Light Age, Inc. pulsed stretched 101PAL
800-1200 nm P2 M3 P1 G T1 M5

Results
LiNbO3 PR1 3-4 m

T2

Alexandrite Laser
M1 780-720 nm

LiF:F2+**
780-720 nm M2

M4

Temporal overlapping of LiF:F2+**color color center laser oscillation (red) and oscillation of the Alexandrite laser (black).

0.06 0.05 Signal, V 0.04 0.03 0.02 0.01 0.00 1 Time, s 2

Pulsewidth: 500 ns Pump wavelength: 737 nm LiF wavelength: 919 nm DFG wavelength: 3.7m Pump energy: 440 mJ Mixed pulses: LiF energy: 27 mJ gy Residual pump: 76 mJ Nonlinear material: Two 24 mm LiNbO3 with walk-off compensation DFG 3.7 m energy: 1.04 mJ

93

FREQUENCY DOWNCONVERSION ( (500-600 ns pump p p p pulse duration) )

1

Energy of 3.7 um DFG radiation, mJ y G

Energ of 3.7 um DFG output, mJ gy

=0.25%

=4%

0 100

0 0 5 10 15 20 25 30

150

200

250

300

350

400

450

500

Alexandrite (737 nm) pump energy , mJ

E Energy of 919 nm LiF output, mJ m J
30 25 20 15 10 5 0 100

Energy of LiF pump radiation, mJ

E Energy of 3.7 um DFG output, mJ m J

=6.2%

=1.5%

0 20 30 40 50 60 70 80

150

200

250

300

350

400

450

500

Alexandrite (737nm) pump energy, mJ

Energy of residual 737 nm, mJ

94

CONCLUSIONS
1. Photo and thermostable regime of LiF:F2+** lasing was realized due to a novel technology of LiF:F2+ stabilized crystal formation. We demonstrated solid-state laser system for deep UV and p g mid IR spectral range. The tunable radiation in 196- 204 nm with 23 % efficiency and up to 0.5 mJ pulse energy has been realized. The difference frequency generation between radiation of alexandrite and LiF:F2+** lasers in 2.2 5.5 m was achieved with 10% efficiency in LiNbO3 crystal at 3 m for 50 ns pulses. Output energies of 1 04 mJ at wavelength of 3 7 m for a 1.04 3.7 long, 600 ns, pulse duration was obtained in LiNbO3 crystal. 2. 3. 4. 4

5. 5

95

Tunable Room Temperature Stable Color Center Distributed Feedback Laser Di t ib t d F db k L

Jason G. Parker, Mentor: Sergey B. Mirov Collaborators: Dmitri Martyshkin, Vladimir V. Fedorov y ,

Laser and Photonics Research Center

Physics Department, University of Alabama at Birmingham 1300 University Blvd., Birmingham, AL 35294-1170, mirov@uab.edu

96

Introduction
Tunable room temperature distributed feedback color center lasers were studied. studied

Motivation
Current tunable lasers: utilize external cavities with dispersive elements that provide tunability across the amplification band. However, utilization of an external cavity makes the overall system not compact and bulky. It is very advantageous to combine inside laser crystals all laser elements (gain medium and positive feedback mirrors and/or dispersive elements). The distributed feedback (DFB) phenomenon makes it possible to do this while still achieving tunable oscillation. Newly discovered LiF:F2+** crystals combine the thermal- and photo-stability of impurity doped laser crystals with the high absorption and emission cross-sections of laser dyes. Until now, no tunable room temperature stable DFB lasers had been created using color center crystals (CCCs).
97

Distributed feedback (DFB) lasers

The DFB laser uses a periodic modulation of its medium to attain selective oscillation. The oscillation This means that this modulation acts as a diffraction grating and thus follows the grating equation.

(sin i sin m ) = m l
=period, i=angle of incident beam from surface normal, m=angle of reflected beam from normal, m=order of diffraction, l=lasing wavelength

Which in our case (i=90, m=-90) reduces to: ( , ) Periodic modulations (excited LiF:F2+)

2 = m l

LiF:F LiF F2+

98

Grating construction by interference

The interference of two equal laser beams creates a fringe normal to the point of intersection and sinusoidal in nature. Our setup uses this fringe to penetrate the crystal periodically and create our (dynamic) grating.
Initial laser beam

Beam split into nearly equal parts Beam rejoined to obtain interference

LiF crystal

99

Picture of setup
Laser Beam Cylindrical lens Mirror Mirror Beam splitter

Mirror Sample DFB output beam Spectroscopic fiber

100

Spectroscopic analysis
Spectroscopy was used to know if DFB was realized Typical lasing with LiF:F2+ Spectroscopy realized. produces a spectrum approximately 15 nm in width. However, because feedback is selective in the DFB laser, DFB lasing should occur at a very specific wavelength, determined by the grating equation. The graph below shows one instance of DFB lasing transposed over one instance of typical LiF:F2+ broadband lasing. The linewidth of DFB lasing was measured and found to be less than 0.2 cm-1 (0.017 nm).
1.2 1.0 Intensity, arb. units 0.8 0.6 0.4 04 0.2 0.0 00 900 920 940 960
101
Broad LiF:F2+ lasing DFB lasing

Wavelength, nm

Proof of lasing due to DFB

If a particular peak is due to DFB, it should completely disappear when either shoulder If DFB is blocked.

6000

Intensi arb. units ity,

Intensity, arb. units

5000 4000 3000

400

Intensi arb. units ity,

600

600 400 200 0

2000 1000 0 900 920 940 960

200

0 900 920 940 960

900

920

940

960

Wavelength, W l th nm

Wavelength, nm W l h

Wavelength, W l th nm

DFB lasing at 945 nm

Right shoulder blocked

Left shoulder blocked

This technique was employed in all instances in which DFB occurred.

102

Tuning results
The LiF DFB laser was fully tunable from 962 to 882 nm This is a large range of nm. tuning for any laser, and we suspect this range can grow considerably. The following figure shows instances taken throughout a tuning run from 962 to 882 nm. The small hump centered around 940 nm is due to normal LiF:F2+ broadband lasing (with oscillation from the crystals faces).

1.2 In ntensity, arb. units a 1.0 10 0.8 0.6 0.4 0.2 0.0 880 900 920 940 960
103
882 nm 900 nm 910 nm 923 nm 932 nm 955 nm 962 nm

Wavelength, nm

Power relationship
The following graph shows the relationship between pumping power and output power for our laser. A linear dependence of output energy on pumping energy was determined. The maximum efficiency reached was 3%. Also, the optical threshold of pumping was found to be 1.2 mJ.

80 60 40 20 0 0

Pump Energy, mJ vs OutPut Energy, um

Pump-fit vs Output-fit

Output En nergy, uJ

10
104

Pump Energy, mJ

Conclusion
For the first time tunable room temperature stable color center DFB lasing has been For time, realized. A dynamic grating was constructed inside the CCC using interference. The laser showed a large tuning range and we believe this range can grow considerably. A linear relationship between pump power and output power was determined, with a maximum pumping efficiency of 3%. Also, the optical pumping threshold was found i i ffi i f 3% Al h i l i h h ld f d to be 1.2 mJ. The results were prepared for presentation in the Photonics West LASE 2004 conference and publication in the physics journal Applied Physics Letters. f d bli ti i th h i j l A li d Ph i L tt

105

Persistent photon-gated spectral hole burning in LiF:F2- color center crystal (V Fedorov S.Mirov Appl Phys. Lett. 79, 2318 2320 (V.Fedorov, S Mirov Appl. Phys Lett 79 2318-2320
(2001).
LiF:F2+** Color Center l C t laser Alexandrite laser, Light A I Li ht Age, Inc.
The Q-switched alexandrite laser =720-800 nm, f= 25, Hz, =80ns, E=80 mJ

ARC-750 spectrometer (=0.2 cm-1) Close Cycle helium refrigerator, Janis Research Co Model CCS450 (14K 425K). (14K-425K)

LiF:F2- crystals was irradiated by a 60Co source with a dose D=107rad

106

Persistent photon-gated spectral hole burning in LiF:F2color center crystal l t t l

F2- + h 1.04m
ZPL absorption
Optical Density

F2-* + h 0.52 m

F2 + e

E E2

h 0.52m
E// E2

h h 1.04m

1038

1039

1040 Wavelength,nm

1041

1042

1.7cm 1 = 1 7 -1
K 1039.0

P1.04 m=5 MW/cm2 , P0.52 m=0.1 MW/cm2 . time -20 min, T=14K. laser=0.2-0.3 cm-1

1039.5

1040.0

1040.5

1041.0

Wavelength, nm

107

S1/2

3d 105s

LASER ATOMIC FLUORESCENCE SPECTROSCOPY RESEARCH GOAL: Develop novel laser atomic fluorescence instrument for heavy metal detection at sub-ppt level for biomedical and industrial applications.
PC HV Pulse Generator PG-200 PG 200 CC CCD Spect og ap Spectrograph ARC-750
70000 RO water 60000
2

2 2

P3/2 P1/2
reg(2)

3d 104p

ex

reg(1)

2 2

D 3/2 D 5/2

3d 94s2

S1/2

3d 104s

ex = 324.754 nm reg1 = 510.554 nm reg2 = 570 024 nm 570.024 2

Fiber Guide
Intensity, arb b.un

Distilled water

Cu - 10 g/l

40000 30000 20000 Cu 10000

3 (2nd order)

r) 3 (2nd order

Cu

Lens Lens Tunable UV laser p Sample (in graphite furnace)

Cu

0 505 510 515 505 510 515 505 510 515

Wavelength, nm

Aperture

LAF detection of Cu atoms in water sample (Cu-10g/L), distilled water, and deionized water (prepared using reverse , (p p g osmosis at 18 megohm resistance)

108

3 (2nd orde er)

50000

Application of LiF laser in Optoacoustic medical i i di l imaging i

104

Absorption Coefficient, a (cm -1) C

1000

Hb HbO2 800 nm 757 nm 1060 nm

Axial in-Depth, mm

10

100

20

30

10

40

920 nm

10

20 30 Lateral, mm

40

0.1 200

0.500

0.550 0.600 Contrast Bar

0.650

400

600

800

1000

1200

Wavelength, nm

109