Rüdiger Wortmann

Organic glasses : A new class of photorefractive materials

The performance of amorphous organic photorefractive (PR) materials in applications such as optical data storage is generally limited by the concentration of active molecules (chromophores) that can be incorporated into the host without forming a crystalline material with poor optical quality. In polymeric PR systems described previously, performance has been limited by the necessity of devoting a large fraction of the material to inert polymer and plasticizing components in order to ensure compositional stability. A new class of organic PR materials composed of multifunctional glass-forming organic chromophores is described that have long-term stability and greatly improved PR properties.

Organic Materials for Second-Order Non-Linear Optics

Publisher Summary Over the past 15–20 years, the non-linear optical (NLO) response of organic molecules has been of wide interest to organic and physical chemists, as well as physicists and chemical engineers. This interest arises from the possible use of such organic materials. In principle, photonics or the hybrid technology optoelectronics, both based on non-linear optical phenomena, can supersede electronics in communication technology. These technologies allow many operations that are currently effected with electron conduction to be replaced by operations based on light conduction. Many problems are encountered when it comes to the translation of a molecular property into a bulk property. It has transpired that some of these problems are not easy to solve with classical NLO-phores that mostly belong chemically to the class of merocyanine dyes. New design strategies for organic molecules and their respective bulk structures, crystals or oriented composite materials like polymers, are needed. Only a more fundamental understanding of these issues will allow rational optimization of molecular and bulk properties. This chapter surveys second-order molecular polarizabilities of organic molecules. Emphasis is given to the underlying of physical principles of non-linear optics (e.g. molecular topology), and to the establishment of structure–property relationships.

Chromophore Design for Photorefractive Organic Materials

During the last years, significant progress has been achieved in understanding the mechanism of the photorefractive effect in amorphous organic materials. New chromophores could be devised which provided a substantial increase in the electrooptical response and lead to photorefractive materials with unprecedented refractive index modulation (delta n = 10(-2) at E = 28 V micron-1) and two-beam coupling gain. These improvements could only be accomplished by optimizing the electronic structure of highly conjugated merocyanine dyes to perfectly balanced dyes in the charge resonance limit (such as aminothienyl oxopyridone (ATOP) and indoline dimethine oxopyridone (IDOP) derivatives), considering effects of supramolecular ordering (dipolar aggregation), and adjusting the compatibility of the dyes to photoconducting polymers (like poly-N-vinylcarbazole). In particular, optimized glass-forming dyes (such as 2BNCM and ATOP-4) combine the dual functionalities of charge transport and electrooptical response and exhibit photorefractivity even in absence of any additional photoconductor.

Effective polarizabilities and local field corrections for nonlinear optical experiments in condensed media

A consistent extension of Onsager’s reaction field model to nonlinear-optical experiments in condensed media is presented. This model is used to derive effective (nonresonant) linear and nonlinear molecular polarizabilities involved in refractive index measurements, electric-field induced second-harmonic generation, hyper-Rayleigh scattering, third-harmonic generation and degenerate four-wave mixing. The commonly applied Lorentz correction, while being a useful approximation in linear optics, is demonstrated to lead to systematic errors of typically 20% in nonlinear optical experiments. This is due to an inherent inconsistency that originates from the implicit assumption of a cavity field factor for the nonlinear molecular response.

Deviations from Kleinman symmetry of the second-order polarizability tensor in molecules with low-lying perpendicular electronic bands

Abstract 4-Nitroaniline (pNA) and 3,5-dinitro-aniline (3,5-DNA) were studied by electric field induced second harmonic generation (EFISH) and electrooptical absorption measurements (EOAM) in dioxane solution at T = 298 K. The measurements were carried out for two polarization conditions, the electric field vector of the linearly polarized incident light being parallel or perpendicular to the static electric field. The second-order polarizability tensor of pNA is confirmed to be Kleinman symmetric, while a strong deviation from index permutation symmetry is observed for 3,5-DNA. The latter is quantitatively interpreted by contributions of a low-lying electronic band with transition dipole perpendicular to the symmetry axis. New design possibilities for second-order nonlinear optical materials are pointed out.

Design of optimized photorefractive polymers: A novel class of chromophores

It is demonstrated that the microscopic mechanism of the photorefractive (PR) effect in organic composites with low glass transition temperatures involves the formation of refractive index gratings through a space‐charge field‐modulated Kerr effect. A tensorial formulation of the macroscopic aspects of the PR Kerr effect and its microscopic interpretation is presented. The second‐order dipole orientation term containing the anisotropy of the first‐order optical polarizability α(−ω;ω) is shown to yield the dominant contribution to the Kerr susceptibility χ(3)(−ω;ω,0,0). A class of special chromophores having negligible second‐order polarizabilities β(−ω;ω,0) and large dipole moments μ has been identified in order to optimize this term. These chromophores are not subject to the efficiency‐transparency tradeoff typically encountered with second‐order nonlinear optical (NLO) chromophores, providing highly transparent materials with large PR Kerr response. Contrary to previous approaches in this field, the bes...

Second-order polarizability of donor-acceptor substituted oligothiophenes : substituent variation and conjugation length dependence

Abstract Second-order polarizabilities and excited state dipole moments of a number of donor—acceptor substituted α-oligothiophenes have been investigated by use of electric field induced second harmonic generation (EFISH), solvatochromism and electrooptical absorption measurements (EOAM). The experimental results reveal that oligothiophenes are very effective conjugation units offering substantial enhancement of the second-order polarizability with increasing chain length.

Elongated push–pull diphenylpolyenes for nonlinear optics: molecular engineering of quadratic and cubic optical nonlinearities via tuning of intramolecular charge transfer

Abstract Push–pull polyenes are of particular interest for nonlinear optics (NLO) as well as model compounds for long-distance intramolecular charge transfer (ICT). In order to tune the ICT phenomenon and control the linear and nonlinear optical properties, we have synthesized and investigated several series of soluble push–pull diphenylpolyenes of increasing length and having various donor (D) and acceptor (A) end groups. Their linear and NLO properties have been studied by performing electro-optical absorption measurements (EOAM) and third-harmonic generation (THG) experiments in solution. Each push–pull molecule exhibits an intense ICT absorption band in the visible characterized by an increase in dipole moment upon excitation (Δ μ ). By lengthening the polyenic chain, linear increases in excited-state dipoles are achieved while the ground-state dipole is maintained constant. The polyenic chain thus allows for long-distance intramolecular charge transfer. In addition, tuning of the magnitude of the ICT phenomenon and of the nonlinear responses is achieved by varying the donor and acceptor end groups: increasing the D/A strength leads to concomitant enhancements of Δ μ , quadratic ( β ) and cubic ( γ ) hyperpolarizabilities values. Giant Δ μ values (up to more than 30 D) and enhanced non-resonant quadratic and cubic NLO molecular responses (i.e. β (0)=500×10 −30 esu and γ (0)=8000×10 −36 esu) have been attained while maintaining suitable solubility, stability and transparency.

Intramolecular charge transfer in elongated donor-acceptor conjugated polyenes

Abstract Intramolecular charge transfer (ICT) has been investigated by electro-optical absorption measurements for two series of donor-acceptor polyenes of increasing length. Each molecule undergoes an increase in dipole moment upon photoexcitation. The experimental results indicate that lengthening the polyenic chain linking the donor and acceptor end groups results in a bathochromic shift of the ICT absorption band and induces marked increases of both excited state and transition dipoles, whereas the ground-state dipole is relatively unaffected. As a result, marked photoinduced changes in the dipole moment (up to 33 D) were obtained with the longest molecules (up to 27 A) leading to highly polar excited states. Elongated donor—acceptor polyenes are therefore particularly interesting compounds for long-distance and low-energy intramolecular charge transfer.

Intramolecular charge transfer and enhanced quadratic optical non-linearities in push-pull polyenes

Abstract Push-pull polyenes, which have an electron-donating group (D) and an electron-withdrawing group (A) grafted on opposite ends of a conjugated polyenic chain, are of particular interest as model compounds for long-distance intramolecular charge transfer (ICT), as well as potent non-linear optical chromophores. Several series of push-pull polyenes of increasing length, combining aromatic donor moieties and various acceptor groups, have been prepared and studied. Their linear and non-linear optical properties have been investigated by performing electro-optical absorption measurements (FOAM) and electric-field-induced second-harmonic generation (EFISH) experiments in solution. Each molecule shows a broad and intense ICT absorption band in the visible associated with an increase in the dipole moment (Δμ). Lengthening the polyenic chain linking the D and A groups results in a bathochromic shift of the ICT absorption band and induces a linear increase in the excited state dipole. In contrast, the ground state dipole remains roughly constant. As a result, the longest molecules exhibit huge Δμ values (up to 42 D) as well as markedly enhanced quadratic hyperpolarizabilities (β). In addition, the nature of the end groups has been found to influence strongly both the ICT and optical non-linearities: larger β and Δ μ values, as well as steeper length dependences, are obtained with push-pull phenylpolyenes bearing strong acceptors.