Strongly non-linear optical ferroelectric liquid crystals for frequency doubling

Abstract

From our research for novel non-linear optical (NLO) materials for frequency doublers and optical modulators we report on new ferroelectric liquid crystals, which for the first time, exhibit second order NLO coefficients (for example d ₂₂ = 5 pm V^?1, which are comparable to those of state of the art inorganic NLO materials. The novel compounds contain 5-amino-2-nitrophenyl groups attached close to the chiral centres. The switching behaviour of the new compounds, their spontaneous polarization, as well as their frequency doubling of Nd:YAG laser pulses in the S*_c and in the glass state, are reported. Moreover their waveguiding properties are presented.     

The synthesis of nitroaniline monomers and polymers as non-linear optical ferroelectric liquid crystals

Chiral 2-amino-4-alkoxy-5-nitrobenzoate and 5-amino-4-alkoxy-2-nitrobenzoate derivatives as well as the corresponding biphenyl derivatives were synthesized. Some of them were also derivatised to the corresponding acrylates and polyacrylates. Many of the new substances exhibit a large spontaneous polarization and large second order NLO coefficients. In addition some of them show a broad range S*_c phase. All these properties depend strongly on small changes in the molecular structures. Here we present the synthesis of these novel NLO FLC materials and discuss some of their properties.     

Low frequency polarization of ferroelectric liquid crystals

The possibility of the separation of free charge carriers in ferroelectric liquid crystals has been investigated in terms of the kinetic equation for the charge density. The non-uniformity of the charge distribution leads to an additional term in the free energy of the system, which can be essential for low-frequency external fields. The corresponding correction to the dielectric response of the system is proportional to the spontaneous polarization of the sample and thus has an anomalous temperature dependence near the phase transition.     

Non-linear optical properties of metallorganic ferroelectric liquid crystals

Second harmonic generation (SHG) efficiencies d eff were determined for Pt-containing ferroelectric liquid crystals (FLCs). A relatively simple method is presented which allows for the simultaneous determination of the second order susceptibility tensor coefficients d ij together with the dispersion and birefringence at the fundamental frequency. The relation between the d ij coefficients is qualitatively interpreted in terms of the molecular shape and of a scheme proposed for the molecular orientation in the ferroelectric phase. Contrary to the usual situation with calamitics, d 23 is much higher than the rest of the coefficients. This peculiarity, which reflects the 3D character of the molecular response, is interesting since d 23 is directly involved in d eff for phase matched SHG.     

Dielectric versus optical response of chevron ferroelectric liquid crystals

Dielectric and optical methods to investigate the response of surface‐stabilized ferroelectric liquid crystals (SSFLCs) of the chevron structure are examined and compared in the case of the azimuthal mode of collective relaxation processes. It is found that the variation of an effective (averaged over the chevron cell volume) dielectric permittivity tensor under the influence of a weak alternating external electric field is approximately equivalent to the transformation of this tensor as a consequence of the rotation of the laboratory frame around the axis perpendicular to the smectic plane about a small angle. Then, using an analytic solution of the equation of motion describing the azimuthal rotation of molecules, it is shown that both of the analysed approaches to calculate and measure the response of SSFLCs yield consistent results for these rotational dynamic processes. This allows the calculation of the spontaneous polarization of the unit volume of chevron slabs, provided that the pretilted azimuthal angle (in the absence of an applied electric field) within the smectic plane is known.     

Dielectric versus optical response of chevron ferroelectric liquid crystals

Dielectric and optical methods to investigate the response of surface-stabilized ferroelectric liquid crystals (SSFLCs) of the chevron structure are examined and compared in the case of the azimuthal mode of collective relaxation processes. It is found that the variation of an effective (averaged over the chevron cell volume) dielectric permittivity tensor under the influence of a weak alternating external electric field is approximately equivalent to the transformation of this tensor as a consequence of the rotation of the laboratory frame around the axis perpendicular to the smectic plane about a small angle. Then, using an analytic solution of the equation of motion describing the azimuthal rotation of molecules, it is shown that both of the analysed approaches to calculate and measure the response of SSFLCs yield consistent results for these rotational dynamic processes. This allows the calculation of the spontaneous polarization of the unit volume of chevron slabs, provided that the pretilted azimuthal angle (in the absence of an applied electric field) within the smectic plane is known.     

Low frequency dielectric spectroscopy on mixtures containing ferroelectric liquid crystals

Dielectric spectroscopy (frequency range 10 ^-1 Hz to 10⁵ Hz, temperature range 300 K to 370 K) was employed to investigate the Goldstone mode in ferroelectric liquid-crystalline mixtures of chiral and achiral compounds. While the spontaneous polarization decreases with increasing fraction of the achiral molecules the Goldstone mode remains constant in its oscillatory strength. As expected the Goldstone mode frequency shifts to lower values with increasing amount of achiral molecules in the ferroelectric liquid-crystalline mixture.     

Low frequency dielectric spectroscopy on mixtures containing ferroelectric liquid crystals

Abstract

Dielectric spectroscopy (frequency range 10 ^?1 Hz to 10⁵ Hz, temperature range 300 K to 370 K) was employed to investigate the Goldstone mode in ferroelectric liquid-crystalline mixtures of chiral and achiral compounds. While the spontaneous polarization decreases with increasing fraction of the achiral molecules the Goldstone mode remains constant in its oscillatory strength. As expected the Goldstone mode frequency shifts to lower values with increasing amount of achiral molecules in the ferroelectric liquid-crystalline mixture.     

Polymeric liquid crystals: structural basis for ferroelectric and nonlinear optical properties

This paper describes the rational design and structure–property relations in three different types of polar LC polymers with interesting material properties, as follows. (i) Chiral LC polymers, which are functionalized with crosslinkable groups, can be converted into LC elastomers with chiral smectic C^* phases. The mechanical orientability of these elastomers leads to new piezoelectric materials. (ii) The curing (dense crosslinking) of a polymer matrix provides one possibility of stabilizing the polar order of dye molecules, which is necessary for frequency doubling. Additionally, LC phases can help to stabilize this polar structure, which leads to large and stable nonlinear optical coefficients. (iii) Polymer analogous esterifications offer a convenient method for the synthesis of chiral smectic C^* polymers with large ferrolectric polarizations.     

Theoretical study of mechanisms of non-linear optical response in liquid crystals

Here, we carry out a theoretical analysis of the z scan experiments used to measure the non-linear optical properties of liquid crystals, with the aim of clarifying the mechanism responsible for the observed non-linearity in the nanosecond regime. We consider various orders of non-linear absorption and non-linear refraction in order to illustrate their effects on the resulting z scan curve. The shape of the z scan curve, in principle, contains information about the order of the non-linearity. Qualitative features of the experimental z scan curves are consistent with a fifth order absorption and a third order refraction. However, given the level of disagreement between the calculated and experimental curves, it is not possible to make quantitative statements about the coeffients of the various orders. The magnitude of the refractive part of the non-linearity is consistent with laser heating due to linear absorption. The temporal profile of a two pulse experiment is also consistent with this mechanism. We suggest that the temperature dependence of the non-linear refraction might be explained in terms of a thermal mechanism by accounting for the temperature dependence of the rate of relaxation of the orientational order.     

New chiral dopants for ferroelectric liquid crystals

New chiral dopants for application in ferroelectric liquid crystal mixtures are presented. They derive from chirally modified biphenylcyclohexylcarbonitriles, lactates and optically active 2-cyano-2-methylalkanoates. Synthetic routes to the new compounds are shown and the physical properties of the new compounds in a non-chiral smectic C host are reported.     

Negative birefringence ferroelectric liquid crystals

The synthesis and evaluation of a negative birefringence material which possesses a wide smectic C phase is reported.     

Hydrogen bond-induced ferroelectric liquid crystals

Abstract

Hydrogen-bonded dimers of 4-alkoxy-4′-stilbazole homologues (C _n OSB, proton acceptors) and the mono-(2-methylbutyl)ester of terephthalic acid (MBTA, proton donor) behaved like conventional thermotropic mesogens. For chiral MBTA mixtures, chiral nematic and blue phases were observed with n = 1 and 2, and chiral smectic C phases were observed with n ≥ 5. Achiral phases were observed for mixtures with racemic MBTA as proton donor. Transition temperatures and enthalpies are similar for the chiral and achiral systems.     

Hydrogen bond-induced ferroelectric liquid crystals

Hydrogen-bonded dimers of 4-alkoxy-4'-stilbazole homologues (C_nOSB, proton acceptors) and the mono-(2-methylbutyl)ester of terephthalic acid (MBTA, proton donor) behaved like conventional thermotropic mesogens. For chiral MBTA mixtures, chiral nematic and blue phases were observed with n = 1 and 2, and chiral smectic C phases were observed with n ≥ 5. Achiral phases were observed for mixtures with racemic MBTA as proton donor. Transition temperatures and enthalpies are similar for the chiral and achiral systems.     

Novel frequency dependence of dielectric biaxiality of surface stabilized ferroelectric liquid crystals

The frequency dependence of the dielectric biaxiality of surface stabilized ferroelectric liquid crystals (SSFLCs) was studied. The principal values of the dielectric tensor ε₁, ε₂ and ε₃ were measured by the MOM (molecular orientational model) method. Three dielectric permittivities were measured for each of two samples. These were the permittivity of the homeotropic cell and the permittivity of the planar homogeneous cell with and without the DC bias. Then the dielectric tensor components were calculated based on the molecular orientational models. We present the theory and experimental procedure of the MOM method. Measurements have been performed on Merck FLC compound SCE-8. The following novel dielectric behaviour was observed, as the DC bias voltage was increased the dielectric permittivity of the planar homogeneous cell decreased at the low frequencies (∼ 1 kHz) while increased at the high frequencies (10kHz ∼). The sign of the dielectric biaxiality ∂εε (= ε₂ - ε₁) inverted around 1 kHz, being negative at low frequencies and positive at high frequencies. The roles of the biaxiality on the dielectric behaviour of SSFLC cells are discussed.     

Photorefractive effect of ferroelectric liquid crystals

This paper reviews our recent work on the photorefractive effect of ferroelectric liquid crystals (FLCs). The photorefractive effect is defined as the optical modulation of the refractive index of a medium as a result of a variety of processes. The interference of two laser beams in a photorefractive material establishes a refractive index grating. This phenomenon enables the creation of different types of photonic applications. FLCs exhibit fast electric field response, and the orientation of the molecular axis of FLCs changes its direction according to the change in direction of the spontaneous polarization (Ps). When two laser beams interfere in a photoconductive FLC, an orientational grating is formed. The mechanism of the formation of the grating is based on the response of the Ps to the photoinduced internal electric field. The time of formation of the refractive index grating is significantly shorter in FLC materials.     

Novel ferroelectric non-symmetric dimeric liquid crystals

The synthesis, characterization, mesomorphism and ferroelectric behaviour of ten new chiral dimeric compounds are reported. These compounds are non-symmetric dimers consisting of two mesogenic units joined by two different flexible spacers derived from S(-)-lactic acid. The mesogenic units contain ester and thioester groups. The effects of the length of the flexible spacer and the structure of the mesogenic units on the mesomorphism of the compounds are investigated. These compounds are ferroelectric and the spontaneous polarizations of some were measured, giving values of c. 10nC cm^-2.     

Anomalous temperature dependence of the dielectric and optical properties in ferroelectric liquid crystals

The anomalous temperature dependence of the sign of the spontaneous polarization in a biphenyl ester series of ferroelectric liquid crystals is reported. The reversal of the sign of the spontaneous polarization in the chiral smectic C phase of 2MBNCBC ((S)-2'-methylbutyl-4'-n- nonylcarbonyloxy-(l,l'-biphenyl)-l-carboxylate) is observed at T_m. This anomaly is studied in detail as functions of the length of the terminal alkyl chain, the applied electric field, the frequency and the applied hydrostatic pressure. T_m has been confirmed to depend on the length of the terminal chain and the applied pressure. However, it is independent of the applied field and the measuring frequency. In the mixture of these compounds, this anomaly is also observed.     

Anomalous temperature dependence of the dielectric and optical properties in ferroelectric liquid crystals

The anomalous temperature dependence of the sign of the spontaneous polarization in a biphenyl ester series of ferroelectric liquid crystals is reported. The reversal of the sign of the spontaneous polarization in the chiral smectic C phase of 2MBNCBC ((S)-2′-methylbutyl-4′-n- nonylcarbonyloxy-(l,l′-biphenyl)-l-carboxylate) is observed at T _m. This anomaly is studied in detail as functions of the length of the terminal alkyl chain, the applied electric field, the frequency and the applied hydrostatic pressure. T _m has been confirmed to depend on the length of the terminal chain and the applied pressure. However, it is independent of the applied field and the measuring frequency. In the mixture of these compounds, this anomaly is also observed.     

Simultaneous determination of fundamental parameters for ferroelectric liquid crystals

An analysis of an experimental technique which allows for a simultaneous determination of several parameters with special interest for ferroelectric liquid crystals is presented. These parameters are the spontaneous polarization, the rotational viscosity and the switching time. In addition, the susceptibility associated with the soft mode free of contributions related to the helicoidal structure can also be obtained. The experimental results for these parameters for the ferroelectric liquid crystal HDOBACEEC are reported. A comparison between the switching time values deduced from the rotational viscosity and those obtained by optical measurements is performed.