Nonlinear optical chromophores containing spirofluorene-isophorone bridging groups, their preparation and application methods

Abstract

This disclosure generally relates to: (1) nonlinear optical (NLO) chromophores containing spirofluorene-isophorone bridging groups; (2) compositions / materials / resistive layers containing NLO chromophores containing spirofluorene-isophorone bridging groups, and methods for preparing compositions / materials / resistive layers containing NLO chromophores containing spirofluorene-isophorone bridging groups (e.g., polarization and / or drying methods, etc.); and (3) the use of NLO chromophores containing spirofluorene-isophorone bridging groups in electro-optic devices (e.g., EOMs).

Description

[0001] Cross-reference to related applications

[0002] This application claims the benefit of U.S. Provisional Application No. 63 / 605,792, filed December 4, 2023, the entire contents of which are incorporated herein by reference. Background Technology

[0003] The rise of silicon photonics has sparked renewed interest in the use of electro-optic (EO) materials in next-generation device applications. Thin-film materials with strong EO response and high-speed phase modulation are crucial for low-power and small-size devices, including those for data acquisition systems, analog I / O modules, field transmitters, laboratory and field instruments, servo drive control modules, DC power supplies, AC and / or electronic loads.

[0004] Typically, the electric field response (EO) reflects the change in a material's optical properties (e.g., refractive index) in response to an electric field, and the intensity of the EO response is related to the intensity of the Pockels effect. The Pockels effect (or linear EO effect) is the direction-dependent linear change in the refractive index of an optical medium in response to the application of an electric field. Macroscopically, the Pockels coefficient is... r The formula relating the change in refractive index to the applied electric field is:

[0005]

[0006] in n 0 is the refractive index in the absence of a field. n When the voltage is equal to E The refractive index of an EO material under a given electric field. Applying an electric field shifts the electron cloud into excited molecular orbitals, thus altering the refractive index. In optical media, the Pockels effect causes a change in birefringence, which is proportional to the strength of the applied electric field. EO coefficient r 33 (Unit: pmV) -1 ) is the principal element of the linear Pockels-EO effect tensor and represents the refractive index shift (Δ) obtained under the application of a low-frequency electric field. The size of ).

[0007] EO materials are generally classified into three categories: (1) liquid crystals, including ferroelectric liquid crystals and / or organic liquid crystals with linear structures, which have a central core, contain several collinear rings, linear unsaturated linkers and two terminal chains; (2) inorganic crystals characterized by a lack of inversion symmetry, such as KH2PO4 (KDP) and KD2PO4 (KD P or DKDP), lithium niobate (LiNbO3), barium metaborate (BBO), barium titanate (BTO); and (3) EO polymers, including nonlinear optical (NLO) chromophore-polymer composites.

[0008] EO materials containing liquid crystals typically exhibit ideal EO coefficients, but their phase modulation speeds are inherently low due to parasitic effects of the crystal substructure. Conversely, EO materials containing lithium niobate and / or other inorganic crystals typically achieve ideal modulation speeds, but their EO effect is inherently limited by optically active site defects that inevitably form during crystal growth.

[0009] NLO chromophore-polymer composites can simultaneously offer high electro-optic coefficients and high modulation speeds. However, the stability of both the NLO chromophore and the polymer component is a key challenge in developing EO polymer materials for practical use in commercial electro-optic devices. To meet the stringent requirements of such devices, the NLO chromophore must be photostable under photolysis and photo-oxidation processing conditions and resistant to thermal degradation at processing temperatures suitable for long-term use. Therefore, there is a need to develop NLO chromophores that not only possess high electro-optic activity but also exhibit robust photostability and thermal stability under environmental conditions. Invention Overview

[0011] This disclosure generally relates to: (1) nonlinear optical (NLO) chromophores; including (2) compositions / materials / resistive layers containing NLO chromophores, and methods for preparing compositions / materials / resistive layers containing NLO chromophores (e.g., polarization and / or drying methods, etc.); and (3) the use of NLO chromophores in electro-optic devices (e.g., EOMs). The NLO chromophores disclosed herein not only exhibit large EO effects but also fast modulation speeds. Furthermore, the NLO chromophores disclosed herein possess excellent photostability and thermal stability compared to other EO materials. Therefore, the NLO chromophores of this invention are particularly suitable for use as EO materials associated with low-power and small-size devices, including devices for data acquisition systems, analog I / O modules, field transmitters, laboratory and field instruments, servo drive control modules, DC power supplies, AC and / or electronic loads.

[0012] On the one hand, NLO chromophores containing spirofluorene-isophorone bridging groups are disclosed. In one example, various embodiments of this disclosure include nonlinear optical chromophores of general formula (I):

[0013] D- -A (I)

[0014] Where D represents an organic electron-donating group; A represents an organic electron-withdrawing group with an electron affinity greater than that of D; and This indicates the relationship between organic electron-withdrawing groups and organic electron-donating groups. -bridge; wherein -The bridge has the following formula (II) 1 ):

[0015] (II 1 )

[0016] Where a and b each independently represent an integer from 1 to 3; where each x independently represents an integer from 0 to 4; where z represents an integer from 1 to 3; where each R' independently represents a substituent selected from the group consisting of hydrogen, halogen, substituted or unsubstituted aryl, substituted or unsubstituted alkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic and substituted or unsubstituted cyclohexyl; where each R independently represents a substituent selected from the group consisting of hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted alkyl, substituted or unsubstituted mercapto, substituted or unsubstituted hydroxyl or substituted or unsubstituted amino.

[0017] Various implementations of nonlinear optical chromophores with spirofluorene-isophorone bridges can achieve high EO coefficients. 33 EO coefficient r 33 Perhaps one of the most important properties of the potential coefficient (EO) is that it represents the relationship between the applied potential change and the change in the material's refractive index. A higher EO coefficient r... 33 This may indicate that nonlinear optical chromophores have better EO properties and better potential applications.

[0018] In the same or another instance, various embodiments of this disclosure may include a nonlinear electro-optic material comprising the aforementioned nonlinear optical chromophores and one or more matrix materials (also referred to as host polymers) into which the nonlinear optical chromophores may be incorporated. The nonlinear optical chromophores can typically be incorporated into the matrix material in virtually any amount, or can be used without a matrix material (i.e., “pure” or 100% chromophores).

[0019] In the same or another example, various embodiments of this disclosure may include a composition comprising the aforementioned nonlinear electro-optic material and a solvent. Solvents suitable for the various embodiments may include conventional solvents and / or high-boiling-point solvents. High-boiling-point solvents may include solvents with a boiling point greater than or equal to 100°C (at 1 atm). Glass transition temperature (Tg) g This is typically the temperature at which an amorphous polymer transitions from a hard / glassy state to a soft / rubbery state (or vice versa).

[0020] In the same or another example, various embodiments of this disclosure may include compositions comprising a nonlinear optical chromophore having a spirofluorene-isophorone bridge. Compositions comprising a nonlinear optical chromophore having a spirofluorene-isophorone bridge can exhibit high stability, including photostability and thermal stability. The thermal stability of the nonlinear optical chromophore can be determined based on the thermal decomposition temperature (T0) of the chromophore. d The assessment is based on the thermal decay of the chromophore and / or the chromophore. For example, the thermal decomposition temperature (T0) is used. d This could be the temperature at which the chromophore chemically decomposes. Similarly, thermal decay could be the percentage of chromophores that chemically decompose within a given time period at a given temperature.

[0021] Meanwhile, high photostability ensures that nonlinear optical chromophores do not degrade under illumination in an air atmosphere. The photostability of nonlinear optical chromophores can be evaluated based on light decay. For example, light decay can be the percentage of a nonlinear optical chromophore that degrades after being exposed to ultraviolet-visible light for a given time.

[0022] In the same or another example, various embodiments of this disclosure include a resistive layer formed from the above composition by one or more processes. These processes may include, but are not limited to, polarization and / or drying.

[0023] During polarization and / or drying, electro-optic materials can be dispersed in a suitable solvent in virtually any amount that provides a homogeneous solution and properties suitable for resistive layer formation. The resistive layer can be polarized by applying a suitable voltage to the material at a suitable temperature. After polarization, the resistive layer can be dried and / or densified by removing the remaining solvent while the applied voltage field is still maintained.

[0024] In the same or another instance, various embodiments of this disclosure may include electro-optic devices comprising one or more of the aforementioned resistive layers and possessing electro-optic functionality. The electro-optic devices may include electro-optic modulators (EOMs), which are optical devices in which a signal control element with an electro-optic effect is used to modulate a light beam. In EOMs, nonlinear electro-optic materials can be spin-coated onto a silicon wafer, and metal electrodes and optical waveguides can be deposited and patterned using standard microfabrication techniques.

[0025] EOMs comprising various embodiments of nonlinear optical chromophores with spirofluorene-isophorone bridges may include modulators applied to, for example, slot modulators (e.g., slot modulators for wafer-level polarization), photonic integrated circuits (e.g., polymer photonic integrated circuits), data center switching, high-voltage sensing devices related to the power industry, electro-optic signal conversion devices for transmitting multiple television signals related to cable television (CATV) or satellite television, broadband acoustic spectrum analyzers, optical gyroscopes, phased array radars (e.g., integrated antenna / electro-optic modulators or W-band optical modulators), photonic detection radars, time-stretching and ultrafast analog-to-digital conversion devices, fiber optic and satellite telecommunications components, ultrafast electric field generation and detection devices, electric field sensors (e.g., electro-optic E-field sensors), mine detection devices, wavelength division multiplexing related devices, optical switches, spatial light modulation related devices (e.g., beam steering related devices), and / or augmented reality (AR) / virtual reality (VR) devices (e.g., full-spectrum visible photoelectric modulators).

[0026] For example, a photonic integrated circuit (PIC) can be a chip that performs optical signal processing. This chip can contain two or more photonic components (e.g., a resistive layer with nonlinear electro-optical material) that form functional circuitry to utilize photons to detect, generate, transmit, and process light. PICs have demonstrated significant potential in providing the performance (e.g., speed, size, and efficiency) required for future applications such as 6G, automotive light detection and ranging (LiDAR), consumer healthcare, artificial intelligence (AI), optical computing, virtual reality (VR), and / or augmented reality (AR). Brief description of the attached diagram

[0028] The foregoing summary of the invention and the following detailed description of preferred embodiments will be better understood when read in conjunction with the accompanying drawings. The embodiments shown in the drawings are for illustrative purposes. However, it should be understood that this disclosure is not limited to the precise arrangements and arrangements shown.

[0029] In the attached diagram:

[0030] Figure 1 This is a schematic diagram of a degenerate four-wave mixer (DFWM) test procedure used to evaluate the third-order NLO performance of thin film composites.

[0031] Figure 2 An example of the polarization process in nonlinear electro-optic materials is shown.

[0032] Figure 3A This is a partial side view cross-sectional diagram of an integrated electro-optical circuit.

[0033] Figure 3B yes Figure 3A A partial cross-sectional view of the integrated electro-optical circuit.

[0034] Figure 4 This is an end view of a slot modulator with highly doped silicon slabs and rails. Invention Details

[0036] Terms and Concepts

[0037] As used in this article, the term "nonlinear optical chromophore" (NLO chromophore) refers to a molecule or part of a molecule that produces a nonlinear electro-optic effect when illuminated.

[0038] The term "electron-donating group" as used in this article refers to the electron-donating group that contributes electrons to conjugated electrons through resonance and / or inductive effects. The system provides a portion of its electron density from atoms and / or functional groups.

[0039] The term "electron-accepting group" as used in this article refers to a group that is conjugated with electrons. Atoms and / or functional groups in the system that accept part of the electron density of electron-donating groups through resonance and / or inductive effects.

[0040] The term "bridging group" used in this article refers to the conjugate... Functional groups that bridge the gap between electron-donating and electron-withdrawing groups in the system.

[0041] The term “four-wave mixing” (FWM) used in this article refers to the interaction of four different fields in space or spectrum.

[0042] The term “r” used in this article 33 "r" refers to the electro-optic coefficient, a function of the first-order hyperpolarizability, representing the relationship between the applied potential change and the material's refractive index change. 33 The unit for "r" is pm / V. 33 " is the principal element of the Pockels EO effect tensor and a function of the first-order hyperpolarizability (β), representing the refractive index shift (Δ) obtained under the application of a low-frequency electric field." The magnitude of ) represents the relationship between the applied potential change and the material refractive index change.

[0043] The term "ε" used in this article refers to the dielectric constant, also known as permittivity. The dielectric constant is a measure of the degree of polarization of a material under an applied (external) electric field. Polarization is equivalent to the net separation of charges in a material.

[0044] The term "susceptibility" used in this article refers to the degree of polarization of a material under the influence of an external electric field. Different orders of susceptibility exist, such as linear susceptibility (χ²). (1)Second-order polarizability (χ) (2) ), third-order polarizability (χ) (3) Second-order polarizability describes a material's response to two electric fields of different frequencies. When an electric field is applied to a material with a non-zero second-order polarizability, an electro-optic effect occurs. When an electric field is applied to such a material, the polarization changes, resulting in a change in refractive index. The change in refractive index is proportional to the magnitude of the externally applied electric field. Third-order polarizability (χ²) and other higher-order polarizabilities. (3) This describes the material's response to three different electric fields. Since polarizability always exhibits dispersion (i.e., frequency dependence), the third-order polarizability coefficients associated with each electric field will differ.

[0045] As used in this paper, the terms “optical nonlinearity,” “nonlinearity,” and “nonlinear” refer to the behavior of light in a nonlinear medium, i.e., a medium in which the polarization density P responds nonlinearly to the electric field (E) of light. Nonlinearity is typically only observed at very high light intensities (when the electric field of light > 10⁸ V / m, thus comparable to the atomic electric field of ~10¹¹ V / m), such as the intensity provided by a laser.

[0046] As used herein, the term "nonlinear electro-optic material" refers to a material containing nonlinear optical chromophores and one or more matrix materials (also called host polymers) in which one or more nonlinear optical chromophores can be incorporated. EO materials can exhibit nonlinear EO effects. Suitable matrix materials can include polymers such as polymethyl methacrylate (PMMA); polyimide; polyamic acid; polystyrene; polyurethane (PU); and amorphous polycarbonate (APC). NLO materials are anisotropic in the presence of electromagnetic radiation. When the electric field strength is very high, electrons in the material will be displaced very large from their equilibrium positions. Therefore, anharmonic behavior appears in the picture of electron oscillations. Thus, the general linear relationship becomes nonlinear. The polarization intensity (P) of the medium is a nonlinear function of the electric field intensity (E), and can be expressed as follows:

[0047] P = χE

[0048] Here, χ is the polarizability. (n) It is a tensor, and n is the process order. (χ) (1) = Linear polarizability, χ (2) , χ (3) …=first, second…hyperpolarizability coefficients, etc.). Nonlinearity can only be observed at very high light intensities (such as those provided by lasers).

[0049] As used herein, the term "composition" refers to one or more mixed compositions that may contain nonlinear electro-optic materials and solvents.

[0050] As used herein, the term "resistive layer" refers to one or more layers formed from the above composition through one or more processes.

[0051] As used herein, the term "electro-optic device" refers to a device that has electro-optic functionality and includes one or more of the aforementioned resistive layers. For example, an electro-optic device may include an electro-optic modulator (EOM), which is an optical device in which a light beam is modulated using a signal control element having an electro-optic effect.

[0052] The term "refractive index" as used in this article is a dimensionless number of an optical medium, representing its ability to bend light. The refractive index determines the degree of bending or refraction of the path of light entering a material, as stated in Snell's law of refraction: n1sinθ1 = n2sinθ2, where θ1 and θ2 are the angles of incidence and refraction, respectively, when light passes through the interface of two media with refractive indices n1 and n2. The refractive index also determines the amount of light reflected when it reaches the interface, as well as the critical angle for total internal reflection, the light intensity (Fresnel's equations), and the Brewster's angle. The refractive index also reflects the rate of radiation and the factor by which the wavelength decreases relative to its vacuum value: the speed of light in a medium is ν = c / n, and similarly, the wavelength in that medium is λ = λ0 / n, where λ0 is the wavelength of the light in a vacuum. This implies that the refractive index of vacuum is 1, and it is assumed that the frequency of the wave (f = ν / λ) is unaffected by the refractive index.

[0053] The term "electro-optic (EO) effect" as used in this paper refers to the change in optical phase retardation (i.e., refractive index) induced by an electric field. The intensity of the EO effect is related to the intensity of the Pockels effect in the material. The Pockels effect (or linear EO effect) is a direction-dependent linear change in the refractive index of an optical medium in response to the application of an electric field. Macroscopically, the Pockels coefficient... r The formula relating the change in refractive index to the applied electric field is:

[0054]

[0055] in n 0 is the refractive index in the absence of a field. n When the voltage is equal to E The refractive index of an EO material under a given electric field. The applied electric field shifts the electron cloud into excited molecular orbitals, thus altering the refractive index. In optical media, the Pockels effect causes a change in birefringence, which is proportional to the strength of the applied electric field.

[0056] Nonlinear optical chromophores

[0057] The electro-optic (EO) effect is the response of a material's optical properties to a change in an electric field that varies slowly compared to the frequency of light. For example, the EO effect can manifest as a change in refractive index under the influence of an electric field. This change in refractive index under an electric field can be explained by the Pockels effect. Under the Pockels effect, an electric field can shift the electron cloud into excited molecular orbitals and alter the material's refractive index, which in turn can cause a phase change in any transmitted optical signal.

[0058] Materials exhibiting electro-optic effects can include liquid crystals, lithium niobate and / or other inorganic crystals, and / or organic nonlinear optical chromophores. Liquid crystals can exhibit large EO effects but slow modulation speeds. Lithium niobate and / or other inorganic crystals can exhibit fast modulation speeds but small EO effects. By comparing organic nonlinear optical chromophores with liquid crystals and lithium niobate and / or other inorganic crystals, organic nonlinear optical chromophores can simultaneously possess both large EO effects and fast modulation speeds.

[0059] As used in this paper, the term "nonlinear optical chromophore" (NLO chromophore) refers to a molecule or molecular unit that produces a nonlinear electro-optic effect when illuminated. A chromophore is any molecular unit that interacts with light to produce a nonlinear optical effect. The desired effect may occur at either resonant or non-resonant wavelengths. The activity of a specific chromophore in a nonlinear electro-optic material is determined by its electro-optic coefficient (r). 33 The coefficient indicates that it is related to the molecular dipole moment and hyperpolarizability. The NLO chromophores of various embodiments of this disclosure are useful structures for generating the NLO effect.

[0060] The nonlinear optical chromophores according to various embodiments of this disclosure have the general formula (I):

[0061] D- -A (I)

[0062] Where D represents an organic electron-donating group; A represents an organic electron-withdrawing group with an electron affinity greater than that of D; and Indicates the relationship between A and D -Bridge. The term refers to an electron-donating group (donor or "D"). - Bridge (bridge foundation or " " and electron-withdrawing groups (acceptors or "A"), and the formation of D- The general methods for synthesizing -A chromophores are well known in the art.

[0063] The donor is an atom or group of atoms with a low oxidation potential, wherein the atom or group of atoms can be converted into an atom or group of atoms through oxidation potential. - The bridge provides electrons to the acceptor. The donor (D) has a lower electron affinity than the acceptor (A), and therefore, at least in the absence of an external electric field, the chromophore is typically polarized, resulting in a relatively low electron density on the donor (D). Typically, the donor group contains at least one heteroatom with a lone pair of electrons capable of conjugating with the p orbital of an atom directly attached to it, thereby forming a resonance structure that moves the lone pair of electrons into the bond of the p orbital of the atom directly attached to the heteroatom. This formally increases the bond order between the heteroatom and the atom directly attached to it (i.e., a single bond formally transforms into a double bond, or a double bond formally transforms into a triple bond), giving the heteroatom a formal positive charge. The p orbital of the atom directly attached to the heteroatom can be empty or part of a multiple bond with another atom different from the heteroatom. The heteroatom can be a substituent of an atom with a π bond or can be in a heterocycle. Exemplary donor groups include, but are not limited to, R2N- and R n X 1 --, where R is an alkyl, aryl, or heteroaryl group, and X 1 It is O, S, P, Se, or Te, and n is 1 or 2. The total number of heteroatoms and carbon atoms in the donor group can be about 30, and the donor group can be further substituted with alkyl, aryl, or heteroaryl groups.

[0064] In some embodiments of this disclosure, D can represent any organic electron-donating group, provided that two atomic positions of D on the core are bonded to the core (these two atomic positions are different from the two atomic positions of A bonded to the core), such that at least a portion of D forms a ring fused to the core.

[0065] Examples of organic electron-donating groups suitable for incorporating chromophores of general formula (I) include, but are not limited to, the following structures, where the dashed lines indicate the two atomic positions where D forms a ring fused with the core:

[0066]

[0067] Each R independently represents a side chain spacer group.

[0068] Among the various nonlinear optical chromophores disclosed in the various embodiments of the present invention, suitable electron-donating groups include those according to the general formula (D a Those:

[0069]

[0070] Where R 5The part representing the group selected from the following: H, substituted or unsubstituted straight-chain or branched alkyl, substituted or unsubstituted straight-chain or branched alkenyl, substituted or unsubstituted straight-chain or branched alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, substituted or unsubstituted cyclohexyl, and (CH2). n -O-(CH2) n Where n is 1-10, and R 5 With R 8 Or R 9 Together they can form a 5- or 6-membered ring; R 8 and R 9 Is it H or R? 5 Forming 5- or 6-membered rings;

[0071] Where R 6 The part selected from the group consisting of: H, halogen, substituted or unsubstituted heteroaryl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted amino, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted thioalkyl, substituted or unsubstituted C1-C 10 Straight-chain or branched alkyl, substituted or unsubstituted C2-C 10 Straight-chain or branched alkenyl, substituted or unsubstituted C2-C 10 Straight-chain or branched alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, substituted or unsubstituted cyclohexyl, substituted or unsubstituted silaneoxymethyl, and CH3-(CH2). n -O-(CH2) n Where n is 1-10; and

[0072] Where R 7 The part selected from the group consisting of: H and substituted or unsubstituted alkyl groups.

[0073] In one embodiment, R 5 and R 6 One or two of them are substituted or unsubstituted phenyl groups.

[0074] In various implementation schemes, there is a general formula (D) a The electron-donating group of the quinoline group can include a quinoline group, which can be substituted or unsubstituted, including hydrogen and alkyl substituents, aryl substituents, and combinations thereof. Such quinoline groups can have one or more adamantyl groups covalently linked to them. Such quinoline groups can include substituted or unsubstituted tetrahydroquinoline groups. For example, a substituted or unsubstituted tetrahydroquinoline group can have the general formula (D...). 1 ):

[0075]

[0076] Where R 1 It may include any aryl or alkyl group, and R 4 It may include hydrogen or methyl portions.

[0077] In various implementations, the general formula (D) is described. 1 The electron-donating group of ) can be:

[0078] .

[0079] Acceptors are atoms or groups of atoms with low reduction potentials, wherein the atoms or groups of atoms can pass through... - The acceptor (A) accepts electrons from the donor. The acceptor (A) has a higher electron affinity than the donor (D), and therefore, at least in the absence of an external electric field, the chromophore is typically polarized in the ground state, resulting in a relatively high electron density on the acceptor (A). Typically, the acceptor group contains at least one electronegative heteroatom that is part of a π bond (double or triple), allowing for the formation of a resonance structure that shifts the electron pair of the π bond to the heteroatom while simultaneously lowering the bond order of the π bond (i.e., a double bond formally converts to a single bond, or a triple bond formally converts to a double bond), thus giving the heteroatom a formal negative charge. The heteroatom can be part of a heterocycle. Exemplary acceptor groups include, but are not limited to, -NO2, -CN, -CHO, COR, CO2R, -PO(OR)3, -SOR, -SO2R, and -SO3R, where R is an alkyl, aryl, or heteroaryl group. The total number of heteroatoms and carbon atoms in the acceptor group is approximately 30, and the acceptor group can be further substituted with alkyl, aryl, and / or heteroaryl groups.

[0080] Among the various nonlinear optical chromophores according to various embodiments of this disclosure, suitable electron-withdrawing groups include those conforming to the general formula (A 1 Those:

[0081] (A) 1 )

[0082] Where R 2 and R 3 Each of the following groups is independently represented: H, substituted or unsubstituted C1-C. 10 Alkyl, substituted or unsubstituted C2-C 10 alkenyl, substituted or unsubstituted C2-C 10 Alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, substituted or unsubstituted cyclohexyl, and (CH2).n -O-(CH2) n Where n is 1-10. As used in this article, This indicates the point where the molecules bond to another part of a larger molecular structure. In various preferred embodiments, R... 2 and R 3 One or both of them represent the halogen-substituted portion. Halogen substitution can refer to mono-substituted, di-substituted, tri-substituted, and higher degrees of substitution. In various preferred embodiments, R 2 and R 3 One of them represents a halogen-substituted alkyl moiety, and the other represents an aromatic moiety. In various preferred embodiments, R 2 and R 3 One of them represents the halogen-substituted aromatic moiety, and the other represents the alkyl moiety.

[0083] General formula (A) 1 An example of an electron-withdrawing group can be:

[0084] .

[0085] In various embodiments, the aforementioned R in the electron-withdrawing group 2 The group can be trifluoromethyl. The R in the electron-withdrawing group... 3 The group may include substituted or unsubstituted phenyl groups, such as phenyl and / or methylbenzyl. Therefore, the general formula for electron-withdrawing groups is (A...). 2 It could be:

[0086] (A 2 )

[0087] Where R 10 The part is selected from the group consisting of: H, substituted or unsubstituted alkyl and substituted or unsubstituted aryl.

[0088] General formula (A) 2 Examples of electron-withdrawing groups include:

[0089]

[0090] “ A "bridge" comprises an atom or group of atoms through which electrons can be delocalized from an electron donor (as defined above) to an electron acceptor (as defined above) via the orbitals of the atoms in the bridge. Such groups are well known in the art. Typically, the orbitals will be double bonds (sp...). 2The bridging orbitals are p orbitals on carbon atoms in a triple bond (sp), such as those found in alkenes, alkynes, neutral or charged aromatic rings, and neutral or charged heteroaromatic ring systems. Alternatively, the orbitals can be p orbitals on atoms such as boron or nitrogen. Furthermore, the orbitals can be p, d, or f organometallic orbitals or hybrid organometallic orbitals. The bridging atom containing the orbital through which electrons delocalize is referred to herein as a "key atom." The number of key atoms in the bridge can range from 1 to about 30. Key atoms can be substituted with organic or inorganic groups. Substituents can be selected to improve the solubility of the chromophore in the polymer matrix, enhance the stability of the chromophore, or for other purposes.

[0091] In various embodiments, the bridging base of the nonlinear optical chromophore according to general formula (I) of this disclosure ( ) including those with general formula (II) 1 The spirofluorene-isophorone bridge,

[0092] (II 1 )

[0093] Each R' may represent a substituent selected from the group consisting of hydrogen, halogen, substituted or unsubstituted aryl, substituted or unsubstituted alkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, and substituted or unsubstituted cyclohexyl; each R may represent a substituent selected from the group consisting of hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted alkyl, substituted or unsubstituted mercapto, substituted or unsubstituted hydroxyl, or substituted or unsubstituted amino; a and b each independently represent an integer from 0 to 3; each x independently represents an integer from 0 to 4; and z represents an integer from 1 to 3.

[0094] General Formula (II) 1 Examples of bridge foundations can be:

[0095] .

[0096] The nonlinear optical chromophore according to various embodiments of this disclosure further includes a spirofluorene-isophorone bridging group connected to an electron-donating group and an electron-withdrawing group. The spirofluorene-isophorone bridging group can function as a bridge in the chromophore. -bridge.

[0097] Examples of chromophores having a spirofluorene-isophorone bridging group according to various embodiments of this disclosure may include the following chromophores:

[0098] .

[0099] First-order hyperpolarizability (β) is one of the most common and useful NLO properties. Electro-optic coefficient (r 33) is a function of β, and r is sufficient 33 The value can indicate good electro-optic properties in a given NLO. For example, sufficient r 33 The value can be equal to or greater than 100 pm / V.

[0100] Second-order hyperpolarizability (γ) or third-order polarizability (χ) (3) The activity of a third-order NLO is a common measure. While several methods exist for measuring these properties, degenerate four-wave mixing (DFWM) is very common. The term four-wave mixing (FWM) generally refers specifically to the interaction between four different fields in space or spectrum. In the most common FWM processes, some frequencies, wave vectors, and polarizations are degenerate. For example, when two or more frequencies are degenerate, FWM can be simplified to the most common FWM processes. The most common FWM processes can include, but are not limited to, coherent anti-Stokes Raman spectroscopy (CARS), coherent Stokes Raman spectroscopy (CSRS), stimulated Raman gain spectroscopy (SRS), inverse Raman effect spectroscopy (TIRES), and / or Raman-induced Kerr effect spectroscopy (RIKES). FWM can be used to probe single-photon or two-photon resonances in materials by measuring the resonance enhancement when one or more frequencies are tuned. One method for evaluating the third-order NLO properties of thin films, referred to in the art as degenerate four-wave mixing (DFWM), can be as follows: Figure 1 As shown. In Figure 1 In the diagram, beams 102 and 104 are picosecond coherent pulses absorbed by the NLO film 110 deposited on the glass substrate 112. Beam 106 is a weaker, slightly delayed beam with the same wavelength as beams 102 and 104. Beam 108 is a product of wave mixing, formed by transient holographic grating diffraction resulting from the interference of beams 102 and 104 in the NLO material of film 110. Beam 106 can be a "control" beam at a telecommunication wavelength, generating a "signal" beam whose frequency is not absorbed by the NLO material.

[0101] The electro-optic (EO) properties of polarized nonlinear electro-optic materials doped with nonlinear optical chromophores can be tested as follows: Polarized light (typically from a laser) is passed through a polarized material doped with polarized nonlinear optical chromophores, then through a polarizing filter, and finally to a light intensity detector. If the light intensity received by the detector changes when the potential applied to the electrodes changes, then the material has been doped with nonlinear optical chromophores and possesses an electro-optically variable refractive index.

[0102] The relationship between the change in applied electric potential and the change in the refractive index of the material can be expressed as its EO coefficient r. 33This effect is commonly referred to as the electro-optic or EO effect. Devices containing materials that change their refractive index in response to an applied potential change are called electro-optic (EO) devices. For the compositions described herein with nonlinear optical chromophores having spirofluorene-isophorone bridges, EO coefficients > 45 pm / V, or > 75 pm / V, or > 110 pm / V, or even greater, can be achieved. 33 .

[0103] Nonlinear electro-optic materials

[0104] As used herein, the term "nonlinear electro-optic material" refers to a material that simultaneously contains nonlinear optical chromophores and one or more matrix materials (also known as host polymers) in which one or more nonlinear optical chromophores can be incorporated. Suitable matrix materials may include polymers such as: polymethyl methacrylate (PMMA); polyimide; polyamic acid; polystyrene; polyurethane (PU); and amorphous polycarbonate (APC).

[0105] Glass transition temperature (T) g The glass transition temperature (T0) is the temperature at which an amorphous polymer transitions from a hard / glassy state to a soft / rubbery state, or vice versa. In various embodiments, the matrix material may include poly(methyl methacrylate), for example, a polymer with a molecular weight of about 120,000 and a glass transition temperature (T0). g Polymethyl methacrylate (PMMA) at approximately 100-165°C, or T g APC is approximately 150-220°C.

[0106] Nonlinear optical chromophores can typically be incorporated into a matrix material in virtually any amount, or can be used without a matrix material (i.e., "pure" or 100% chromophore). For example, based on the total weight of the combined nonlinear optical chromophore and matrix material, a suitable electro-optic material may contain from about 1% to 90% by weight of nonlinear optical chromophores. In various embodiments, based on the total weight of the combined nonlinear optical chromophore and matrix material, a suitable electro-optic composition may contain from about 2% to 80% by weight of nonlinear optical chromophores. In various embodiments, based on the total weight of the combined nonlinear optical chromophore and matrix material, a suitable electro-optic composition may contain from about 3% to 75% by weight of nonlinear optical chromophores. For example, one or more chromophores may be combined with a mixture of amorphous polycarbonate or matrix material at a ratio of 70% chromophore / 30% matrix material. In various embodiments, the chromophore may be crosslinked with the matrix material or other polymers.

[0107] Composition

[0108] As used herein, the term "composition" refers to one or more mixed compositions that may simultaneously contain a nonlinear electro-optic material and a solvent. Suitable solvents may include conventional boiling point solvents and high-boiling point solvents. As used herein, "high-boiling point solvent" refers to a solvent with a boiling point greater than or equal to 100°C (at 1 atmosphere). In various embodiments, suitable solvents have boiling points greater than or equal to 110°C, greater than or equal to 120°C, greater than or equal to 130°C, greater than or equal to 140°C, greater than or equal to 150°C, greater than or equal to 160°C, greater than or equal to 170°C, greater than or equal to 180°C, greater than or equal to 190°C, greater than or equal to 200°C, greater than or equal to 210°C, greater than or equal to 220°C, greater than or equal to 230°C, greater than or equal to 240°C, and greater than or equal to 250°C.

[0109] Solvents suitable for various embodiments are capable of forming a homogeneous solution of the composition and typically include high-boiling-point, relatively nonpolar aprotic solvents. Suitable solvents include, for example... N Methylpyrrolidone, dimethyl sulfoxide, carbonates (such as ethylene carbonate and propylene carbonate), and glycol ethers (such as diethylene glycol dibutyl ether). Solvents considered "polar," such as DMSO, may also be used, and are considered relatively nonpolar in terms of their ability to dissolve both polar and nonpolar solutes simultaneously. In various embodiments, suitable high-boiling solvents may include diethylene glycol dibutyl ether. In various embodiments, the high-boiling solvent may be mixed with a co-solvent that does not have a high boiling point.

[0110] The nonlinear optical chromophores with spirofluorene-isophorone bridges described herein, and compositions containing nonlinear optical chromophores with spirofluorene-isophorone bridges, exhibit high stability, including photostability and thermal stability. The thermal stability of the nonlinear optical chromophore can be determined based on the chromophore's thermal decomposition temperature (T0). d The thermal decay of the chromophores and / or chromophores is used for evaluation. Thermal decomposition temperature (T) d The temperature at which the chromophore undergoes chemical decomposition is called the temperature at which the chromophore decomposes. For example, the decomposition temperature of the nonlinear optical chromophore with a spirofluorene-isophorone bridge described herein can be greater than or equal to 200°C, or greater than or equal to 225°C, or greater than or equal to 250°C, or even higher. Thermal decay is the percentage of the chromophore that chemically decomposes within a given time period at a given temperature. For example, the thermal decay of the nonlinear optical chromophore with a spirofluorene-isophorone bridge described herein within 90 minutes at 180°C can be < 15%, or < 10%, or < 5%, or even lower.

[0111] Photostability is one of the most useful properties of nonlinear optical chromophores. High photostability is important because it ensures that the chromophore will not degrade under light exposure in an atmospheric atmosphere. Degradation of the chromophore occurs under light exposure in air if the double bonds in the nonlinear optical chromophore react with molecular oxygen. Molecular oxygen in the atmospheric atmosphere can be either triplet or singlet oxygen. Triplet oxygen is the electronic ground state of molecular oxygen, meaning it is the most stable and common allotrope of oxygen and does not react with double bonds. Light converts triplet oxygen molecules into singlet oxygen molecules, which react very readily with double bonds. In short, singlet oxygen is the reason why chromophores degrade under light exposure in an atmospheric atmosphere. The reaction of singlet oxygen with the chromophore's double bonds inactivates the chromophore by rendering the double bonds optically inactive. Therefore, if a nonlinear optical chromophore can resist degradation by singlet oxygen, it will possess high photostability, and less resources will be needed to remove oxygen from the working device.

[0112] The photostability of chromophores can be assessed based on light decay. Light decay is the percentage of a chromophore that degrades after being exposed to UV-Vis light for a given period of time. For example, the nonlinear optical chromophores with spirofluorene-isophorone bridges described herein may exhibit light decay of <15%, <10%, <5%, or even lower after 20 hours of light exposure.

[0113] Nonlinear optical chromophores with spirofluorene-isophorone bridging groups exhibit high photostability. For example, after 20 hours of exposure to broadband UV-Vis light, the photostability of nonlinear optical chromophores with spirofluorene-isophorone bridging groups can be <15%, <10%, <5%, or even lower. Photostability was measured by calculating the percentage of chromophores degraded by UV-Vis after irradiating the chromophores for 20 hours at ambient temperature and pressure using a 6 mW broadband lamp (e.g., wavelength range of 360 nm to 2600 nm). For example, 45% photostability means that after 20 hours of illumination, 45% of the nonlinear optical chromophores were degraded by light and / or singlet oxygen, while 55% remained unchanged. Therefore, low photostability indicates high photostability of the chromophore.

[0114] The optical attenuation data for various implementation schemes with nonlinear optical chromophores having spirofluorene-isophorone bridging groups are summarized below:

[0115]

[0116] To obtain the above light attenuation data, all chromophores were tested by UV-Vis after 20 hours of irradiation with a 6mW broadband lamp (e.g., wavelength range of 360nm to 2600nm) under ambient temperature and pressure.

[0117] Nonlinear optical chromophores with spirofluorene-isophorone bridging groups exhibit high thermal stability. In one example, the decomposition temperature (T0) of the nonlinear optical chromophores with spirofluorene-isophorone bridging groups described herein is [missing information]. d The temperature can be greater than or equal to 200°C, or greater than or equal to 225°C, or greater than or equal to 250°C, or even higher. In another example, the nonlinear optical chromophores with spirofluorene-isophorone bridges described herein exhibit thermal decay of less than 15%, or less than 10%, or less than 5%, or even lower, when exposed to a pure nitrogen atmosphere at ambient pressure and 180°C for 90 minutes. For example, a 5% thermal decay means that within 90 minutes at 180°C, 5% of the chromophores are decomposed or degraded, while 95% remain unchanged. Therefore, low thermal decay and high TT... d This can indicate that the chromophore has high thermal stability.

[0118] Thermal attenuation data and To of various implementation schemes of nonlinear optical chromophores with spirofluorene-isophorone bridging groups d and glass transition temperature (T g In summary:

[0119]

[0120] To obtain the above thermal decay data, all chromophores were tested by exposing them to a pure nitrogen atmosphere at ambient pressure at 180°C for 90 minutes.

[0121] Methods for forming a resistive layer

[0122] As used herein, the term "resistive layer" refers to one or more layers formed from the above composition through one or more processes. These processes may include, but are not limited to, spin coating and / or atomic layer deposition (ALD) processes. Spin coating can be a process of depositing nonlinear electro-optic materials onto a flat substrate to form a resistive layer. For example, a small amount of nonlinear electro-optic material can be applied to the center of the substrate. The substrate can be rotated at speeds up to 10,000 rpm, spreading the nonlinear electro-optic material by centrifugal force to form the resistive layer. ALD can be an ultrathin film deposition technique controlled by a gas-phase and sequential self-limiting chemical reaction of precursors on the material surface.

[0123] Furthermore, the composition can be dried and / or polarized prior to one or more steps to achieve the desired EO effect. Electro-optic materials can be dispersed in a suitable solvent in virtually any amount that provides a homogeneous solution and properties suitable for resistive layer formation. For example, according to the various embodiments described herein, the solid content of the electro-optic material in the solvent can be adjusted according to the desired resistive layer thickness and the spin-coating speed of the spin-coating equipment. As is known in the art, lower viscosity solutions generally result in thinner spin-coated resistive layers. In various embodiments, the solid content of the electro-optic material in the solvent can be from about 1% to about 25%. In various embodiments, the solid content of the electro-optic material in the solvent can be from about 2% to about 20%. In various embodiments, the solid content of the electro-optic material in the solvent can be from about 5% to about 15%.

[0124] According to various embodiments of this disclosure, exemplary methods include providing a composition as described herein, forming a resistive layer comprising the composition, drying the resistive layer (i.e. removing the solvent), and polarizing the resistive layer.

[0125] A suitable resistive layer can be formed on a substrate using methods such as spin coating or inkjet printing. Suitable substrates can include indium tin oxide (ITO) coated surfaces, conductive materials, silicon, semiconductors, etc. The resistive layer can be formed in various thicknesses ranging from submicron to several micrometers.

[0126] Figure 2 An example of the polarization process in a nonlinear electro-optic material is illustrated. Due to the non-uniform distribution of electron density within the nonlinear optical chromophore, the electron density of the electron-withdrawing groups is higher than that of the electron-donating groups. Therefore, each nonlinear optical chromophore molecule can contain a dipole 202, which presents a positive charge on the electron-donating group side and a negative charge on the electron-withdrawing group side. When no voltage 204 is applied, there is no charge on the electrode 206. The dipoles are randomly oriented and not aligned. However, when voltage 204 is applied, the electrode 206 can have a charge (e.g., positive or negative), and an electric field is formed therebetween. The dipoles 202 are polarized and aligned under the influence of the electric field, thereby producing a non-centrosymmetric nonlinear electro-optic material.

[0127] The resistive layer prepared according to the various methods disclosed herein can be polarized by applying a suitable voltage to the material at a suitable temperature. In various devices and structures, electrodes can be formed or positioned on opposite sides of the resistive layer, or above and below the resistive layer, and a suitable voltage can be applied to the resistive layer in this manner. The electrodes can be formed of, for example, gold. The suitable voltage can be from about 50 V / μm to about 150 V / μm. The suitable temperature for polarizing the resistive layer is typically higher than the glass transition temperature (T0) of the nonlinear optical chromophore. g The temperature is high enough to allow nonlinear optical chromophores to align within the material. Furthermore, the solvent is completely removed from the composition before polarization.

[0128] After polarizing the resistive layer, while maintaining the applied voltage field, the resistive layer according to the various embodiments described herein can be dried or densified by removing the residual solvent. Typically, the solvent is removed until the glass transition temperature of the resistive layer approaches the Tg of the chromophore. g Solvent drying or removal can be performed, for example, by slowly and slightly increasing the temperature while maintaining the polarization field until the solvent is removed, followed by cooling. Alternatively, solvent drying or removal can be performed, for example, by cooling to a lower temperature while maintaining the applied polarization field to ensure that depolarization does not occur at a significant rate, followed by applying a vacuum to remove the solvent.

[0129] The resistive layer according to the various embodiments described herein can be incorporated into a variety of devices, including electro-optic devices with open tops or coplanar designs, and devices with permeable layers, openings, etc., to allow solvent to drain after polarization. Examples of various devices may include, but are not limited to, hybrid electro-optic polymer and TiO2 dual-groove waveguide modulators, ultrawideband electro-optic modulators based on hybrid silicon polymer dual vertical groove waveguides, plate-type groove polymer waveguide modulators, electro-optic polymer / TiO2 multilayer groove waveguide modulators, and / or coplanar electrode polymer modulators.

[0130] As mentioned above, first-order hyperpolarizability (β) is one of the most common and useful NLO properties. Higher-order hyperpolarizability is useful in other applications, such as all-optical (optic-switching-optical) applications. To determine whether a nonlinear electro-optic material (e.g., a compound or polymer) contains hyperpolarizability and a sufficient electro-optic coefficient (r... 33 A nonlinear optical chromophore (which is a function of β) is used to place the material in an electric field as a resistive layer to align the dipoles. This can be achieved, for example, by sandwiching a resistive layer of nonlinear electro-optic material between electrodes such as an indium tin oxide (ITO) substrate, a gold film, or a silver film. To generate a polarization electric field, the nonlinear electro-optic material is heated to its glass transition (T0). g Simultaneously with the temperature change, an electric potential is applied to the electrodes. After a suitable time period, the temperature is gradually decreased while maintaining the polarization electric field. Alternatively, the nonlinear electro-optic material can be polarized using a corona polarization method, where a charged needle at an appropriate distance from the resistive layer provides the polarization electric field. In either case, the dipoles in the nonlinear electro-optic material tend to align with the electric field. Various embodiments of this disclosure may include electro-optic materials with a glass transition temperature greater than or equal to 150°C, or greater than or equal to 175°C, or even higher.

[0131] Electro-optic devices

[0132] As used herein, the term "electro-optic device" refers to a device that includes one or more of the aforementioned resistive layers and has electro-optic functionality. For example, an electro-optic device may include an electro-optic modulator (EOM), an optical device in which a light beam is modulated using a signal control element having an electro-optic effect. Modulation may be applied to the phase / frequency, amplitude, and / or polarization of the light beam. An EOM may perform one or more (e.g., one or all) of phase / frequency, amplitude, or polarization modulation.

[0133] Phase modulation (PM) is a modulation scheme that encodes information as instantaneous phase changes of a carrier wave. The phase of the carrier signal is modulated to follow changes in the voltage level (amplitude) of the modulating signal. The peak amplitude and frequency of the carrier signal remain constant, but the phase of the carrier changes accordingly as the amplitude of the information signal changes.

[0134] Amplitude modulation is the process of transmitting a wave signal by modulating the amplitude of the modulated signal. Take the Mach-Zehnder (MZ) interferometer as an example. MZ interferometers are commonly used in integrated optics where phase stability requirements are easier to achieve. A beam splitter can split a laser into two paths, one of which has a phase modulator. The beams can then be recombined. Changing the electric field along the phase modulation path determines whether the two beams interfere constructively or destructively at the output, thus controlling the amplitude or intensity of the outgoing light. In one example of an MZ interferometer, the modulator can have two electro-optic arms. One arm can have electrodes to which a varying voltage can be applied. The other arm can be unvoltageed.

[0135] Polarization modulation in EO materials can be used as a time-resolved measurement technique for unknown electric fields. Depending on the type and orientation of the EO material and the direction of the applied electric field, the phase delay can depend on the polarization direction. For example, polarization modulation can be performed on EO materials used in antennas.

[0136] In EOMs (Electro-Optical Objects), nonlinear electro-optic materials are spin-coated onto a silicon wafer, and standard microfabrication processes are used to deposit and pattern metal electrodes and optical waveguides. For example, a well-known EOM device is the Mach-Zehnder interferometer described above. The light output is altered by changing the relative phase between the two arms. A common technique to double the effect for the same available drive voltage is to drive the two arms in opposite directions (push-pull mode). Nonlinear electro-optic materials have an interesting advantage compared to most other crystalline electro-optic materials: the direction of the electro-optic activity of a nonlinear electro-optic material is entirely determined by the direction of the applied polarization electric field. By polarizing the two arms of the Mach-Zehnder interferometer in opposite directions, the resulting device can automatically achieve push-pull operation with only a single applied signal.

[0137] Each EOM may include one or more integrated polymer electro-optic semiconductor circuits. Figure 3A and 3BThese are a side cross-sectional view and a cross-sectional view of an integrated polymer electro-optic semiconductor circuit 301 according to one embodiment. The semiconductor substrate 302 includes at least one doped layer 304 patterned on the semiconductor substrate to form a portion of a semiconductor device. At least one resistive layer 306 is patterned on the semiconductor substrate. A planarization layer 308 is arranged to be at least partially coplanar with the at least one conductive layer 306. A polymer optical stack 310 is disposed on the planarization layer 308.

[0138] At least one via 312 may extend at least partially through the polymer optical stack 310. The at least one via may be operatively coupled to a corresponding location on the at least one patterned conductor layer 306. A top conductor layer 314 is disposed on the polymer optical stack and electrically connected to the at least one via 312.

[0139] As an alternative to via 312, other conductors may be used to electrically couple the top conductor layer to at least one location on the at least one patterned conductor layer 306. For example, the at least one conductor may be formed entirely or in combination from vias, wire bonds, conductive bumps, and / or anisotropic conductive regions.

[0140] For example, the top conductor layer 314 may be formed to include a metal layer or a conductive polymer. The top conductor may be electroplated to increase its thickness. The top conductor layer may include at least one high-speed electrode 316 patterned in the top conductor layer 314, which is operatively coupled to receive signals from the at least one via 312 or from other conductive structures at corresponding locations on the at least one patterned conductor layer 306. Thus, the at least one via 312 or other conductive structure is configured to transmit electrical signals from a semiconductor circuit system formed on the semiconductor substrate 302 to the at least one high-speed electrode 316, the transmission passing through or around the polymer optical stack 310.

[0141] According to an embodiment, the at least one patterned conductor layer 306 is configured to form a ground electrode 318 parallel to the at least one high-speed electrode 316. An active region 320 of the polymer optical stack 310 is positioned to receive modulation signals from the high-speed electrode 316 and the ground electrode 318. The active region 320 includes a polarization region comprising at least one hyperpolarizable organic chromophore.

[0142] The polymer optical stack 310 is configured to support the active region 320 and to receive and guide light 322 into and out of the active region. The polymer optical stack 310 may include at least one lower cladding layer 324 and at least one upper cladding layer 326, respectively disposed below and above the electro-optic layer 328. The lower cladding layer 324 and upper cladding layer 326, optionally cooperating with the planarization layer 308, are configured to guide the injected light 322 along the plane of the electro-optic layer 328. A light guiding structure 330 is formed in the polymer optical stack 310 to guide the light 322 along one or more light propagation paths through the electro-optic layer 328 and / or a non-active core structure (not shown). Figure 3A and 3B In one embodiment, the light guide structure 330 is formed as a trench waveguide, which includes a path etched in at least one lower cladding 324.

[0143] The integrated polymer electro-optic semiconductor circuit 301 includes a semiconductor circuit formed by a composite of a doped layer pattern 304 and at least one patterned conductor layer 306. According to one embodiment, the semiconductor circuit is configured to drive electrodes 316, 318 with a series of modulated electrical pulses during operation. The resulting modulated electric field is applied to an active region 320, causing modulated hyperpolarization of the polarized organic chromophores embedded therein. A composite of electrodes 316, 318, active region 320, and light guide structure 330 is formed. Therefore, the modulated hyperpolarization can modulate the speed of light passing through the polarized active region 320 of the polymer optical stack 310. Repeated modulation of the transmitted light speed can generate a phase-modulated optical signal emitted from the active region. Such an active region 320 can be combined with beam splitters, combiners (not shown), and other active regions to create an optical amplitude modulator. The optical amplitude modulators described herein include MZ optical modulators. Other optical amplitude modulators may include ring resonator modulators, which comprise one or more ring resonators, a set of waveguides, at least one of which is a closed loop coupled to some optical input and output. Other optical amplitude modulators may include in-phase and quadrature (I / Q) modulators, which modulate based on the superposition of two orthogonal I / Q signals.

[0144] A combination of at least one electro-optic active region 320, at least two electrodes 316, 318, and corresponding light guide structures 324, 326, 330 can be considered as electro-optic devices 332, 334. A dual-channel electro-optic device 334 can be formed by a ground electrode 318 and corresponding paired active regions 320 and high-speed electrodes 316a, 316b. The two channels of the dual-channel electro-optic device 334 can work collaboratively, for example, forming an MZ optical modulator in a push-pull configuration.

[0145] Other devices can be formed using the electrode or resistor 336 that is not configured for high-speed operation. The operation of one of the illustrated devices is described below in conjunction with the description of the optical phase bias device.

[0146] Figure 4 An end view of a slot modulator with a highly doped silicon plate and ribs is shown. See details. Figure 4 The figure shows an end view of a slot modulator 400. In this example, the slot modulator is a Mach-Zehnder modulator, comprising two parallel slot waveguides 412 and 414, driven in a push-pull manner by a single coplanar transmission line 416. It should be understood that, according to the invention, a single slot waveguide can be used to form the slot modulator. In this example, a typical SiO2 cell 418 is formed on a silicon substrate 419. The transmission line 416 is formed of spaced-apart aluminum conductors located on the SiO2 cell 418, which has G conductors 420 and 421 at each edge and an S conductor 422 extending in the middle. The slot waveguide 412 includes a plate 424 extending inward from the G conductor 420 and a plate 426 extending inward from the S conductor 422. Vertically extending ribs 428 are attached to the inner end of plate 424, and vertically extending ribs 430, spaced apart from ribs 428, are attached to the inner end of plate 426. Ribs 428 and 430 primarily form slot waveguide 412. The region between conductor G 420 and conductor S 422, including the slot formed between ribs 428 and 430, is filled with EO polymer cladding material 432. Slot waveguide 414 is a mirror image of slot waveguide 412, and the positions and connections of its plates and ribs are identical to those described in slot waveguide 412. In the following disclosure, only slot waveguide 412 is discussed in detail; it should be understood that all details also apply to slot waveguide 414.

[0147] To aid in understanding the dimensions of the structure under discussion, transmission line 416 has a thickness of 1 μm, and plates 424 and 426 are both 70 nm high and 0.5 to 1 μm wide. Ribs 428 and 430 have a height (from the bottom surface to the top) of 220 nm, a width of 240 nm, and a center-to-center spacing of 200 nm. The slot waveguide 412 has a total length of 10 μm from G conductor 420 to S conductor 422.

[0148] In the prior art, plate 424 and rib 428 are integrally formed, and also integrally formed with G conductor 420. Similarly, plate 426 and rib 430 are integrally formed, and also integrally formed with S conductor 422. In a similar manner, the plate and rib of slot waveguide 414 are integrally formed with G conductor 421 and S conductor 422. In slot modulator 400, plates 424 and 426, as well as ribs 428 and 430, are made of highly doped (N... +++ Silicon is formed to reduce resistivity and achieve high bandwidth.

[0149] EOMs comprising various embodiments of nonlinear optical chromophores according to this disclosure may include modulators applied to, for example, slot modulators (e.g., slot modulators for wafer-level polarization), photonic integrated circuits (e.g., polymer photonic integrated circuits), data center switching, high-voltage sensing devices related to the power industry, electro-optic signal conversion devices for transmitting multiple television signals related to cable television (CATV) or satellite television, broadband acoustic spectrum analyzers, optical gyroscopes, phased array radars (e.g., integrated antenna / electro-optic modulators or W-band optical modulators), photonic detection radars, time-stretching and ultrafast analog-to-digital conversion devices, fiber optic and satellite telecommunications components, ultrafast electric field generation and detection devices, electric field sensors (e.g., electro-optic E-field sensors), mine detection devices, wavelength division multiplexing related devices, optical switches, spatial light modulation related devices (e.g., beam steering related devices), and / or augmented reality (AR) / virtual reality (VR) devices (e.g., full-spectrum visible photoelectric modulators).

[0150] For example, a photonic integrated circuit (PIC) can be a chip that performs optical signal processing. This chip can contain two or more photonic components (e.g., a resistive layer with nonlinear electro-optical material) that form functional circuitry to utilize photons to detect, generate, transmit, and process light. PICs have demonstrated significant potential in providing the performance (e.g., speed, size, and efficiency) required for future applications such as 6G, automotive light detection and ranging (LiDAR), consumer healthcare, artificial intelligence (AI), optical computing, virtual reality (VR), and / or augmented reality (AR).

Claims

1. A nonlinear optical chromophore of general formula (I): D- -A (I) Where D represents an organic electron-donating group; A represents an organic electron-withdrawing group with an electron affinity greater than that of D; and This indicates the relationship between organic electron-withdrawing groups and organic electron-donating groups. -bridge; wherein -The bridge has the following formula (II) 1 ): (I 1 ) Where a and b each independently represent an integer from 1 to 3; where each x independently represents an integer from 0 to 4; where z represents an integer from 1 to 3; where each R' independently represents a substituent selected from the group consisting of hydrogen, halogen, substituted or unsubstituted aryl, substituted or unsubstituted alkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic and substituted or unsubstituted cyclohexyl; where each R independently represents a substituent selected from the group consisting of hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted alkyl, substituted or unsubstituted mercapto, substituted or unsubstituted hydroxyl or substituted or unsubstituted amino.

2. The nonlinear optical chromophore according to claim 1, wherein a, b and z each represent 1.

3. The nonlinear optical chromophore according to claim 1, wherein x represents 0 and R represents an aryl sulfhydryl substituent.

4. The nonlinear optical chromophore according to claim 2, wherein each R' independently represents hydrogen, and R represents an aryl thiol substituent.

5. The nonlinear optical chromophore according to claim 1, wherein D represents a chromophore of the general formula (D a Electron-donating groups: Where R 5 The part representing the group selected from the following: H, substituted or unsubstituted straight-chain or branched alkyl, substituted or unsubstituted straight-chain or branched alkenyl, substituted or unsubstituted straight-chain or branched alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, substituted or unsubstituted cyclohexyl, and (CH2). n -O-(CH2) n Where n is 1-10, and R 5 With R 8 or R 9 Together they can form a 5- or 6-membered ring; R 8 and R 9 Is it H or R? 5 Forming 5- or 6-membered rings; Where R 6 The part selected from the group consisting of: H, halogen, substituted or unsubstituted heteroaryl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted amino, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted thioalkyl, substituted or unsubstituted C1-C 10 Straight-chain or branched alkyl, substituted or unsubstituted C2-C 10 Straight-chain or branched alkenyl, substituted or unsubstituted C2-C 10 Straight-chain or branched alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, substituted or unsubstituted cyclohexyl, substituted or unsubstituted silaneoxymethyl, and CH3-(CH2). n -O-(CH2) n Where n is 1-10; and wherein R 7 represents a moiety selected from the group consisting of H and substituted or unsubstituted alkyl.

6. The nonlinear optical chromophore according to claim 5, R 5 and R 6 One or two of them are substituted or unsubstituted phenyl groups.

7. The nonlinear optical chromophore of claim 1, wherein D represents a quinolyl electron-donating group having the formula (D 1 ): wherein R 1 represents a substituent selected from the group consisting of substituted or unsubstituted aryl and substituted or unsubstituted alkyl groups, and R 4 represents hydrogen or a methyl moiety.

8. The nonlinear optical chromophore according to claim 1, wherein A represents an electron-withdrawing group having the following formula (A¹): （A 1 ） Where R 2 and R 3 Each of the following groups is independently represented: H, substituted or unsubstituted C1-C. 10 Alkyl, substituted or unsubstituted C2-C 10 alkenyl, substituted or unsubstituted C2-C 10 Alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, substituted or unsubstituted cyclohexyl, and (CH2). n -O-(CH2) n Where n is 1-10.

9. The nonlinear optical chromophore according to claim 1, wherein A represents an electron-withdrawing group having the following formula (A²): (A 2 ) wherein R 10 represents a substituted or unsubstituted phenyl group.

10. A resistive film comprising the nonlinear optical chromophore according to claim 1, the nonlinear optical chromophore being dispersed and polarized in a matrix material.

11. An electro-optic device comprising one or more resistive films, wherein each of the one or more resistive films comprises a nonlinear optical chromophore dispersed and polarized in a host polymer matrix, wherein the nonlinear optical chromophore has the general formula (I): D- -A (I) Where D represents an organic electron-donating group; A represents an organic electron-withdrawing group with an electron affinity greater than that of D; and This indicates the relationship between organic electron-withdrawing groups and organic electron-donating groups. -bridge; wherein -The bridge has the following formula (II) 1 ): (II 1 ) Where a and b each independently represent an integer from 1 to 3; where each x independently represents an integer from 0 to 4; where z represents an integer from 1 to 3; where each R' independently represents a substituent selected from the group consisting of hydrogen, halogen, substituted or unsubstituted aryl, substituted or unsubstituted alkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic and substituted or unsubstituted cyclohexyl; where each R independently represents a substituent selected from the group consisting of hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted alkyl, substituted or unsubstituted mercapto, substituted or unsubstituted hydroxyl or substituted or unsubstituted amino.

12. The electro-optic device according to claim 11, wherein a, b and z each represent 1.

13. The electro-optic device according to claim 11, wherein x represents 0 and R represents an aryl mercapto substituent.

14. The electro-optic device of claim 12, wherein each R' independently represents hydrogen, and R represents an aryl mercapto substituent.

15. The electro-optical device of claim 11, wherein D represents an electron-donating group having the general formula (D a ). Where R 5 The part representing the group selected from the following: H, substituted or unsubstituted straight-chain or branched alkyl, substituted or unsubstituted straight-chain or branched alkenyl, substituted or unsubstituted straight-chain or branched alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, substituted or unsubstituted cyclohexyl, and (CH2). n -O-(CH2) n Where n is 1-10, and R 5 With R 8 Or R 9 Together they can form a 5- or 6-membered ring; R 8 and R 9 Is it H or R? 5 Forming 5- or 6-membered rings; Where R 6 The part selected from the group consisting of: H, halogen, substituted or unsubstituted heteroaryl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted amino, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted thioalkyl, substituted or unsubstituted C1-C 10 Straight-chain or branched alkyl, substituted or unsubstituted C2-C 10 Straight-chain or branched alkenyl, substituted or unsubstituted C2-C 10 Straight-chain or branched alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, substituted or unsubstituted cyclohexyl, substituted or unsubstituted silaneoxymethyl, and CH3-(CH2). n -O-(CH2) n Where n is 1-10; and wherein R 7 represents a moiety selected from the group consisting of H and substituted or unsubstituted alkyl.

16. The electro-optical device of claim 15, wherein one or both of R 5 and R 6 is a substituted or unsubstituted phenyl group.

17. The electro-optical device of claim 11, wherein D represents a quinolinyl electron-donating group having the following formula (D 1 ): Where R 1 The substituent is selected from the group consisting of substituted or unsubstituted aryl groups and substituted or unsubstituted alkyl groups, and R 4 It indicates the hydrogen or methyl part.

18. The electro-optic device according to claim 11, wherein A represents an electron-withdrawing group having the following formula (A¹): （A 1 ） Where R 2 and R 3 Each of the following groups is independently represented: H, substituted or unsubstituted C1-C. 10 Alkyl, substituted or unsubstituted C2-C 10 alkenyl, substituted or unsubstituted C2-C 10 Alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, substituted or unsubstituted cyclohexyl, and (CH2). n -O-(CH2) n Where n is 1-10.

19. The electro-optical device of claim 11, wherein A represents an electron- withdrawing group having the following formula (A2): ###0002### (A 2 ) wherein R 10 represents a substituted or unsubstituted phenyl group.

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