1. Resonance enhancement of two- photon cross-section for optical storage in the presence of hot band absorption N. Makarov, A. Rebane, M. Drobizhev, D. Peone (Department of Physics, Montana State University, Bozeman, MT 59717, USA) H. Wolleb, H. Spahni (Ciba Specialty Chemicals Inc, P.O. Box Ch-4002 Basle, Switzerland) E. Makarova, E. Luk’yanets (Organic Intermediates and Dyes Institute, Moscow, Russia)

2. Outline Principles of 3D 2PA optical memory 2PA-sensitive photochromes Resonance enhancement 2PA vs. 1PA 2PA in phthalocyanines Summary

3. Principles of 3D 2PA optical memory hvhv dvdv h dhdh write form Bform A M L L read form Bform A PD DM L L

4. Need for 2PA-sensitive photochromes Access with 1 pulse: 100fs, 100MHz => 1TB read/write in 24 hrs Each bit have to be written and read by only 1 femtosecond pulse! Compound  1, cm 2 (, nm)  2,GM (, nm) FF ABAB Fulgide-based 3.38  10 -16 (650) 2 (780)0.160.045 Spiropyrans-based 8.27  10 -18 (352) 100 (694)0.050.01 Diarylethene-based 1.33  10 -16 (530-600) 600 (410)0.50.4

5. 2PA resonance enhancement A fundamental trade-off between 2PA and 1PA: tune laser frequency as close as possible to the resonance tune as far as possible to decrease 1PA background

6. 2PA vs. 1PA Power dependence of the fluorescence signal Absorption spectra at different temperatures as calculated from fluorescence spectrum 10 -4 1 Absorbance, a.u. 05001000150020002500 10 -3 10 -1 10 -5 10 -2 Frequency detuning 1PA - L, cm -1 240K 300K Fluorescence 240K 850-900 nm 900 nm 850 nm 860 nm 870 nm 880 nm 890 nm

7. 2PA-sensitive phtalocyanines 31 N N NH NH N N N N Bu t 2 45 6 QxQx QyQy QxQx QyQy QxQx QyQy Q x +Q y QyQy QxQx QxQx QyQy

8. 2PA-sensitive phtalocyanines Compound , M -1 cm -1 Qx, nm Qy, nm  2 (2 Qx), GM  2 (2 Qy), GM 11110007587090.342.7 21200007296860.161.8 31410007427120.401.0 4113000727-0.52- 51520007397110.511.2 61130007577150.553.4 1)The change of substituents from butyl groups at  -positions to alkoxy groups at  -positions (molecule 1 vs. 2) increases 2PA cross-sections by a factor of nearly 2. This also results in the red shift of entire 1PA spectrum by 30 nm (500 cm -1 ). The 2PA spectrum also experiences the red shift. This shows that addition of oxygen atoms increases  -conjugation. 2)Addition of extra CHO group (molecule 1 vs. 6) results in a slight decrease of 2PA cross-section as compared to better purified compound 1 and in slight increase of the cross-sections compared to 1a and 1b. The 1PA spectrum practically does not change. 3)Substituting an external benzene ring with another alkoxy group (molecule 4 vs. 6) produces a nearly symmetrical molecule. This shifts both Q x and Q y peaks closer to each other so that they overlap. A similar shift appears in 2PA spectrum. The value of 2PA cross-section reduces by a factor of nearly 2, which is probably because of reduce of the difference in dipole moments in more symmetrical molecule. 4)Addition of extra hydrogen atoms (molecule 3 vs. 4) reduces degree of symmetry. This slightly increases the 2PA cross- section for molecule 3. However, its cross-section is smaller than for molecules 1 and 6. The reason is more symmetry and thus less difference in dipole moments in the molecule 3 5)Change of substituent from molecule 3 to 5 makes the molecule less symmetrical, and thus increase 2PA cross-section. However, molecule 6, and especially 1 have the highest 2PA cross-sections among all studied samples.

9. 2PA-sensitive phtalocyanines: comparison for 3D memory Molecule 1Molecule 2Molecule 3Molecule 4Molecule 5Molecule 6 0.0480.0110.0370.0120.0460.010 12.212.012.8*13.129.4*11.1 *For molecules 3 and 5 absorption spectra of tautomer forms T 1 and T 2 significantly overlaps that makes them not practical as photochromes for 3D optical memory

10. SNR-SBR comparison  1, cm 2 (, nm)  2,GM (, nm) FF ABAB 4.8  10 -16 (752) 816 (865)0.320.0080

11. Summary Because of the requirement of fast speed writing and readout, the storage materials need to have high molecular 2PA cross section,  2 >10 3 - 10 4 GM It is evident that the crucial points in this approach are the two-photon sensitivity of a molecule and the possibility of its photochemical transformation from one form to another Careful choice of excitation frequency, along with suitable combination of 1PA and 2PA properties allow minimizing the negative impact of underlying near resonance hot band absorption A brief analysis of changes in 2PA spectra and cross-sections due to different substituent groups is provided and allow to deduce structure-to- properties relations We conclude that from the set of studied molecules compound 1 is the most promising for rewritable 3D optical memory.

12. References 1. D.A. Parthenopoulos, P.M. Rentzepis, “Three-Dimensional Optical Storage Memory”, Science, 245, 843-845 (1989). 2. M. Drobizhev, A. Karotki, M. Kruk, A. Rebane, “Resonance enhancement of two-photon absorption in porphyrins”, Chem. Phys. Lett., 355, 175-182, (2002). 3. M. Drobizhev, Y. Stepanenko, Y. Dzenis, A. Karotki, A. Rebane, P.N. Taylor, H.L. Anderson, “Understanding Strong Two-Photon Absorption in -Conjugated Porphyrin Dimers via Double-Resonance Enhancement in a Three-Level Model”, J. Am. Chem. Soc., 126, 15352-15353 (2004). 4. M. Drobizhev, F. Meng, A. Rebane, Y. Stepanenko, E. Nickel, C.W. Spangler, “Strong two-photon absorption in new asymmetrically substituted porphyrins: interference between charge-transfer and intermediate-resonance pathways”, J. Phys. Chem. B, 110, 9802-9814 (2006). 5. M. Drobizhev, Y. Stepanenko, Y. Dzenis, A. Karotki, A. Rebane, P.N. Taylor, H.L. Anderson, “Extremely strong near-IR two- photon absorption in conjugated porphyrin dimmers: quantitative description with three-essential-states model”, J. Phys. Chem. B, 109, 7223-7236 (2005). 6. M. Drobizhev, A. Karotki, M. Kruk, N. Zh. Mamardashvili, A. Rebane, “Drastic enhancement of two-photon absorption in porphyrins associated with symmetrical electron-accepting substitution”, Chem. Phys. Lett., 361, 504-512 (2002). 7. I. Renge, H. Wolleb, H. Spahni, U.P. Wild, “Phthalonaphthalocyanines: New Far-Red Dyes for Spectral Hole Burning”, J. Phys. Chem. A 101, 6202-6213, (1997). 8. A.A. Gorokhovskii, R.K. Kaarli, L.A. Rebane, “Hole Burning in Contour of a Pure Electronic Line in a Shpolskii System”, JETP Lett., 20, 216-218, (1974). 9. M. Drobizhev, A. Karotki, A. Rebane, “Persistent Spectral Hole Burning by Simultaneous Two-Photon Absorption”, Chem. Phys. Lett., 334, 76-82, (2001). 10. A. Rebane, M. Drobizhev, A. Karotki, Y. Dzenis, C.W. Spangler, A. Gong, F. Meng, “New two-photon materials for fast volumetric rewritable optical storage”, in: Proc. SPIE, Advanced Optical and Quantum Memories and Computing, Eds. H.J. Coufal, Z.U. Hasan, (SPIE, Belligham, WA, 2004), 5362, pp. 10-19. 11. M. Drobizhev, A. Karotki, M. Kruk, A. Krivokapic, H.L. Anderson, A. Rebane, “Photon energy upconversion in porphyrins: one- photon hot-band absorption versus two-photon absorption”, Chem. Phys. Lett., 370, 690-699 (2003). 12. A. Karotki, M. Drobizhev, Y. Dzenis, P.N. Taylor, H.L. Anderson, A. Rebane, “Dramatic enhancement of intrinsic two-photon absorption in a conjugated porphyrin dimer”, Phys. Chem. Chem. Phys., 6, 7-10 (2004). 13. M. Drobizhev, A. Karotkii, A. Rebane, “Dendrimer molecules with record large two-photon absorption cross section”, Opt. Lett., 26, 1081-1083 (2001). 14. M. Drobizhev, N.S. Makarov, A. Rebane, E.A. Makarova, E.A. Luk’yanets, “Two-photon absorption in tetraazachlorin and its benzo-and 2,3-naphtho-fused derivatives: Effective symmetry of  -conjugation pathway”, J. Porphyrines and Phtalocyanines, Proc. Of the International Conference on Porphyrines and Phtalocyanines, ICPP-4, Rome, Italy, 2-7 July, 2006 (to be published).

13. M.E. Marhic, “Storage limit of two-photon-based three-dimensional memories with parallel access”, Opt. Lett., 16, 1272-1273 (1991). “For systems that use parallel access by simultaneous writing or reading of bits located in an entire common plane, diffraction sets a limit to the storage density that is far smaller than that for sequential operation. Comparable densities can be achieved by using a three-dimensional waveguiding structure.”