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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:
    This field is for additional information such as application,
    comments, add. requirements etc.
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    Literature:
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • R. Balda, M. Voda, M. Al-Saleh, and J. Fernández. Visible luminescence in KPb2Cl5:Pr3+ crystal. Journal Luminescence, (2002) v. 97, p. 190
  • 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
  • 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
  • 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.
  • 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
  • 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