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Definitions

• the present disclosure relates to chiral polymers and use thereof in electro-optical modulators.
• Electro-optic modulators for conversion of electrical signals to optical signals are known in which the EOM contains a material having a non-zero hyperpolarizability in the solid state, i.e. the refractive index of the material changes with applied electric field.
• An inorganic material known for use in electro-optic switching is lithium niobate (LiNbCh).
• Verbiest et al ref ‘Strong enhancement of nonlinear optical properties through supramolecular chirality’, Science, 1998, vol. 282, 913 discloses Langmuir-Blodgett films of a chiral helicene composed of supramolecular arrays of the molecules.
• the present disclosure provides a chiral polymer comprising a repeat unit having a first planar group disposed in a first plane; a second planar group disposed in a second plane different from the first plane; a bond or group linking the first planar group and the second planar group; and a first divalent binding group linking the first planar group and the second planar group.
• the present disclosure provides an electrooptic modulator comprising a polymer film and electrodes for applying an electric field across the polymer film wherein the polymer film comprises a chiral polymer.
• a chiral polymer as described herein is a polymer containing an enantiomeric excess of a chiral repeat unit.
• a chiral monomer as described herein is a monomer containing an excess of an enantiomer of the monomer.
• a chiral monomer or polymer as described herein is optically active, e.g. it has a non-zero circular dichroism.
• the repeat unit is bound to adjacent repeat units by first and second bonds and wherein the angle between the first and second bonds is 180° ⁇ 10°.
• the first and second bonds are collinear.
• repeat unit comprises a second divalent binding group.
• the angle between the first plane and the second plane is in the range of 1-89°.
• first and second planar groups are, respectively, a first arylene or heteroarylene group and a second arylene or heteroarylene group and wherein each of the first and second arylene or heteroarylene groups is independently unsubstituted or substituted with one or more substituents.
• first and second arylene or heteroarylene groups are linked by a direct bond.
• the direct bond is parallel to an axis of the polymer.
• the direct bond is perpendicular to an axis of the polymer.
• repeat unit is selected from formulae (I) - (III):
• Ar 1 is an arylene or heteroarylene group which is unsubstituted or substituted with one or more substituents
• Ar 2 is an arylene or heteroarylene group which is unsubstituted or substituted with one or more substituents
• B 1 is a divalent binding group and B 2 in each occurrence is independently a divalent binding group
• repeat unit is selected from formulae (la)-(IIIa):
• the present disclosure provides a monomer of formula (I’), (If) or (nr): wherein Ar 1 is an arylene or heteroarylene group which is unsubstituted or substituted with one or more substituents and which is disposed in a first plane; Ar 2 is an arylene or heteroarylene group which is unsubstituted or substituted with one or more substituents and which is disposed in a second plane different from the first plane; B 1 in each occurrence is independently a divalent binding group; B 2 in each occurrence is independently a divalent binding group; LG 1 in each occurrence is independently a leaving group; and LG 2 in each occurrence is independently a leaving group.
• LG 1 in each occurrence is a halide, pseudohalide or boronic acid or ester bound to an aromatic carbon atom of Ar 1 or Ar 2 ; and LG 2 is H bound to an N atom of B 2 .
• the present disclosure provides a method of forming a polymer comprising polymerisation of a monomer as described herein.
• the present disclosure provides an electrooptic modulator comprising a polymer film wherein the polymer film comprises a chiral polymer.
• the chiral polymer comprises a repeat unit having a first planar group disposed in a first plane; a second planar group disposed in a second plane different from the first plane; a bond or group linking the first planar group and the second planar group; and a first divalent binding group linking the first planar group and the second planar group.
• the present disclosure provides an optical interconnect for transmitting data, comprising: the electrooptic modulator as described herein; and a light source coupled to an input of the electrooptic modulator; wherein the electrooptic modulator is configured to modulate light emitted by the light source.
• the optical interconnect further comprises an optical fibre coupled at a first end to an output of the electrooptic modulator to receive the modulated light.
• the optical interconnect further comprises a photodetector coupled to a second end of the optical fibre.
• the present disclosure provides a system comprising: the optical interconnect as described herein; a first device; and a second device; wherein the optical interconnect is configured to transmit data from the first device to the second device.
• the system comprises a second optical interconnect as described herein, the second optical interconnect being configured to transmit data from the second device to the first device.
• FIG. 1 illustrates different possible conformations of polythiophene chains
• Figure 2 illustrates a repeat unit according to some embodiments
• FIG. 3 schematically illustrates an electro-optic modulator according to some embodiments
• FIG 4A schematically illustrates light input to an electro-optic modulator as shown in Figure 3;
• FIG 4B schematically illustrates an electrical signal applied to an electro-optic modulator as shown in Figure 3;
• Figure 4C schematically illustrates light output from an electro-optic modulator as shown in Figure 3.
• references to a layer “over” another layer when used in this application means that the layers may be in direct contact or one or more intervening layers are may be present. References to a layer “on” another layer when used in this application means that the layers are in direct contact. References to a specific atom include any isotope of that atom unless specifically stated otherwise.
• a chiral polymer i.e. a polymer in which the polymer chains contain an enantiomeric excess of a chiral repeat unit, may be used as an active material in an electro-optic modulator.
• the chirality of the repeat unit may be “locked in” to provide a thermodynamically stable enantiomer.
• Figure 1 schematically illustrates different configurations that a polymer chain may be able to adopt, depending on the values taken for the intermonomer twist angle.
• Figure 1 illustrates polythiophene chains however it will be understood that this may be any chain of repeat units of an aromatic or heteroaromatic ring. Possible configurations include right-handed helices, left-handed helices and non-helical conformations, e.g. linear or other random, non-helical conformations. Due to the large number of unconstrained intermonomer twist angle possibilities, individual chains of poly(hetero)arylenes such as polythiophene may adopt a large number of such conformations, depending on the environment, each of which will give a contribution to the hyperpolarizability. Without wishing to be bound by any theory, it is believed that axially ordered films of such polymer chains in the solid state may result in a positive, negative or zero net electro-optic response (r33).
• the present inventors have found that by providing a non-planar chiral repeat unit having a twist in the monomer structure, the resulting polymer chains can be constrained to adopting a static, helical conformation with non-zero chiral hyperpolarizability components. Enantiomeric excess in the chirality of the polymer chains can be achieved by polymerisation of such monomers having an excess of one of a (+) or (-) enantiomer.
• the enantiomeric excess of the chiral repeat units may be at least 25%, more preferably at least 50%, yet more preferably 75% or 100%.
• the enantiomeric excess of the chiral repeat units may correspond directly with the enantiomeric excess of the corresponding monomers used to form the polymer.
• chirality of polymers as described herein arises from the topology of the polymer chains, e.g. ratio of right-handed helical polymer chains : left-handed helical polymer chains which is not 1 : 1.
• the repeat units described herein may or may not contain a stereogenic centre or axis of chirality.
• Such an enantiomeric excess of the monomer to form the chiral repeat units may be achieved by a monomer synthesis including an enantioselective reaction step and / or a chiral resolution step.
• the chiral resolution step may take place at any point in the monomer synthesis, including chiral resolution of a racemic mixture of any one of a starting material, a monomer intermediate or the monomer. Any suitable chiral resolution known to the skilled person may be used including, without limitation, crystallisation or reaction with an enantiomerically pure chiral reagent, separation of the resulting diasteromers.
• Chiral polymers as described herein are suitably static, i.e. conversion of the chiral repeat unit to its optically active mirror image is not thermodynamically favourable at 25°C in the solid state or in solution.
• a chiral monomer as described herein has a racemisation energy of at least 2kT, optionally at least lOkT, at 298K.
• a static configuration may be achieved by providing at least one binding group between first and second planar groups of a repeat unit of the polymer such that the most thermodynamically favourable conformation of the repeat unit is one in which the first and second planar groups lie in different planes, i.e. are twisted. It will be appreciated that such a binding group limits the freedom of movement of the first and second planar groups relative to one another, and preferably locks the first and second planar groups into a twisted configuration.
• the polymer is conjugated, i.e. repeat units in the polymer backbone are directly pi-conjugated to adjacent repeat units.
• a carbon ring atom of an aromatic or heteroaromatic repeat unit of a repeat unit of the conjugated polymer is directly bound to a carbon ring atom of an aromatic or heteroaromatic repeat unit of an adjacent repeat unit.
• the polymer is non-conjugated.
• the polymer may comprise repeat units which contain conjugated groups, e.g. aromatic or heteroaromatic groups, which are not conjugated to adjacent repeat units.
• the polystyrene-equivalent number-average molecular weight (Mn) measured by gel permeation chromatography of a polymer as described herein is in the range of about IxlO 3 to IxlO 8 , and preferably IxlO 4 to 5xl0 6 .
• the polystyrene-equivalent weight-average molecular weight (Mw) of the polymer may be IxlO 3 to IxlO 8 , and preferably IxlO 4 to IxlO 7 .
• the twisted repeat unit of the polymer comprises a first arylene or heteroarylene group Ar 1 and a second arylene or heteroarylene group Ar 2 wherein Ar 1 and Ar 2 are linked by a single bond and are further linked by at least one binding group.
• the angle between the plane of Ar 1 and the plane of Ar 2 is 1-89°, and preferably 20-60°, as measured using quantum computing optimized monomer structures.
• Quantum chemical computations were performed using Gaussian 09, Revision D.01 software.
• the structures were optimized using DFT model at B3LYP/6-31 g(d) level of theory. Ground-state minima were confirmed based on the analysis of their analytical frequencies computed at the same level, which show no imaginary frequencies.
• Molecular static and frequency-dependent hyperpolarizabilities were computed on preoptimized geometries using DFT model at B3LYP/6-31 g(d) level of theory and Polar job type and its options as implemented in Gaussian 09, Revision D.01.
• Ar 1 and Ar 2 are each preferably selected from the group consisting of monocyclic or polycyclic aromatic or heteroaromatic groups.
• Ce-20 arylene groups are preferred, e.g. phenylene or naphthylene groups.
• Ar 1 and Ar 2 may be the same or different, preferably the same.
• the binding groups or groups may be selected so as to induce a twist between Ar 1 and Ar 2 .
• the angle between the repeat unit’s bonds Al and A2 to adjacent repeat units is preferably 180°, as shown in Figure 2.
• the range may be 180 ⁇ 35°, preferably 180 ⁇ 20°, more preferably 180° ⁇ 10°
• the bonds Al and A2 may be parallel.
• the bonds Al and A2 are collinear, i.e. they lie on a common axis.
• the twisted repeat unit may be selected from formulae (I) - (III): wherein B 1 in each occurrence is independently a divalent binding group and B 2 in each occurrence is independently a divalent binding group.
• Ar 1 and Ar 2 are each independently unsubstituted or substituted with one or more substituents.
• Substituents may, independently in each occurrence, be selected from F; Cl; NO2; CN; NH2; OH; an aryl or heteroaryl group Ar 3 which may be unsubstituted or substituted with one or more substituents; and C1.12 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 6 wherein R 6 is H or a substituent, CO or COO and one or more H atoms may be replaced with F.
• An aryl or heteroaryl substituent of Ar 1 or Ar 2 may be unsubstituted or substituted with one or more substituents selected from F, Cl, CN, NO2 or C1.12 alkyl wherein one or more non- adjacent C atoms may be replaced with O, S, NR 6 , CO or COO and one or more H atoms may be replaced with F.
• the aryl or heteroaryl substituent may be a C6-20 aryl, e.g. phenyl or naphthyl; a monocyclic 5- or 6-membered heteroaromatic ring; or a fused heteroaromatic group.
• R 6 is a substituent, it is preferably a C1.20 hydrocarbyl group.
• Preferred groups Ar 1 and Ar 2 are phenylene and naphthalene.
• the chirality axis of formula (I) or (II), i.e. the bond between Ar 1 and Ar 2 is parallel to the polymer backbone.
• the chirality axis of formula (III) is perpendicular to the polymer backbone.
• B 1 together with Ar 1 and Ar 2 , forms a 7 membered ring.
• Exemplary B 1 groups include, without limitation: wherein R 2 -R 4 in each occurrence is independently H or a substituent; R 7 is a substituent, optionally a C1.20 hydrocarbyl group; and * represents a bond to Ar 1 or Ar 2 .
• R 3 and R 4 in each occurrence are preferably H or a C1.20 hydrocarbyl group.
• Ci -20 hydrocarbyl group as described anywhere herein is preferably selected from C1.12 alkyl; unsubstituted phenyl; and phenyl substituted with one or more C1.12 alkyl groups.
• B 2 together with Ar 1 and Ar 2 , forms a 7 membered ring.
• An exemplary binding group B 2 is:
• Formulae (I), (II) and (III) are selected from, respectively, Formulae (la)-(IIIa): wherein X in each occurrence is CR 1 or N; R 1 in each occurrence is H or a substituent and substituents R 1 attached to adjacent carbon atoms may be linked to form an aromatic or non- aromatic ring.
• non-H groups R 1 are selected from: F; Cl; NO2; CN; NH2; OH; Ar 3 ; and C1.12 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 6 , CO or COO and one or more H atoms may be replaced with F.
• Ar 3 is an aryl or heteroaryl group as described above. Exemplary twisted repeat units are:
• Ar 1 and Ar 2 are the only two arylene or heteroarylene groups of the chiral repeat unit in the polymer backbone which are not in the same plane.
• the chiral repeat unit may comprise more than two arylene or heteroarylene groups which are not in the same plane.
• the polymer is a homopolymer, e.g. a homopolymer comprising a repeat unit of formula (Ila) or (lib).
• the polymer is a copolymer comprising a twisted repeat unit as described herein and one or more co-repeat units, e.g. an AB copolymer comprising a repeat unit of formula (Ila), (lib) or (lie) and a co-repeat unit.
• the angle between the co repeat unit’s bonds to adjacent repeat units is 180°.
• the co-repeat units’ bonds to adjacent repeat units lie on the same axis.
• a preferred co-repeat unit has formula (IV): wherein X in each occurrence is N or CR 1 wherein R 1 is H or a substituent as described above.
• a particularly preferred co-repeat unit is 1,4-phenylene.
• Polymers described herein may be formed by any method known to the skilled person.
• An exemplary method is polymerisation of one or more monomers for forming a homopolymer or copolymer, respectively, wherein each monomer has two halide leaving groups, e.g. Cl, Br or I, and including at least one monomer for forming a repeat unit as described herein, for example as disclosed in T. Yamamoto, "Electrically Conducting And Thermally Stable pi-Conjugated Poly(arylene)s Prepared by Organometallic Processes", Progress in Polymer Science 1993, 17, 1153-1205, the contents of which are incorporated herein by reference;
• Another exemplary method is polymerisation of one or more monomers having halide or pseudohalide (e.g. sulfonate) leaving groups and boronic acid or boronic ester leaving groups.
• the monomers include one or more monomers substituted with two halide or pseudohalide groups and one or more monomers substituted with two boronic acid or boronic ester groups, wherein the monomers include at least one monomer for forming a repeat unit as described herein.
• the monomers may comprise or consist of a monomer substituted with one halide or pseudohalide group and one boronic acid or boronic ester groups.
• polymerisations according to this method are described in, for example, WO 00/53656, WO 2003/035796, and US 5777070, the contents of which are incorporated herein by reference.
• Another exemplary method is polymerisation of one or more monomers having halide or pseudohalide (e.g. sulfonate) leaving groups and an amino (NH or NH2) group.
• the monomers include one or more monomers substituted with two halide or pseudohalide groups and one or more monomers substituted with two amino groups, wherein the monomers include at least one monomer for forming a repeat unit as described herein.
• the monomers may comprise or consist of a monomer substituted with one halide or pseudohalide group and one amino group.
• Polymerisations according to this method are described in, for example, US 9,598,539, the contents of which are incorporated herein by reference.
• a film comprising or consisting of a chiral helical polymer as described herein may be formed by deposition of a solution comprising the polymer.
• the solution comprises the polymer and any other materials of the film dissolved in one or more solvents.
• the solution may be deposited onto a substrate followed by evaporation of the solvent(s).
• the solution may be deposited by any method known to the skilled person, e.g. spin-coating, dip-coating, roll-coating, spray coating, doctor blade coating, wire bar coating or slit coating.
• Alignment of the polymer chains may be controlled during and / or after deposition of the solution.
• Methods to control alignment of the polymer chains include one or more of deposition by doctor blade coating; rubbing a deposited film at a temperature above its glass transition temperature; and alignment on a surface having surface features such as pores and / or channels or a surface patterning to cause alignment in a particular direction.
• a majority of the polymer chains of a polymer film i.e. > 50 mol% of the polymer chains of a polymer film are arranged parallel ⁇ 10° to an alignment axis of the polymer film.
• the degree of alignment of the polymer film may be determined from the film’s dichroic ratio.
• the polymer film may consist of the chiral helical polymer in an enantiomeric excess or it may comprise one or more further materials, e.g. one or more insulating polymers.
• Figure 3 illustrates an electrooptic modulator (EOM) 1 according to some embodiments of the present disclosure.
• the EOM 1 comprises a waveguide 2 having an input 3, an output 4, a first path 5 extending between the input 3 and the output 4 and a second path 6 extending between the input 3 and the output 4.
• the input 3 and output 4 may each take the form of a bifurcated junction, although other structures serving to divide incident light 7 substantially equally between the first and second paths 5, 6 may be used instead of a bifurcated junction structure.
• the incident light 7 is substantially unmodulated and has a narrow bandwidth.
• the incident light 7 is supplied from a laser source, for example a laser diode, coupled to the waveguide 2.
• the incident light may be of any wavelength compatible with good transmission through the polymer film 8 and stability of the film.
• Typical communication wavelengths may be used such as, for example, wavebands including 600 nm, 850 nm, 1310 nm, 1550 nm and so forth.
• the first path 5 comprises a polymer film 8 formed using a polymer as described herein and providing a section of waveguide through which light traversing the first path 5 passes.
• First and second electrodes 9, 10 are arranged to oppose one another across the polymer film 8 for applying an electric field across the polymer film 8.
• the electrodes 9, 10 may be directly applied to the polymer film 8.
• one or both of the electrodes 9, 10 may be separated from the polymer film 8 by insulating layers 11. Insulating layers 11 may be formed of an organic or inorganic insulating material, and may serve to improve dielectric breakdown resistance between the electrodes 9, 10 and/or may serve as more conventional optical cladding for the waveguide segment provided by the polymer film 8.
• the film has a thickness in the range of 100 nm - 10 microns.
• the polymer film 8 may extend between the input 3 and output 4.
• the electrodes 9, 10 do not need to be co-extensive with the polymer film 8.
• polymer chains of the polymer film 8 are aligned at an angle of 45° ⁇ 10° to the waveguide propagation axis.
• a time varying voltage signal V Sig (t) is applied across the electrodes 9, 10 to produce a time varying electric field E Sig (t) across the polymer film 8.
• the time varying voltage signal V Sig (t) is a binary signal switching between an on- state 12 and an off state 13.
• the refractive index n of the polymer film 8 will also switch between a first value m corresponding to the on-state 12 of the signal V Sig (t) and a second value corresponding to the off-state 13 of the signal V Sig (t).
• the length of the first and second paths 5, 6 are arranged so that when the polymer film 8 has the second value , the light passing along the first and second paths 5, 6 has an optical path difference of n*X, with n being an integer n > 0. The light interferes constructively and the output light 14 has a relatively high intensity state 15.
• the polymer film 8 has the first value m
• the light passing along the first and second paths 5, 6 has an optical path difference of (n ⁇ ’A)x .
• the light interferes destructively and the output light 14 has a relatively low intensity state 16.
• the output light 14 signal is a binary signal which is inverse of the time varying voltage signal V S ig(t)
• the first value nl may instead correspond to the high intensity state 15 whilst the second value corresponds to the low intensity state 16.
• the second path 6 may also include a polymer film 8 and corresponding electrodes 9, 10.
• the first and second paths 5, 6 may be arranged such that the first path 5 provides an optical path difference of (n + ’A)x during the on-state 12 whilst the second path provides an optical path difference of (m - ’A)x (with m an integer m > 0) for a total optical path difference which include a half wavelength ’AX.
• the input 3, output 4, and both paths 5, 6 may all be formed of the polymer film 8 to assist with index matching to waveguides providing incident light 7 and/or receiving output light 14.
• An optical interconnect (not shown) for transmitting data may include the EOM 1.
• a light source (not shown) can be coupled to input 3 of the EOM to provide incident light 7.
• the light source (not shown) may be any suitable light source such as, for example, a lightemitting diode (LED), and organic light emitting diode (OLED), a laser diode, an organic laser diode and so forth.
• the light source (not shown) may be directly coupled to the input 3 of the EOM 1, or may be coupled to the EOM 1 via one of more optical fibres (not shown) or other waveguides.
• the EOM 1 can be used to modulate the light 7 emitted by the light source as described hereinbefore.
• the optical interconnect may also include an optical fibre (not shown), or any other suitable waveguide structure, coupled to the output 4 to receive the modulated output light 14.
• the optical interconnect may also include a photodetector (not shown) coupled to an opposite end of the optical fibre (or other waveguide structure) to receive the modulated output light 14.
• the photodetector may be of any suitable type, for example a photodiode, but should have a bandwidth (response time) at least as fast as the intended modulation rate of the EOM 1.
• the second of waveguide 2 leading up to the input 3 may be coupled to the light source (not shown) without any intervening optical fibre (not shown). Additionally or alternatively, the section of waveguide 2 leading away from the output 4 may extend up to the photodetector (not shown) without any intervening optical fibre (not shown) or a transition to a separate waveguide structure. Extension of the sections of waveguide 2 may be preferred for short range interconnects, whereas longer interconnects may be provided more easily using optical fibres (not shown).
• Optical interconnects (not shown) including the EOM 1 may be configured to connect between a first device (not shown) and a second device (not shown), in order to transmit data from the first device to the second device or vice versa.
• a second optical interconnect may optionally transmit data in the reverse direction.
• the first and second devices may be any type of data processing devices, and do not need to be of the same type.
• Optical interconnects (not shown) including the EOM 1 may be configured to connect between a first device (not shown) and a second device (not shown) at a range of scales, for example, between two entirely separate computers, between internal components of a single computer (e.g. connecting a digital electronic processor to a memory, hard disc and so forth), between components mounted to the same circuit board, or even between components formed from a single semiconductor wafer.
• an optical interconnect may connect a pair of servers, a pair of racks within a server, a digital electronic processor to memory or other computer component, between a pair of cores of a multi-core digital electronic processor and so forth.
• Chiral intermediate formation A racemic mixture of P and M may be crystallised with chiral auxiliary, such as quinine as a as described in J. Org. Chem. 2002, 67, 3479-3486, the contents of which are incorporated herein by reference, to form a diasteromeric salt which may be separated to give a pure enantiomer.
• chiral auxiliary such as quinine as a as described in J. Org. Chem. 2002, 67, 3479-3486, the contents of which are incorporated herein by reference
• a chiral monomer as described herein containing a binaphthyl group may be formed from a BINOL, as illustrated in General Scheme 1, in which B, together with the hydroxyl groups of the binol starting material, forms a binding group:

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