Status and perspectives for molecular nonlinear optics: From crystals to polymers and fundamentals to applications

Current Opinion in Solid State and Materials Science

Volumn 1, Issue 4, 1996, Pages 533-546

  Zyss, Joseph ^a   Nicoud, Jean François ^b  

^a ORANGE LABS   (France)

^b INSTITUT DE PHYSIQUE ET CHIMIE DES MATÉRIAUX DE STRASBOURG   (France)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000437845     PISSN: 13590286     EISSN: None     Source Type: Journal    
DOI: 10.1016/s1359-0286(96)80069-6     Document Type: Article

References (80)

1. Quillec M (Ed): Materials for Optoelectronics. Dordrecht: Kluwer Academic Publisher; 1996:341-374. This book presents a comprehensive and up-to-date in depth review of the three main material families that qualify for optoelectronics applications, namely III-V semiconductors, mineral oxides and organics (with emphasis on electro-optic poled polymers, see fourth of this paper). Rather than adopting a competitive presentation, this book enhances the respective merits and problems associated with each of these families.
2. Zyss J (Ed): Molecular Nonlinear Optics: Materials, Physics and Devices. Boston: Academic Press; 1994.
3. Bosshard, Sutter K, Prêtre P, Hulliger J, Flörsheimer M, Kaatz P, Günter P: Organic Nonlinear Optical Materials, vol 1. In Advances in Nonlinear Optics Series. Amsterdam: Gordon & Breach; 1996.
4. Burland DM (Ed): Optical Nonlinearities in Chemistry. Chem Rev 1994, 94:3-278.
5. Kajzar F, Zyss J: Organic Nonlinear Optics: Historical survey and present trends. Nonlinear Optics 1995, 9:3-24.
6. Dalton L, Harper AW, Ghosn R, Steier WH, Ziari M, Fettermann H, Shi Y, Mustachich RV, Jen AK-Y, Shea KJ: Synthesis and processing of improved organic second-order nonlinear optical materials for applications in photonics. Chem Mater 1995, 7:1060-1081. This review paper is devoted to the various steps involved in the preparation of poled polymeric NLO materials. It starts with a description of the state of the art for NLO chromophores with large hyperpolarizabilities, then goes on to describe the processing steps required to achieve prototype electro-optic modulators.
7. Long NJ: Organometallic compounds for nonlinear optics - The search for enlightenment1 Angew Chem Int Ed Engl 1995, 34:21-38. This review attempts to critically appraise Organometallic compounds and points-out how their unique characteristics, such as diversity of metals, oxidations states, ligands and geometries, can contribute to nonlinear optical materials.
8. •].
9. -48esu) and thermally stable (275-315°C) thiophene derived NLO chromophores are described.
10. •].
11. -30 esu and good thermal stability which suggests possible application of these chromophores in the development of NLO devices.
12. Andraud C, Brotin T, Garcia C, Pelle F, Goldner P, Bogot B, Collet A: Theoretical and experimental investigations of the nonlinear optical properties of vanillin, polyenovanillin and bisvanillin derivatives. J Am Chem Soc 1994, 116:2094-2102.
13. Marder S, Cheng L-T, Tiemann BG, Friedli AC, Blanchard-Desce M, Perry J, Skindhoj J: Large first hyperpolarizabilities in push-pull polyenes by tuning of the bond length alternation and aromaticity. Science 1994, 263:511-514.
14. Wong MS, Nicoud J-F: Synthesis of novel non-centrosymmetric crystalline materials for quadratic non-linear optics. J Chem Soc: Chem Commun 1994:249-250.
15. Wong MS, Nicoud J-F, Runser C, Fort A, Barzoukas M, Marchal E: Intramolecular dipolar coupling enhancement of first-order molecular hyperpolarizability in polar solvent. Chem Phys Lett 1996, 253:141.
16. Bahl A, Grahn W, Stadler S, Feiner F, Bourhill G, Bräuchle C, Reisneir A, Jones PG: Novel, blue-transparent frequency doublers based on 1,8-di(hetero)arylnaphtha-lenes. Angew Chem Int Ed Engl 1995, 34:1485-1488.
17. Wong MS, Nicoud J-F: Synthesis and computational studies of hyperpolarizable zig-zag chromophores. Tetrahedron Lett 1994, 33:6113-6116.
18. Di Bella S, Fragala I, Ledoux I, Marks TJ: Role of metal electronic properties in tuning the second-order nonlinear optical response of coordination complexes. A combined experimental and theoretical investigation of a homologous series of (N,N4-disalicylidene-1,2-phenylenediaminato) M(II) (M-Co, Ni, Cu) complexes. J Am Chem Soc 1995, 117:9481-9485. This paper first recalls the possible role of transition metal complexes as potential building blocks for second-order NLO materials (with many references). Then the title compounds are investigated both experimentally and theoretically. The metal electronic configuration is shown to play a major role in determining the second-order nonlinear optical response. In particular, the large nonlinearities of Cu and Co complexes are due to more intense low energy charge-transfer transitions and the existence of either higher (Cu) or lower (Co) lying metal-to-ligand charge-transfer (MLCT) states.
19. Zyss J, Ledoux I: Nonlinear optics in multipolar media: Theory and experiments. Chem Rev 1994, 94:77-105.
20. Brasselet S, Zyss J: Relation between quantum and geometric dimensionalities in molecular nonlinear optics: beyond the two-level model for anisotropic systems. In Proceedings of the Fourth French-Israeli Symposium on Nonlinear and Quantum Optics, les Arcs, 21-25 January 1996. J Nonlinear Opt Physics Mat 1996, in press.
21. Dhenaut C, Ledoux I, Samuel IDW, Zyss J, Bourgault M, Le Bozec H: Chiral metal complexes with large octupolar optical nonlinearities. Nature 1995, 374:339-342. Ruthenium trisbipyridine derivatives exhibiting a chiral propeller shape trigonal structure are shown, based on harmonic light scattering measurements performed at 1.34 μm, to sustain record high nonlinearities. This paper is accompanied by a News & Views comment pointing out the departure from usual polar systems.
22. Sastre A, Torres T, Diaz-Garcia MA, Agullo-Lopez F, Dhenaut C, Brasselet S, Ledoux I, Zyss J: Subphthalocyanines: novel targets for remarkable second-order optical nonlinearities. J Am Chem Soc 1996, 118:2746-2747.
23. Stadler S, Braüchte Ch, Brandl S, Gompper R: Experimental determination of the first hyperpolarizability of new chiral and achiral octupolar tertiary amines by Hyper-Rayleigh scattering. Chem Mater 1996, 8:414-417.
24. Lequan M, Branger C, Simon J, Thami T, Chauchard E, Persoons A: Hyperpolarizability of tetraorganotin compounds determined by the hyper-Rayleigh scattering technique. Chem Phys Lett 1994, 229:101-104.
25. Fiorini C, Charra F, Nunzi JM, Samuel IDW, Zyss J: Light-induced second-harmonic generation in an octupolar dye. Optics Letters 1995, 20:2469-2471. This paper may represent a significant advance as it provides an answer for the major bottleneck that had, up till now, been hampering the exploitation of octupolar structures in materials, namely by achieving a noncentrosymmetric arrangement of ionic entities, furthermore deprived of dipole moments, in a sol-gel solid solution via coherent illumination at 1.06 μm and 0.53 μm The orientation mechanism involves nonlinear absorbtion and a so-far elusive transient photochemical process.
26. Verbiest T, Kauranen M, Persoons A, Ikonen M, Kurkela J, Lemmetyinen H: Nonlinear optical activity and biomolecular chirality. J Am Chem Soc 1994, 116:9203-9205.
27. Angelute AA, Ozheredov IA, Shkurinov AP, Korotecv NI: JETP Lett 1996, 63:N3.
28. Samuel IDW, Ledoux I, Dhenaut C, Zyss J, Fox HH, Schrock RR, Silbey RJ: Saturation of cubic optical nonlinearity in long-chain polyene oligomers. Science 1994, 265:1070-1072. Highly soluble polyenes with up to 120 double bonds have been synthesized by living polymerization techniques. Their cubic properties display a saturation versus chainlength starting around 30 double bonds and a nonresonant γ value at saturation as high as 10-31 esu for 60 double bonds. Note that the initially proposed saturation length of the order of 100 double bonds has been renormalized to 50 due to later corrections in the molecular mass distribution of successive polyene oligomers following the implementation of more precise laser desorption ionization mass spectroscopy (MALDI) techniques (K Biemann, RR Schrock, personal communication).
29. Samuel IDW, Ledoux I, Dhenaut C, Zyss J, Fox HH, Schrock RR, Silbey RJ: Saturation of cubic optical nonlinearity in long-chain polyene oligomers. Science 1994, 265:1070-1072. Highly soluble polyenes with up to 120 double bonds have been synthesized by living polymerization techniques. Their cubic properties display a saturation versus chainlength starting around 30 double bonds and a nonresonant γ value at saturation as high as 10-31 esu for 60 double bonds. Note that the initially proposed saturation length of the order of 100 double bonds has been renormalized to 50 due to later corrections in the molecular mass distribution of successive polyene oligomers following the implementation of more precise laser desorption ionization mass spectroscopy (MALDI) techniques (K Biemann, RR Schrock, personal communication).
30. Dirck CW, Herndon WC, Cervantes-Lee F, Selnau H, Martinez S, Kalamegham P, Tan A, Campos G, Velez M, Zyss J, Ledoux I, Cheng LT: Squarylium dyes: Structural factors pertaining to the negative third-order nonlinear response. J Am Chem Soc 1995, 117:2214-2225.
31. Diaz-Garcia MA, Ledoux I, Duro JA, Torres T, Agullo-Lopez F, Zyss J: Third-order nonlinear optical properties of soluble octasubstituted metallophthalocyanines. J Phys Chem 1994, 98:8761-8764.
32. Diaz-Garcia MA, Ledoux I, Femandez-Lazaro F, Sastre A, Torres T, Agullo-Lopez F, Zyss J: Third-order nonlinear optical properties of soluble metallotriazolohemiporphyrszines. J Phys Chem 1994, 98:4495-4497.
33. Bosshard C, Spreiter R, Günter P, Tykwinski RR, Schreiber M, Diederich F: Structure-property relationships in nonlinear optical tetraethynylethenes. Advan Mater 1996, 8:231-235.
34. Chen G, Mukamel S: Nonlinear susceptibilities of donor-acceptor conjugated systems: Coupled oscillator representation. J Am Chem Soc 1995, 117:4945-4964.
35. Del Zoppo M, Castigliono C, Zerbi G: A novel approach to estimate NLO response in organic conjugated molecules from vibrational spectra: Molecules with large β values. Nonlinear Opt 1995, 9:73-86.
36. Lu D, Chen G, Perry JW, Goddard WA: Valence-bond charge transfer model for nonlinear optical properties of charge transfer organic molecules. J Am Chem Soc 1994, 116:10679-10685.
37. zxx using multiple substitutions. Chem Phys Lett 1995, 236:475-484.
38. Kanis RD, Lacroix PG, Ratner MA, Marks TJ: Electronic structure and quadratic hyperpolarizabilities in organotransition-metal chromophores having weakly coupled it networks. Unusual mechanisms for second-order response. J Am Chem Soc 1994, 116:10089-10102.
39. Serbutoviez C, Nicoud J-F, Fischer J, Ledoux I, Zyss J: Crystalline zwitterionic stilbazolium derivatives with large quadratic optical nonlinearities. Chem Mater 1994, 6:1358-1368. The use of zwitterionic derivatives is proposed as a new crystal engineering approach to get efficient SHG materials. 4-methyHhio-4′-(3-sulfonatopropyl]stilbazolium (MTSPS) presents two highly SHG-active monohydrated crystalline phases. The X-ray structure of the most active phase is presented that points out the role of the water molecule involved in a hydrogen bond network linking the ribbonlike NLO chromophores in a noncentrosymmetric arrangement (see Fig. 4 for the crystal packing of MTSPS).
40. Kitazawa M, Higuchi R, Takahashi M, Wada T, Sasabe H: Novel molecular design for second-harmonic generation: Azlactone derivatives. J Phys Chem 1995, 99:14784-14792.
41. Rao SM, He KX, Lal RB, Evans RA, Loo BH, Chang JM, Metzger RM, Lee WJ, Shields AS: Crystal growth and investigation of efficient non-linear optical materials in the mixed (2,4-dinitrophenyl)-(L)-alanine (DPA) and 2-methyl-4-nitroaniline (MNA) system. J Mater Sci 1995, 30:179-184.
42. Hulliger J, König O, Hoss R: Polar inclusion compounds of perhydrotriphenylene (PHTP) and efficient nonlinear optical molecules. Advan Mater 1995, 7:719-721. In this paper a new method to induce polar ordering of NLO chromophores is based on inclusion in channels of perhydrotriphenylene crystals. Several inclusion materials show high SHG signals. Other advantages of this type of material are the absence of intermolecular π-interactions between chromophores, and a restricted photochemical degradation.
43. Le Fur Y, Bagieu-Beucher M, Masse R, Nicoud J-F, Lévy J-P: Crystal engineering of noncentrosymmetric structures based on 2-amino-5-nitropyridine and n-chloroacetic acid assemblies. Chem Mater 1996, 8:68-75. The co-crystallization of 2-amino-5-nitropyridine with mono-, di- and trichloroacetic acids is investigated, following a strategy first to 2-amino-5-nitropyridinium dihydrogen phosphate. In both cases, a noncentrosymmetric structure based on herringbone motifs is systematically formed leading to materials that exhibit SHG signals comparable to that of POM (3-methyl-4-nitropyridine-1-oxide).
44. Hulliger J: Chemistry and crystal growth. Angew Chem Int Ed Engl 1994, 33:143-162. This is a very comprehensive review on different single crystal growth strategies. Several methods are discussed and illustrated by experimental set-ups addressing and solving different problems in chemical crystallization. A special part of the paper is dealing with organic nonlinear optical materials.
45. Shekunov BY, Shepherd EEA, Sherwood J, Simpson GS: Growth and perfection of nonlinear optical materials. Kinetics and mechanism of the growth of N-(4-nitrophenyl)prolinol (NPP) crystals from methanol and toluene solution. J Phys Chem 1995, 99:7130-7136. This paper describes the investigation of the mechanism of NPP growth in solvents of widely different polarity in an attempt to optimize growth parameters. It has been shown that thin needle-like crystals obtained from a toluene solution are ideal seeds for subsequent growth from methanol solution. Optically perfect NPP crystals, that contain no visible striations or inclusions are obtained.
46. Fkyerat A, Guelzim A, Baert F, Paulus W, Heger G, Zyss J, Perigaud A: Electron density study by X-ray and neutron diffraction of an NLO compound: N-(4-nitrophenyl)-L-prolinol. Description of quadratic hyperpolarizability. Acta Crystallogr B - Struct Sci 1995, 51:197-209.
47. Horiuchi N, Lefaucheux F, Robert MC, Josse D, Khodja S, Zyss J: Gel growth of 2-amino-5-nrtropyridinium dihydrogen phosphate organomineral crystals: X-ray and nonlinear optics characterization. J Cyst Growth 1995, 147:361-368.
48. Minemoto H, Ozaki Y, Sonoda N, Sasaki T: Crystal growth and the nonlinear optical properties of 4-nitrophenol sodium salt dihydrate and its deuterated material. J Appl Phys 1994, 76:3975-3980.
49. Kitazawa M, Takahashi M, Matsuoka M: Growth behavior of L-pyrrolidone-2-carboxylic acid (L-PCA) single crystals. J Cryst Growth 1994, 141:425-436.
50. Marcy HO, Rosker MJ, Warren LF, Cunningham PH, Thomas CA, Velsko SP, Ebbers CA, Liao J-H, Kanatzidis MG: L-Histidine tetrafluoroborate: A solution-grown semiorganic crystal for nonlinear frequency conversion. Optics Lett 1995, 20:252-254.
51. Kawaga K, Sawaga M, Kakuta A, Kaji M, Nakayama H, Ishii K: Single crystal growth and caharacterization of a new organic nonlinear optical material: 8-(4′-acetylphenyl)-1,4-dioxa-8-azaspiro[4.5]decane (APDA). J Cryst Growth 1994, 139:309-318.
52. Yokoo A, Tomaru S, Yokohama I, Itho H, Kaino T: A new growth method for long rod-like organic nonlinear optical crystals with phase-matched direction. J Cryst Growth 1995, 156:279-284.
53. Schuerlein TJ, Schmidt A, Lee PA, Nebesny KW, Armstrong NR: Large molecule epitaxy on single crystal metals, insulators and single crystals and MBE-grown layered semiconductors. Jpn J Appl Phys 1995, 34:3837-3845
54. Fuchigami H, Tanimura S, Uehara Y, Kurata T, Tsunoda S: Preparation and characterization of 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) film deposited by organic molecular beam deposition technique. Jpn J Appl Phys 1995, 34:3852-3857.
55. . thick film displays a SHG efficiency 72% of that of a 1 mm thick powder sample.
56. Schlesser R, Dietrich T, Sitar Z, Gitmans F, Kündig A, Eng L, Münch B, Günter P: Organic molecular beam deposition of highly nonlinear optical 4′-nitrobenzylidene-3-acetamino-4-metoxy-aniline. J Appl Phys 1995, 78:4943-4945.
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58. Hattori Y, Kubata M, Uemiya T, Tanaka G: Preparation of large single crystal thin film of polydiacetylene by graphoepitaxy. Jpn J Appl Phys 1995, 34:3871-3875.
59. Josse D, Khodja S, Badan J, Samuel IDW, Zyss J: Low-threshold and broad tunability of an organic OPO. Appl Phys Lett 1994, 64:3655-3657.
60. -2 for a 7 ns pump duration and 10Hz repetition rate. The tunable domain extends from 1.0 μm to 1.5 μm for a corresponding pump excursion from 583 nm to 590 nm. The NPP crystal is indefinitely stable under air exposure room temperature conditions.
61. Samuel IDW, Villacampa B, Josse D, Khodja S, Zyss J: Efficient optical parametric generation in an organomineral crystal. Appl Phys Lett 1995, 66:2019-2021.
62. Khodja S, Josse D, Zyss J: Thermooptic tuning sensitivity of phase-matched second-harmonic generation in 2-amino-5-nitropyridinium-dihydrogen crystals. Appl Phys Lett 1995, 67:3081-3083.
63. Endoh H, Kawaharada M, Hasegawa E: Noncritical phase-matched SHG with and organic crystal, 4-(isopropylcarbamoyl)nitrobenzene. Appl Phys Lett 1995, 68:293-295.
64. Sawaga M, Kagawa H, Kakuta A, Kaji M, Saeki M, Namba Y: Blue light emission from a laser diode pumped ring resonator with an organic second-harmonic generation crystal of 8-(4′-acetylphenyl)-1,4-dioxa-8- azaspiro[4.5] decane. Appl Phys Lett 1995, This report on the so-called APDA organic crystal is remarkable for at least three major reasons. First, the crystal is stable and transparent down to 384 nm and noncritically phase-matchable at 810 nm fundamental wavelength. Second, the configuration used for frequency doubling to the blue of a cw-laser diode is a resonant cavity. Third, the crystal faces are coated by a fluorinated polymer leading to high transparency.
65. Boulanger B, Zyss J: Nonlinear Optical Properties. In International Tables for Crystallography, vol D: Physical Properties of Crystals. Edited by A Authier. This chapter provides an extensive presentation of nonlinear propagative phenomena in crystals with emphasis on conventions and notations for uniaxial and biaxial crystal classes. Nonlinear optical data pertaining to both organic and inorganic crystals are gathered in tables.
66. 2/W range.
67. Kim DY, Torruellas WE, Kang J, Bosshard C, Stegeman GI, Vidakovic P, Zyss J, Moemer WE, Twieg R, Bjorklund G: Second-order cascading as the origin of large third-order effects in organic single crystal core fibers. Optics Lett 1994, 19:868-870.
68. Joffre M, White JO, Hulin D, Migus A, Toussaere E, Hierle R, Gauvin S, Zyss J: Femtosecond ultrabroad-band frequency mixing in MNA and KDP thin crystals. Nonlinear Opt 1995, 11:5-12.
69. Kondo T, Ito R: Quadratic nonlinear optical effects in crystalline waveguiding structures. In Molecular Nonlinear Optics: Materials, Physics and Devices. Edited by Zyss J. Boston: Academic Press; 1994:201-243.
70. Burland DM, Miller RD, Walsh CA: Second-order nonlinearity in poled polymer systems. In Optical Nonlineearities in Chemistry. Edited by Burland DM. Chem Rev 1994, 94:31-75. A thorough review encompassing chemistry, physical properties (in particular orientational relaxation issues) and device fabrication/performances in the realm of polymer-based optoelectronics.
71. Wang W, Chen D, Fetterman HR, Shi Y, Steier WH, Dalton LR, Chow PMD: Optical heterodyne detection of 60 GHz electrooptic modulation from polymer waveguide modulators. Appl Phys Lett 1995, 67:1806-1808. This paper represents an important milestone illustrating the feasibility of an advanced polymer-based technology, all the way to the demonstration of useful and efficient modulator devices for high data rate optical processing. The authors claim therein the soon to be reached possibility of a 100 GHz bandwidth.
72. Levenson R, Zyss J: Polymer based Optoelectronics: From Molecular Nonlinear Optics to Device Technology. In Materials for Optoelectronics. Edited by Quillec M. Dordrecht: Kluwer Academic Publisher; 1996:341-374. This book chapter details the various ways and means to implement a polymer based technology and provides recent results in the realm of monolithic integration of III-V semiconductor-based functions (e.g. lasers) with polymer-based ones (e.g. waveguides).
73. Lebeau B, Sanchez C, Brasselet S, Zyss J, Froc G, Dumont M: Large second-order nonlinearities in azo-dyes grafted hybrid sol-gel coatings. New J Chem 1996, 20:13-20.
74. Zhang Y, Burzynski R, Ghosal S, Casstevens MK: Photorefractive polymers and composites. Advan Mater 1996, 8:111-125.
75. Meerholz K, Volodin BL, Sandalphon X, Kippelen B, Peyghambarian N: A photorefractive polymer with high optical gain and diffraction efficiency near 100%. Nature 1994, 371:497-500. This work demonstrates the remarkable gains achievable in functionalized polymers for real-time holography and image amplification (see also accompanying News and Views by WE Moerner in same issue, pp 475-477).
76. Meerholz K, Volodin BL, Sandalphon X, Kippelen B, Peyghambarian N: A photorefractive polymer with high optical gain and diffraction efficiency near 100%. Nature 1994, 371:497-500. This work demonstrates the remarkable gains achievable in functionalized polymers for real-time holography and image amplification (see also accompanying News and Views by WE Moerner in same issue, pp 475-477).
77. Moerner WE, Silence SM, Hache F, Bjorklund GC: J Opt Soc AM B 1994, 11:321.
78. Twieg R, Wortmann R, Poga C, Geletneky C, Moylan CR, Lundquist P, DeVoe RG, Cotts PM, Burland DM: Multifunctional photorefractive chromophores with high transparency and optimized birefringence. Communication J Tu B3-1 in Proceedings of 'Nonlinear Optics: Materials, Fundamentals and Applications': 1996 July 8-12; Maui, Hawaii. 1996:172-174.
79. Bosshard C, Otomo A, Stegeman GI, Kupfer M, Florsheimer M, Günter P: Appl Phys Lett 1994, 64:2076.
80. 3 nanocomposites with large second-order optical nonlinearity and permanent magnetization. Science 1994, 263:658-660. This first demonstration of a combination of highly efficient second-harmonic generation and magnetization up to 40°C is opening new perspectives towards optomagnetic effects in organics and related applications. The mechanism of self-alignment of the intercalated chromophores sandwiched in between metallic layers is very efficient but its origin still remains to be elucidated.