Two-photon or higher-order absorbing optical materials and methods of use
Patent 6267913 Issued on July 31, 2001. Estimated Expiration Date: November 7, 2017. Estimated Expiration Date is calculated based on simple USPTO term provisions. It does not account for terminal disclaimers, term adjustments, failure to pay maintenance fees, or other factors which might affect the term of a patent.
252/582, LIGHT TRANSMISSION MODIFYING COMPOSITIONS252/301.17, Scintillating or lasing compositions252/583, Modification caused by energy other than light252/586, Displaying color change544/296, Plural 1,3-diazine rings548/303.7, The other cyclo is a five-membered hetero ring having one sulfur and four carbons (e.g., cis-tetrahydro-2-oxothieno [3,4-d]-imidazoline 4-valeric acid or biotin, etc.)549/49, Bicyclo ring system having the hetero ring as one of the cyclos564/443Hydroxy, bonded directly to carbon, or ether containing (H of -OH may be replaced by a substituted or unsubstituted ammonium ion or a Group IA or IIA light metal)
Compositions capable of simultaneous two-photon absorption and higher order absorptivities are disclosed. Many of these compositions are compounds satisfying the formulae D-.PI.-D, A-.PI.-A, D-A-D and A-D-A, wherein D is an electron donor group, A is an electron acceptor group and .PI. comprises a bridge of π-conjugated bonds connecting the electron donor groups and electron acceptor groups. In A-D-A and D-A-D compounds, the π bridge is substituted with electron donor groups and electron acceptor groups, respectively. Also disclosed are methods that generate an electronically excited state of a compound, including those satisfying one of these formulae. The electronically excited state is achieved in a method that includes irradiating the compound with light. Then, the compound is converted to a multi-photon electronically excited state upon simultaneous absorption of at least two photons of light. The sum of the energies of all of the absorbed photons is greater than or equal to the transition energy from a ground state of the compound to the multi-photon excited state. The energy of each absorbed photon is less than the transition energy between the ground state and the lowest single-photon excited state of the compound is less than the transition energy between the multi-photon excited state and the ground state.
Other References
Cassstevens, Martin K., et al., "A New Class of Materials for Optical Power Limiting", in Nonlinear Optical liquids and power limiters; Proceedings of the Meeting, San Diego, CA, Jul. 30-31, 1997 (A98-22080 05-74), Bellingham, Society of Photo-Optical Instrumentation Engineers (SPIE Proceedings, vol. 3146), 1997, pp. 152-159
He, et al., "Two-photon absorption and optical-limiting properties of novel organic compounds," Opt. Lett. 20 (18), pp. 435-437 (1995)
He, et al., "Two-photon absorption based optical limiting and stabilization in organic molecule-doped solid materials," Opt. Comm., 117, pp. 133-136 (1995)
Zhao, et al., "Newly Synthesized Dyes and Their Polymer/Glass Composites for One-and Two-Photon Pumped Solid-State Cavity Lasing," Chem. Mater. 7 (10), pp. 1979-1983 (1995)
Narang, et al., "Characterization of a New Solvent-Sensitive Two-Photon-Induced Fluorescent (Aminostyrl)pyridinium Salt Dye," J. Phys. Chem. 100 (11), pp. 4521-4525 (1996)
Bhawalkar, et al., "Efficient, two-photon pumped green upconverted cavity lasing in a new dye," Opt. Comm. 124, pp. 33-37 (1996)
He, et al., "Studies of two-photon pumped frequencey-upconverted lasing properties of a new dye material," J. Appl. Phys. 81 (6), pp. 2529-2537 (1997)
He, et al., "Nonlinear optical properties of a new chromophore," J. Opt. Soc. Am B 14 (5), pp. 1079-1087 (1997)
Zhao, et al., "Influence of two-photon absorption on third-order nonlinear optical processes as studied by degenerate four-wave mixing: The study of soluble didecyloxy substituted polyphenyls," J. Chem. Phys. 95 (6), pp. 3991-4001 (1991)
Prasad, et al., "Multiphoton Resonant Nonlinear Optical Processes in Organic Molecules," ACS Symposium, Chapter 13, pp. 225-236 (1996)
He, et al., "Upconversion dye-doped polymer fiber laser," Appl. Phys. Lett. 68 (25), pp. 3549-3551 (1996)
Xu, et al., "Measurement of two-photon excitation cross sections of molecular fluorophores with data from 690 to 1050 nm," J. Opt. Soc. Am. B 13 (3), pp. 481-491 (1996)
Kennedy, et al., "p-Bis(o-methylstyryl)benzene as a Power-Squared Sensor for Two-Photon Absorption Measurements between 537 and 694 nm," Anal. Chem. 58 (13), pp. 2643-2647 (1986)
Maiti, et al., "Measuring Serotonin Distribution in Live Cells with Three-Photon Excitation," Science 275, pp. 530-532
Lin, et al., "Dual Fluorescence of p,p'-Disubstituted 1,6-Diphenyl-1,3,5-hexatrienes: Evidence of a Twisted Intramolecular Charge Transfer State," J. Phys. Chem. 93 (1), pp. 39-43 (1989)
Rice, et al., "Two-Photon, Thermal Lensing Spectroscopy of Monosubstituted Benzenes in the 1 B2u (1 Lb) .rarw. 1 Alg (1 A) and 1 B1u (1 La) .rarw. 1 Alg (1 A) Transition Regions", J. Phys. Chem. 90, pp. 6793-6800 (1986)
Goodman, et al., "Two-Photon Spectra of Aromatic Molecules," Acc. Chem. Res. 17, pp. 250-257 (1984)
Strickler, et al., "3-D Optical Data Storage by Two-Photon Excitation," Adv. Mater. 5 (6), pp. 479-481 (1993)
Maruo, et al., "Three-dimensional microfabrication with two-photon-absorbed photopolymerization," Opt. Lett. 22 (2), pp. 132-134 (1997)
Denk, et al., "Anatomical and functional imaging of neurons using 2-photon laser scanning microscopy," J. Neuroscience Methods 54, pp. 151-162 (1994)
Anderson, et al., "Two-photon absorptivities of the all trans , ω-diphenylpolyenes from stilene to diphenyloctatetraene via three wave mixing," J. Chem. Phys. 70 (9), pp. 4310-4315 (1979)
Sutherland, et al., "Two-photon absorption and second hyperpolarizability measurements in diphenylbutadiene by degenerate four-wave mixing," J. Chem. Phys. 98 (4), pp. 2593-2603 (1993)
McEwan, et al., "Picosecond-induced Nonlinear Absorption in Liquid Crystal Media," J. Nonlinear Opt. Phys. and Mater. 4 (1), pp. 245-260 (1995)
Said, et al., "Third- and fifth-order optical nonlinearites in organic materials," Chem. Phys. Lett. 228, pp. 646-650 (1994)
Lakowicz, et al., "Two Photon-Induced Fluorescence Intensity and Anisotropy Decays of Diphenylhexatriene in Solvents and Lipid Bilayers," Journal of Fluorescence 2 (4), pp. 247-258 (1992)
Denk, et al., "Two-Photon Laser Scanning Fluorescence Microscopy," Science 248, pp. 73-76 (1990)
Strickler, et al., "Three-dimensional optical data storage in refractive media by two-photon point excitation," Optics Letters 16 (22), pp. 1780-1782 (1991)
Williams, et al., "Two-photon molecular excitation provides intrinsic 3-dimensional resolution for laser-based microscopy and microphotochemistry, " The FASEB Journal 8, pp. 804-813 (1994)
Strickler, et al., "Two-photon excitation in laser scanning fluorescence microscopy," SPIE 1398, pp. 107-118 (1990)
Hunter, et al., "Potentials of two-photon based 3-D optical memories for high performance computing," Applied Optics 29 (14), pp. 2058-2066 (1990)
Kim, et al., "Synthesis of Electroluminescent Polymer containing charge Transport and Emissive Chromophores on Polymer Skeleton," Chemistry Letters, pp. 587-588 (1995)
Parthenopoulos, et al., "Three-Dimensional Optical Storage Memory," Science 245, pp. 843-845 (1989)
Fuke, et al., "Two-Photon Absorption Spectrum of Trans-Stilbene, Trans-Cis Photoisomerization via Upper 1 Ag State," Chem. Phys. Ltrs. 74 (3), pp. 546-548 (1980)
Plakhotnik, et al., "Nonlinear Spectroscopy on a Single Quantum System: Two-Photon Absorption of a Single Molecule," Science 271, pp. 1703-1705 (1996)
Jones, et al., "Direct observation of the 2.1 Ag- electronic state of carotenoid molecules by consecutive two-photon absorption spectroscopy," J. Photochem. Photobiol. A: Chem. 68, pp. 59-75 (1992)
Wong, et al., "Measurements of .chi..sup.(3) (ω;ω,-ω, ω) in conducting polymers at λ=620 nm," Synthetic Metals 49-50, pp. 13-20 (1992)
Tackx, et al., "Distinction of two-photon absorption from other nonlinear loss mechanisms by phase-conjugate interferometry," Appl. Phys. Lett. 65 (3), pp. 280-282 (1994)
Luo, et al., "One- and Two-Photon Absorption Sepctra of Short Conjugated Polyenes," J. Phys. Chem. 98 (32), pp. 7782-7789 (1994)
Itoh, et al., "Fluorescence quantum yields of , ω-diphenylpolyenes," Spectrochimica Acta 50A (13), pp. 2261-2263 (1994)
Kumar, et al., "Optical nonlinearity in a mode-locking dye: optical limiting and four wave mixing," Chemical Physics Letters, 245, pp. 287-291 (1995)
Xu, et al., "Determination of absolute two-photon excitation cross sections by in situ second-order autocorrelation," Optics Letters 20 (23), pp. 2372-2374 (1995)
Mertz, et al., "Single-molecule detection by two-photon-excited fluorescence," Optics Letters 20 (24), pp. 2532-2534 (1995)
Beljonne, et al., "Two-photon absorption and third-harmonic generation of di-alkyl-amino-nitro-stilbene (DANS): A joint experimental and theoretical study," J. Chem. Phys. 103 (18), pp. 7834-7843 (1995)
Couris, et al., "Concentration and wavelength dependence of the effective third-order susceptibility and optical limiting of C60 in toluene solution," J. Phys. B: At. Mol. Opt. Phys. 28, pp. 4537-4554 (1995)
Brede, et al., "Photo- and Radiation-induced Chemical Generation and Reactions of Styrene Radical Cations in Polar and Non-polar Solvents," J. Chem. Soc. Perkin Trans. 2, pp. 23-32 (1995)
Desai, et al., "Laser-Induced Polymerization within Carbon Disulfide Clusters," J. Phys. Chem., 99 (6), pp. 1786-1791 (1995)
Roux, et al., "Two-photon-absorption-induced luminescence in organic waveguide couplers," J. Opt. Soc. Am. B, 12 (3), pp. 428-433 (1995)
El-Shall, et al., "Comparative Polymerization in the Gas Phase and in Clusters. 2. Electron Impact and Multiphoton-Induced Reactions in Isobutene and Benzene/Isobutene Clusters," J. Am. Chem. Soc., 117 (29), pp. 7744-7752 (1995)
Puccetti, et al., "Chain-Length Dependence of the Third-Order Polarizability of Disubstituted Polyenes. Effects of End Groups and Conjugation Length," J. Phys. Chem., 97 (37), pp. 9385-9391 (1993)
Carre, et al., "Biphotonic process for recording holograms with continuous-wave lasers in the near infraraed," Optics Letters, 12 (9), pp. 646-647 (1987)
Kohler, et al., "Saturation kinetics of the S0 to S2 optical transition in isolated diphenylhexatriene," J. Chem. Phys., 82 (7), pp. 2939-2941 (1985)
Rava, et al., "Regularities in the two-photon spectra of polysubstituted benzenes," J. Chem. Phys., 77 (10), pp. 4912-4919 (1982)
Stachelek, et al., "Detection and assignment of the `phantom` photochemical singlet of trans-stilbene by two-photon excitation," J. Chem. Phys., 66 (10), pp. 4540-4543 (1977)
Itoh, et al., "Dual Fluorescence of Diphenylpolyenes," J. Phys. Chem., 91 (7), pp. 1760-1764 (1987)
Birnbaum, et al., "Location of a 1 Ag state in bithiophene," J. Chem. Phys., 96 (4), pp. 2492-2495 (1992)
Birnbaum, et al., "Low lying singlet states of , ω-dithienylpolyenes: , ω-dithienylbutadiene, , ω-dithienylhexatriene, and , ω-dithienyloctatetraene," J. Chem. Phys., 94 (3), pp. 1684-1691 (1991)
Kohler, et al., "Fluorescence from the 11 Bu State of Diphenylhexatriene: Inversion of the 11 Bu and 21 Ag Levels in CS2," J. Phys. Chem., 92 (18), pp. 5120-5122 (1988)
Birge, "An Introduction to Two-Photon Spectroscopy," Spectroscopy of Biological Molecules: Theory and Applications--Chemistry, Physics, Biology, and Medicine, No. 39, pp. 457-471 (1983)
Cha, et al., Two photon absorption of di-alkyl-amino-nitro-stilbene side chain polymer, Appl. Phys. Lett. 65 (21), pp. 2648-2650 (1994)
Parma, et al., "Two-Photon Absorption of 7-Hydroxycoumarine," Chem. Phys. Lett. 54 (3), pp. 541-543 (1978
November 7, 2017. Estimated Expiration Date is calculated based on simple USPTO term provisions. It does not account for terminal disclaimers, term adjustments, failure to pay maintenance fees, or other factors which might affect the term of a patent.
