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New laser crystals of double halogenides RE:MPb2X5 (M= K, Rb X= Cl, Br)
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Crystals of group RE:MPb2X5 ( M=K, Rb X= Cl, Br) is a new promising active media for lasers, operating on different wavelengths in the range from UV to mid-IR, including those for TV amplifiers with diode pumping. Interest to this material, which has high RE segregation coefficients and a set of attractive properties increased considerably to date, while:
  • Low energy of phonons in halogenides provides mainly radiative transitions between adjacent levels with the gap = 1500 cm-1 as a result emission bands cover the wide spectral region from UV (transitions from upper excited levels) to 9-10 µm in the mid-IR (transitions within both excited and ground RE multiplets);
  • Complex of long decay times for lower states, high values of absorption cross-sections and low rates of the nonradiative multiphonon relaxation makes these crystals promising for their application as active media for UV/VIS lasers with up-conversion pumping;
  • Broad variations of RE type and dopant concentrations are possible for RE:MPb2X5 crystals;
  • Relatively broad, structureless luminescence bands in RE:MPb2X5 crystals allow fine tuning of the stimulated emission frequency;
  • To date stimulated emission has been obtained for 1.064 µm (Nd), 1.3 and 2.4 µm (Dy) and 4.6 µm (Er);
  • It is important that intense absorption bands match the laser diodes emission for many RE ions in MPb2X5 crystals.
Protective/antireflection coatings may be performed on the aperture surfaces of the produced elements. Typical sizes of optical elements are 4 x 4 x (5-15) mm3.

Example of laser element material:
Chemical formula
KPb2Cl5 : Dy3+
Transition
6H9/2 + 6F11/2 => 6H15/2
Concentration of Dy ions
1 %
Quantum yield
100 %
Lifetime of excited state
1.19 µs
Transition cross section, 10-21cm2
9.5
Wavelength, µm
1.3
Main characteristics of RE:MPb2X5 (M=K,Rb X=Cl,Br) crystals:
 
KPb2Cl5
RbPb2Cl5
KPb2Br5
RbPb2Br5
Transparency range, µm
0.3 - 20
0.3 - 20
0.3 - 30
0.3 - 30
Space group
P22 / c
P22 / c
P22 / c
I4mcm
Melting temperature, C°
434
423
382
382
Density, G/cm3
4.629
5.041
5.619
5.83
Refraction index (632.8 nm)
2.019
2.019
2.2
2.2
Thermal conductivity, W/m x K
4
4
-
-
Mohs hardness
2.5
2.5
2.5
2.5
Phonon energy, cm-1
203
203
133
133
Lattice parameters,
a,A
8.854(2)
8.959
9.256(2)
8.41
b,A
7.927(2)
7.973
8.365(2)
8.365(2)
c,A
12.485(3)
12.493
13.025(3)
14.5
(deg)
90.05(3)
90.12
90.00(3)
90.00(3)
V
876.3(4)
895.3
1008.4(4)
1025.6
Z
4
4
4
4
Rare Earth ion
Pr
Nd
Dy [lit.]
Er
Yb [lit.]
Tm
Ho
Maximum peak absorbtion cross section,σp (λ max), 10-20cm 2
10.9
14.9
51.8
21.5
1.78
2.85
11
Wavelength (λ max), nm
487
589
129.7
379.4
982
797.9
453
Peak absorption cross section for LD pumping σp(λ), 10-20cm 2
-
6.22
0.9
4.8
1.78
-
-
Wavelength (λ ), nm
-
808.2
810.4
982.6
982
800
900
The teams of Prof. Isaenko and MolTech are also interested in joint investigations of the stimulated emission at RE:MPb2X5 using different lasing configurations.
I N Q U I R Y    F O R M :
Rare Earth Dopant:
Pr
Nd
Dy
Er
polished:
 a-b b-c a-c or d  -->BLOCKor BLOCK
Dimensions/Tolerances:
 a = mm;         b = mm;
Rare Earth Dopant:
Yb
Tm
Ho
other
 c = mm; or dia. = mm
Dopant conc. (max 10%):
Host:
KPb2Cl5
RbPb2Cl5
KPb2Br5
RbPb2Br5
Coating:
Quantity of elements:
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Literature:
  1. Isaenko L.I., Yelisseyev A.P., Nadolinny V.A., Paskov V.M., Payne S., Solarz R, Dirnstorfer I., Meyer B., Growth and spectroscopic properties of rare earth doped chloride crystals for telecommunication amplifiers. - Abstr. II Intern. Symp. Modern Problems of Laser Physics, 1997, Novosibirsk, p.II - 10.
  2. Isaenko L.I., Yelisseyev A.P., Nadolinny V.A., Paskov V.M., Nostrand M., Page R., Payne S., Solarz R. Spectroscopic investigation of rare earth doped chloride single crystals for telecommunication amplifiers - Proceedings SPIE, 1998, p. 3424-3430.
  3. Isaenko L.I., Yelisseyev A.P., Nadolinny V.A., Paskov V.M., Payne S., Solarz R. Growth and spectroscopic properties of rare earth doped chlorides - Proceedings Second Intern. Symp. On Modern Problems of Laser Physics, 1998, Novosibirsk., p. 397-414.
  4. Nostrand M.C., Page R.H., Payne W.F., Krupke W.F., Schunemann S. and Isaenko L.I. Spectroscopic data infrared transitions in CaGa2S4: Dy3+ and KPb2Cl5: Dy3+. - ASSL TOPS XIX (OSA/IEEE), Washington, D.C., 1998, p.524.
  5. Tkachuk A., Ivanova S., Isaenko L., Yelisseyev A., Payne S., Solarz R., Nostrand M., Page R., Payne S. Comparative spectroscopic study of Dy3+ doped double chloride and double fluoride crystals for telecommunication amplifiers and IR lasers. - Acta Physica Polonica A, 1999, v.95(3), p.381-394.
  6. Tkachuk A., Ivanova S., Isaenko L., Yelisseyev A., Payne S., Solarz R., Nostrand M., Page R, Payne S. Dy 3+ doped double chloride and double fluoride crystals as active media for IR lasers and telecommunication amplifiers. - J. Optical Technology, 1999, v.66, N5 p.95-97.
  7. Tkachuk A., Ivanova S., Isaenko L., Yelisseyev A., Payne S., Solarz R., Nostrand M., Page R, Payne S. Spectroscopic study of Dy3+ and Yb3+ doped double chloride and double fluoride crystals for telecommunication amplifiers and IR lasers. - Tec. Digest of 18th Congress of the Int. Commisions for Optics: ICO XVIII Optics for the Next Millenium, Proc. SPIE, 1999, vol.3749, p.660-661.
  8. Isaenko L., Yelisseyev A., Payne S.., Zondy J.-J. Nonlinear and laser crystals for mid IR region. - Abstracts the 1st Asian Conference on Crystal Growth and Crystal Technology, Japan, Aug.-Sept. 2000, p.110-111.
  9. Isaenko L., Yelisseyev A., Tkachuk A., Ivanova S., Vatnik S., Merkulov A., Payne S., Nostrand M., Page R. New laser crystals based on KPb2Cl5 for IR region. - Abstracts the PE-MRS-IU MRS ICEM2000, Strasbourg, France, May 2000, p.K-10.
  10. Kaing T., Zondy J.-J., Yelisseyev A.. Lobanov S., Isaenko L. Compact, broadly tunable, mid-IR source for the spectroscopic investigation of molecular reference lines in the 27- to 33- THz range. - IEEE Transactions on Ultrasonics, Ferroelectrics, and Frequency Control, 2000, v.47, No 2, p.506-511.
  11. Nostrand M.C., Page R.H., Payne W.F., Krupke W.F., Schunemann P.G. and Isaenko L.I. Laser demonstration of rare-earth in low-phonon-chloride and sulfide crystals. - in Advanced Solid State Lasers, H. Injeyan, U. Keller and C.Marshall, eds., OSA TOPS (USA), 34, 2000, p.459-463.
  12. Payne S. A., Page R H., Shumenan P.G., Isaenko L.I. Laser demonstration of rare elements ions in low phonon chloride and sulfite crystals. - Abstracts. ASSL Topical Meetings, 13-16 Feb. 2000, Davos, p.26.
  13. Tkachuk A., Ivanova S., Isaenko L., Yelisseyev A., Nostrand M., Page R., Payne S. Luminescence and laser action of Nd(3+) doped double chloride crystal. - Abstracts. CLEO/IQEC, Nice, France, September, 2000, p. CtuK42.
  14. Tkachuk A., Ivanova S., Isaenko L., Yelisseyev A., Krupke W., Payne S., Solarz R., Nostrand M., Page R., Payne S. Spectroscopic study of TR3+ doped double chloride crystals promising for VIS and IR solid state lasers (TR3+ = Dy3+, Nd3+, Tb3+ and Yb3+ (poster). - Technical Program of X conf. On Laser Optics, June 26-30, St. Petersburg, Russia, p.63, ThA1-p50.
  15. Virovets A., Naumov D., Merkulov A., Isaenko L., V. Pashkov The investigation of crystal structure of KPb2Cl5 - The proceeding of V international conference “Crystals: Growth, properties, real structure, applications”. Alexandrov, 2001, vol. 1, p. 83-86 (in Russian).
  16. Tkachuk A., Ivanova S., Isaenko L., Yelisseyev A., Payne S., Solarz R., Page R., Nostrand M. The spectroscopic investigation of double chloride potassium-lead crystals doped by neodymium KPb2Cl5: Nd3+ - Optics and spectroscopy, vol. 91, 6, 2001, p. 942-954 (in Russian).
  17. Isaenko L., Yelisseyev A., Tkachuk A., Ivanova S., Vatnik S., Merkulov A., Payne S., Nostrand M. , Page R. New laser crystals based on KPb2Cl5 for IR region. - Materials Science and Engineering, B81, 2001, p.188-190.
  18. Nostrand M.C., Page R.H., Payne S.A., Isaenko L.I. , Yelisseyev A. Optical properties and laser action for rare earth-doped KPb2Cl5. - Journal of Optical Society of America (JOSA), 2001 v.18, p.264-276.
  19. Ogorodnikov I. N., Pustovarov V.A., Kirm M., Kruzhalov A.V., Isaenko L.I., Yelisseyev A.P. Ŕ time-resolved vacuum ultraviolet spectroscopy study of KPb2Cl5:RE single crystals (RE=Nd, Er, and Yb) - HASYLAB Annual Report 2001 Part 1. edited Gehrke R., Krell U., Schneider J.R.,/Hamburger, Synchotronstranstrahlungslabor HASYLAB at Deutsches Elecrtronen-Synchrotron DESY, p.233-234.
  20. Isaenko L., Yelisseyev A., Tkachuk A., Ivanova S., Payne S., Page R., Nostrand M. New low-phonon frequency crystals, based on rare earth doped double chlorides and bromides for multiwavelengths diode pumped solid-state lasers. Proceedings SPIE / Proceedings 7th International Symposium on Laser Metrology Applied to Science, Industry and Everyday Life, 2002, v.4900, part 2, (Eds. Yu. Chugui, S. Bagaev, A. Weckenmann, P.Osanna), p.962-972.
  21. Ivanova S., Tkachuk A., Joubert M.F., Guyot Y., Isaenko L., Yelisseyev A., and Payne S. Up-conversion in Er3+ : KPb2Cl5 crystals under laser diode pumping. - Technical Digest of International Conference on PHYSICS OF LASER CRYSTALS, ICPLC'2002, August 26 - September 2, 2002, Kharkiv - Stary Saltov, 2002, p.O2.
  22. Tkachuk A., Ivanova S., Isaenko L., Yelisseyev A., Mironov D., Nostrand M., Page R. and Payne S. Spectroscopic properties of TR3+ doped double chloride crystals. - Proceeding SPIE/The XI Feofilov Symposium on spectroscopy of crystals activated by rare earth and transitional metal ions, Kazan Republic Tatarstan, Russian Federation, September 24-28, 2002, v.4766, (Ed. B.Z. Malkin, A.A. Kaplyanskii), p. 537-541.
  23. Tkachuk A., Ivanova S., Isaenko L., Yelisseyev A., Mironov D., Nostrand M., Page R., Payne S. Spectroscopic properties of TR3+ doped chloride crystals promising for VIS and IR solid state lasers (TR3+ = Dy3+, Nd3+, Tb3+ and Yb3+). - Technical Program of X Conferency on Laser Optics, June 26-30, 2002, St. Pterrsburg, Russia, p.63, ThA1-p.50.
  24. Tkachuk A., Ivanova S., Isaenko L., Yelisseyev A., Payne S., Page R., and Nostrand M. Rare Earth Doped Double Chloride Crystals (TR3+ : KPb2Cl5) as New Materials for UV, VIS and Mid-IR Solid State Lasers - Technical Digest of International Quantum Electronics Conference IQEC/LAT 2002, June 22-27, Moscow, RUSSIA p. 223. QMA6.
  25. Tkachuk A., Ivanova S., Isaenko L., Yelisseyev A., Payne S., Joubert M.F., and Guyot Y. Population of High Excited Levels in Erbium Doped Double Chloride Crystal Er3+ : KPb2Cl5 as Potential Material for UV and VIS Lasers - Technical Digest of International Quantum Electronics Conference IQEC/LAT 2002, June 22-27, Moscow, RUSSIA. p. 104. QsuR7.
  26. R. Balda, M. Voda, M. Al-Saleh, and J. Fernández. Visible luminescence in KPb2Cl5:Pr3+ crystal. Journal Luminescence, (2002) v. 97, p. 190
  27. A. Mendioroz, J. Fernandez, , M. Voda, M. Al-Saleh, A J.Garcia-Adeva, and R.. Balda. Anti-Stockes laser cooling in Yb3+-doped KPb2Cl5 crystal. Optics Letters, 2002, v. 27, p. 1525
  28. Tkachuk A.M., Ivanova S.E., Isaenko L.I., Yelisseyev A.P., Joubert M.-F., Guyot Y., Payne S. The spectroscopic investigation of Er-doped crystals of potassium- rubidium binary chlorine Pb2Cl5:Er3+. I. Optic spectra an relaxation of exited state Er-ions in the crystals of potassium- rubidium binary chlorine. – Solid State Spectroscopy, 2003, 93, 3, p. 416-435
  29. R. Balda, J. Fernandez, A. Mendioroz, M. Voda and M. Al-Saleh. Infrared to visible upconversion in Pr3+-doped KPb2Cl5 crystal. Optical Materials, 2003 v. 24, p.91.
  30. R. Balda, J. Fernandez, A. Mendioroz, M. Voda, and M. Al-Saleh. Infrared to visible upconversion processes in Pr3+/Yb3+-codoped KPb2Cl5. Physical Review, 2003, B 68, 165101
  31. Rolindes Balda, Mihail Voda, Arantza Mendioroz, Mohammed Al-Saleh, Joaquin Fernandez. Upconversion Processes in Neodymium-Doped Potassium Lead Chloride Low Phonon Crystal. Fifteenth American Conference on Crystal Growth and Epitaxy, July 20 - 24, 2003, Keystone, Colorado