# Patent

## Title
Crosslinkable polymer host containing a nonlinear optical chromophore guest

## Abstract

Crosslinked films having electro-optic activity, methods for making the films, and devices that include the films. The films include a crosslinked polymer host and guest polarizable chromophore compounds.

## Background
BACKGROUND OF THE INVENTION
Organic second-order nonlinear optical (NLO) materials have received increasing interest due to their promising application in high-speed electro optic (E-O) devices with very broad bandwidth and low driving voltages. One of the most challenging tasks in this area is to effectively translate high molecular nonlinearities (μβ) into large macroscopic E-O activities (r33) in a bulk system. To realize large r33 values, research has been directed toward making chromophores with large dipole moments μ and first hyperpolarizabilities β, increasing loading density of chromophores in a host polymer, and improving poling efficiency.
Recent theoretical analysis has shown that dipole-dipole interactions between chromophores make it impossible to achieve a high degree of noncentrosymmetric order unless undesirable anisotropic intermolecular electrostatic interactions are minimized by steric shape modification of chromophores. A spherical shape has been proposed as means to increase loading density and improve poling efficiency. Dendritic chromophores, NLO dendrimers, and dendronized E-O polymers have recently been developed to isolate the interactions between chromophores and polymers. In comparison with conventional E-O polymers, the screening effect of dendrons allows the chromophores to be spatially isolated, and larger void-containing structures can provide space for efficient reorientation of the chromophores. Furthermore, the globular geometry of dendrimers is well suited for shape modification of chromophores. Although these chromophores have shown encouraging results in improving poling efficiency, pushing the loading density above a certain level (25 to 30 wt %) often results in micro-aggregation and phase separation due to limited miscibility and an incompatibility between chromophores and polymers.
Despite the advances in the development of NLO materials noted above, there exists a need for improved materials and methods. The present invention seeks to fulfill this need and provides further related advantages.
SUMMARY OF THE INVENTION
The present invention provides crosslinked films having electro-optic activity, methods for making the films, and devices that include the films.
In one aspect, the invention provides a method for making a crosslinked film having electro-optic activity. In one embodiment, the method includes applying a crosslinking agent, a polarizable chromophore compound, and a passive crosslinkable polymer to a substrate to provide a film; subjecting the film to an electric field to align at least a portion of the chromophore compounds to provide a film containing aligned chromophore compounds; and heating the film containing aligned chromophore compounds to a temperature sufficient to crosslink the passive crosslinkable polymer and the crosslinking agent to provide a crosslinked film having electro-optic activity.
In another aspect of the invention, films having electro-optic activity are provided. In one embodiment, the film includes aligned, polarizable chromophore guest compounds and a host matrix.
In another aspect, the invention provides electro-optic devices that include the films described above.



BRIEF DESCRIPTION OF THE DRAWINGS
The foregoing aspects and many of the attendant advantages of this invention will become more readily appreciated as the same become better understood by reference to the following detailed description, when taken in conjunction with the accompanying drawings, wherein:
FIG. 1 is a schematic illustration of representative crosslinking agents and representative guest chromophore compounds useful in the invention;
FIG. 2 is a schematic illustration of a representative method for making a crosslinked film of the invention;
FIG. 3 is a schematic illustration of a representative method for making a crosslinked film of the invention; and
FIG. 4 is a schematic illustration of a representative electro-optic device of the invention.



DETAILED DESCRIPTION OF THE INVENTION
The present invention provides crosslinked films having electro-optic (E-O) activity, methods for making the films, and devices that include the films. The films of the invention include a passive crosslinkable polymer and nonlinear optically active (polarizable) chromophore compounds. The passive crosslinkable polymer serves as a host for the guest chromophore compounds that impart electro-optic activity to the film when aligned, typically by electrostatic poling. The passive crosslinkable polymer acts to preserve the alignment of the chromophore compounds in the film after poling by restricting relaxation of the chromophore compounds thereby preserving the film's electro-optic activity.
In one aspect, the invention provides a method for making a crosslinked film having electro-optic activity. In one embodiment, the method includes the following multi-step process:
(1) applying a crosslinking agent, a polarizable chromophore compound, and a passive crosslinkable polymer to a substrate to provide a film;
(2) subjecting the film to an electric field to align at least a portion of the chromophore compounds to provide a film containing aligned chromophore compounds; and
(3) heating the film containing aligned chromophore compounds to a temperature sufficient to crosslink the passive crosslinkable polymer and the crosslinking agent to provide a crosslinked film having electro-optic activity.
In one embodiment, the crosslinking agent, polarizable chromophore compound, and passive crosslinkable polymer are applied to the substrate as a blend by spin coating.
In the method, the crosslinking agent and passive crosslinkable polymer are reactive to form crosslinks. Suitable crosslinking agents are polyfunctional crosslinking agents including two or more crosslinkable groups. Crosslinking agents useful in the invention are passive, meaning that they are not nonlinear optically active. The crosslinking agent is not a chromophore. Suitable crosslinking agents include bifunctional and trifunctional crosslinking agents. The crosslinking agents include functional groups that allow for crosslinking with the passive crosslinkable polymer.
As used herein, the term “passive crosslinkable polymer” refers to a polymer that is not nonlinear optically active. The passive crosslinkable polymer is not a chromophore. In one embodiment, the passive crosslinkable polymer and crosslinking agent are reactive to form 4+2 cycloaddition product crosslinks. In this embodiment, the crosslinkable groups are dienes and dienophiles. For this embodiment, the passive crosslinkable polymer includes one or more dienes (e.g., a plurality of dienes) for reaction with a crosslinking agent that includes two or more dienophiles. Alternatively, the passive crosslinkable polymer includes one or more dienophiles (e.g., a plurality of dienophiles) for reaction with a crosslinking agent that includes two or more dienes. In one embodiment, the crosslinking agent includes two or more dienophiles. Representative crosslinking agents include bismaleimides (e.g., BMI) and trismaleimides (e.g., TMI), as illustrated in FIG. 1. In one embodiment, the passive crosslinkable polymer includes one or more dienes. Representative diene moieties include anthracene moieties. In one embodiment, the passive crosslinkable polymer is a graft copolymer having one or more dienes.
In one embodiment, the passive crosslinkable polymer includes from about 0.01 to about 1 percent by weight (wt %) diene based on the total weight polymer.
A representative passive crosslinkable polymer useful in the method of the invention is a copolymer polymethylmethacrylate-co-9-anthrylmethyl methacrylate (PMMA-co-AMA) prepared by copolymerizing 9-anthrylmethyl methacrylate (AMA) and methylmethacrylate (MA). The preparation of PMMA-co-AMA is described in the Example.
The method of the invention provides a film having electro-optic activity. The electro-optic activity is imparted to the film by aligned, nonlinear optically active chromophore compounds present in the film. In this embodiment, the guest chromophore compounds do not include a crosslinkable moiety and do not form covalent bonds with the host polymers of the film or crosslinking agents useful in making the films. The guest chromophores are a separate film component and reside in the polymer network of the host. The specific guest chromophore compounds useful in the methods and films of the invention are not particularly critical. Suitable chromophore compounds include compounds with large dipole moments μ and first hyperpolarizabilities β, high molecular nonlinearities (μβ), which translate into large macroscopic E-O activities (r33) in a bulk system. Representative chromophore compounds AJL28 and AJC146 are illustrated in FIG. 1. The preparation of a representative film of the invention is described in the Example and illustrated in FIG. 2.
The chromophore compounds are second-order nonlinear optical chromophore compounds. As used herein, the term “chromophore” refers to a compound that can absorb a photon of light. In the context of the invention, the term “nonlinear” refers second order effects that arise from the nature of the polarizable chromophore compound (i.e., “push-pull” chromophore compound) having the general structure D-π-A, where D is an electron donor, A is an electron acceptor, and π is a π-bridge that conjugates the donor to the acceptor.
A “donor” (represented by “D”) is an atom or group of atoms with low electron affinity relative to an acceptor (defined below) such that, when the donor is conjugated to an acceptor through a π-bridge, electron density is transferred from the donor to the acceptor.
An “acceptor” (represented by “A”) is an atom or group of atoms with high electron affinity relative to a donor such that, when the acceptor is conjugated to a donor through a π-bridge, electron density is transferred from the acceptor to the donor.
A “π-bridge” or “conjugated bridge” (represented in chemical structures by “π” or “πn” where n is an integer) is comprised of an atom or group of atoms through which electrons can be delocalized from an electron donor (defined above) to an electron acceptor (defined above) through the orbitals of atoms in the bridge. Preferably, the orbitals will be p-orbitals on multiply bonded carbon atoms such as those found in alkenes, alkynes, neutral or charged aromatic rings, and neutral or charged heteroaromatic ring systems. Additionally, the orbitals can be p-orbitals on multiply bonded atoms such as boron or nitrogen or organometallic orbitals. The atoms of the bridge that contain the orbitals through which the electrons are delocalized are referred to here as the “critical atoms.” The number of critical atoms in a bridge can be a number from 1 to about 30. The critical atoms can also be substituted further with the following: “alkyl” as defined below, “aryl” as defined below, or “heteroalkyl” as defined below. One or more atoms, with the exception of hydrogen, on alkyl, aryl, or heteroalkyl substituents of critical atoms in the bridge may be bonded to atoms in other alkyl, aryl, or heteroalkyl substituents to form one or more rings.
“Alkyl” is a saturated or unsaturated, straight or branched, cyclic or multicyclic aliphatic (i.e., non-aromatic) hydrocarbon group containing from 1 to about 30 carbons. Independently the hydrocarbon group, in various embodiments: has zero branches (i.e., is a straight chain), one branch, two branches, or more than two branches; is saturated; is unsaturated (where an unsaturated alkyl group may have one double bond, two double bonds, more than two double bonds, and/or one triple bond, two triple bonds, or more than three triple bonds); is, or includes, a cyclic structure; is acyclic. Exemplary alkyl groups include C1alkyl (i.e., —CH3 (methyl)), C2alkyl (i.e., —CH2CH3 (ethyl), —CH═CH2 (ethenyl) and —C≡CH (etheynyl)) and C3alkyl (i.e., —CH2CH2CH3 (n-propyl), —CH(CH3)2 (i-propyl), —CH═CH—CH3 (1-propenyl), —C≡C—CH3 (1-propynyl), —CH2—CH═CH2 (2-propenyl), —CH2—C≡CH (2-propynyl), —C(CH3)═CH2 (1-methylethenyl), —CH(CH2)2 (cyclopropyl), and adamantly. The term “alkyl” also includes groups where at least one of the hydrogens of the hydrocarbon group is substituted with at least one of the following: alkyl; “aryl” as defined below; or “hetereoalkyl” as defined below. One or more of the atoms in an alkyl group, with the exception of hydrogen, can be bonded to one or more of the atoms in an adjacent alkyl group, aryl group (aryl as defined below), or heteroalkyl group (heteroalkyl as defined below) to form one or more ring.
“Aryl” is a monocyclic or polycyclic aromatic ring system or a heteroaromatic ring system (“heteroaryl”) containing from 3 to about 30 carbons. The ring system may be monocyclic or fused polycyclic (e.g., bicyclic, tricyclic, etc.). Preferred heteroatoms are nitrogen, oxygen, sulfur, and boron. In various embodiments, the monocyclic aryl ring is C5-C10, or C5-C7, or C5-C6, where these carbon numbers refer to the number of carbon atoms that form the ring system. A C6 ring system, i.e., a phenyl ring, is a preferred aryl group. A C4-S ring system (i.e., a thiophene) is another preferred aryl group. In various embodiments, the polycyclic ring is a bicyclic aryl group, where preferred bicyclic aryl groups are C8-C12, or C9-C10. A naphthyl ring, which has 10 carbon atoms, is a preferred polycyclic aryl group. The term “aryl” also includes groups where at least one of the hydrogens of the aromatic or heteroaromatic ring system is substituted further with at least one of the following: alkyl; halogen; or hetereoalkyl (as defined below). One or more of the atoms in an aryl group, with the exception of hydrogen, can be bonded to one or more of the atoms in an adjacent alkyl group, aryl group, or heteroalkyl group (heteroalkyl as defined below) to form one or more rings.
“Heteroalkyl” is an alkyl group (as defined herein) wherein at least one of the carbon atoms or hydrogen atoms is replaced with a heteroatom, with the proviso that at least one carbon atom must remain in the heteroalkyl group after the replacement of carbon or hydrogen with a heteroatom. Preferred heteroatoms are nitrogen, oxygen, sulfur, silicon, and halogen. A heteroatom may, but typically does not, have the same number of valence sites as the carbon or hydrogen atom it replaces. Accordingly, when a carbon is replaced with a heteroatom, the number of hydrogens bonded to the heteroatom may need to be increased or decreased to match the number of valence sites of the heteroatom. For instance, if carbon (valence of four) is replaced with nitrogen (valence of three), then one of the hydrogens formerly attached to the replaced carbon must be deleted. Likewise, if carbon is replaced with halogen (valence of one), then three (i.e., all) of the hydrogens formerly bonded to the replaced carbon must be deleted. Examples of heteroalkyls derived from alkyls by replacement of carbon or hydrogen with heteroatoms are shown immediately below. Exemplary heteroalkyl groups are methoxy (—OCH3), amines (—CH2NH2), nitriles (—CN), carboxylic acids (—CO2H), other functional groups, and dendrons. The term “heteroalkyl” also includes groups where at least one of the hydrogens of carbon or a heteroatom of the heteroalkyl may be substituted with at least one of the following: alkyl; aryl; and heteroalkyl. One or more of the atoms in a heteroalkyl group, with the exception of hydrogen, can be bonded to one or more of the atoms in an adjacent alkyl group, aryl group, or heteroalkyl group to form one or more rings.
Representative chromophores, donors, acceptors, and 1-bridges are described in U.S. Pat. Nos. 6,361,717; 6,348,992; 6,090,332; 6,067,186; 5,708,178; and 5,290,630; each expressly incorporated herein by reference in its entirety. Representative chromophores are also described in WO 02/08215; U.S. patent application Ser. No. 10/212,473, filed Aug. 2, 2002; U.S. patent application Ser. No. 10/347,117, filed Jan. 15, 2003; and U.S. Provisional Patent Application No. 60/520,802, filed Nov. 17, 2003; Adv. Mater. 14(23):1763-1768, 2002; and Adv. Mater. 14(19):1339-1365, 2002; each expressly incorporated herein by reference in its entirety.
In another aspect of the invention, films having electro-optic activity are provided. In one embodiment, the film includes aligned, polarizable chromophore guest compounds a host matrix. The host matrix includes passive crosslinked polymers, and the passive crosslinked polymers include one or more 4+2 cycloaddition crosslinks.
As noted above, the film is made by crosslinking a passive crosslinkable polymer with a crosslinking agent in the presence of nonlinear optically active chromophore compounds. The crosslinks are 4+2 cycloaddition product crosslinks that are the product of the reaction of a diene and a dienophile. In one embodiment, the diene is an anthracene and the dienophile is a maleimide.
In one embodiment, the crosslinked polymers are crosslinked PMMA-co-AMA copolymers.
In films of the invention, guest chromophore compounds are present in an amount from about 5 to about 50 wt % based on the total weight of the film. As noted above, the nature of the chromophore compound is not particularly critical and suitable chromophore compounds are described above.
The preparation of representative films of the invention are described in the Example and illustrated schematically in FIG. 3. These films have r33 values from about 200 to about 300 pm/V.
Several factors are considered when making films of the invention. The composition of a film is determined by the amount of chromophore, polymer, and crosslinking agent. In a representative example, the chromophore is present in an amount from about 5 to about 50 wt %, the crosslinking agent is present in an amount from about 0.1 to about 1.0 wt %, and the polymer is the remaining weight of the film. The solids are dissolved in a solvent, typically in an amount from 1-20 wt % based on the total weight of solids. A representative solvent is 1,1,2-trichloroethane. The solution containing the dissolved mixture of polymer, chromophore, and crosslinking agent is then spin-coated onto a substrate. The spin-coating speed and the viscosity of the solution will determine the thickness of the film of the invention. The desired film thickness is determined by the final use for the film, and may range from about 100 nm to about 100 μm for typical applications.
For measurement of r33, an ITO-coated glass substrate is typically used. The substrate used when fabricating electro-optic devices incorporating films of the invention, such as Mach-Zehnder interferometers, will typically be a cladding material having a lower refractive index than the film. The cladding material will typically be one layer of a multi-layer device that is based on a foundation substrate of silicon, quartz, or glass. Typical electro-optic (E-O) coefficient values are measured using the reflection technique at 1310 nm light according to Teng, C. C.; Man, H. T., Appl. Phys. Lett. 56:1734, 1990.
Films of the invention spin-coated on substrates are typically dried under vacuum in an oven. Typical drying times range from 1 hour to 48 hours and typical temperatures range from 30 to 150° C. The drying temperature and time will affect the E-O strength of the film because extensive crosslinking before poling will exclude the possibility of aligning the chromophores so as to produce a large E-O coefficient. Typical films of the invention are dried for a minimum amount of time and at a minimum temperature so as to adequately remove the solvent with minimal crosslinking. Drying factors are dictated by the solvent used and the film components. The use of an un-optimized process is expected to give low E-O activity due to premature crosslinking of the polymer before applying the poling field to the chromophores. To minimize the detrimental effect of crosslinking, poling is performed before the polymer film becomes substantially crosslinked. At higher temperature and longer vacuum drying times, the E-O activity of the polymers is significantly reduced due to crosslinking before reorientation of chromophores. For example, the r33 value of a representative film after being dried at 50° C. for 10 hours is 215 pm/V under a 125 V/μm poling field. However, a similar film after vacuum drying for 10 hours at 70° C. and for 24 hours at 50° C. with the same material and poling condition measured 127 and 145 pm/V, respectively.
Crosslinking of the polymer in films of the invention typically proceeds in two stages: during drying (described above) and poling. Because crosslinking films of the invention typically is a temperature-driven process, drying the solution-deposited film typically begins the crosslinking process. Therefore, it is critically important that, during drying, a minimal amount of crosslinking occurs. Minimal crosslinking will typically allow for a maximum E-O activity of the final film because crosslinking of the film before poling will result in the guest chromophores being prematurely (i.e., before being aligned by poling) locked into place within the film.
Poling dried films is typically accomplished by electrostatic poling between two electrodes with the film intermediate. Corona (plasma-onset) poling is another poling technique useful for aligning chromophores in films of the invention. Electrostatic poling typically involves a film intermediate two electrodes. For electro-optic devices incorporating films of the invention, a cladding layer may be intermediate the film and one, or both, of the poling electrodes. Poling fields for electrostatic poling are typically from about 50 to about 150 V/μm. An inert environment (e.g., under nitrogen) is typically beneficial to the poling process.
After a poling field is applied, the chromophores in the film are aligned in the direction of the field and crosslinking via elevated temperature locks the oriented chromophores into place. Optimizing the E-O effect of the film is typically accomplished by gradually raising the temperature of the film while poling, as well as raising the poling field along with the temperature. Representative poling procedures for making films of the invention include starting at a temperature of from about 50 to about 75° C. and ramping, over the course of 5 to 60 minutes, to from about 100 to about 150° C. Typical voltages are from about 40 to about 75 V/μm increasing to from about 75 to about 150 V/μm over the course of the temperature ramp. Upon completion of crosslinking, the poling voltage typically remains applied while the film gradually cools to room temperature.
FIG. 3 illustrates the formation of a representative film of the invention 140. An uncrosslinked film is formed 100 from a polymer 110 having a backbone 112 and pendant diene groups 114; a chromophore having a dipole moment 120; and a crosslinking agent 130 having two dienophile endgroups 132. After electrostatic poling and crosslinking, a representative crosslinked and poled film of the invention 140 is formed. The poled film includes a crosslinked polymer 150 having a backbone 152 and crosslinks 154 resulting from the reaction of the diene groups 114 and the crosslinking agent dienophile groups 132 to form 4+2 cycloaddition products 155. The poled film additionally includes aligned chromophore molecules 160.
Table 1 summarizes the E-O properties of representative films of the invention made using PMMA-AMA. A representative procedure for synthesizing and testing films of the invention is described in the Example.







TABLE 1







Electro-optic properties of representative films of the invention.












Chromophore


Poling
Maximum



guest (in
Content of
Crosslinking
Temperature
Poling Field
E-O activity -


PMMA-AMA)
Chromophore
agent
(° C.)
(V/μm)
r33 (pm/V)





AJC146
25
None
110
100
156


AJC146
25
BMI
115
125
197


AJC146
30
BMI
112
125
215


AJC146
35
BMI
110
100
196


AJL28
46
TMI
110
125
300









The first entry in Table 1 has no crosslinking agent and the E-O activity is relatively low. As the concentration of crosslinking agent increases, so does the E-O activity (for samples made using the same poling field strength). Use of a tri-functional (TMI) crosslinking agent shows improved E-O activity over samples made with a bi-functional (BMI) crosslinking agent.
In some embodiments, electro-optic films of the invention include at least two structurally different chromophores. The at least two structurally different chromophores may have different donors, different π-bridges, different acceptors, different substituents, or any combination thereof. In one embodiment, the guest chromophore compounds are present in an amount from about 5 to about 50 wt % based on the total weight of the film.
In another aspect, the invention provides electro-optic devices that include the films described above. The materials and methods described herein can be useful in a variety of electro-optic applications. In addition, these materials and methods may be applied to polymer transistors or other active or passive electronic devices, as well as OLED (organic light emitting diode) or LCD (liquid crystal display) applications.
Representative E-O devices of the invention include E-O modulators, useful in converting electrical signals into optical signals. An exemplary E-O modulator is a Mach-Zehnder (M-Z) interferometer modulator, as illustrated in FIG. 4. The M-Z modulator 400 is typically fabricated on a substrate 410. Representative substrate materials include semiconductors (e.g., silicon wafers), glass, quartz, and polymers. Flexible E-O devices are possible if fabricated on a flexible polymer substrate.
A lower electrode 420 is typically a metal or a conductive polymer. A representative lower electrode material is gold. The lower electrode may be two or more materials, such as is typically the case when using gold as an lower electrode material because of its poor adhesion to typical substrates. Chromium and a mixture of titanium tungsten are typical adhesion promoting materials used at the interface of the substrate 410 and the lower electrode 420.
The lower cladding layer 430, in-plane cladding layer 440, and upper cladding layer 460 serve as a buffer between the optically detrimental electrodes 420, 470 and the waveguiding layers of the device (such as 450, 452, 456, 458). The in-plane cladding layer 440 and upper cladding layer 460 are typically the same material and deposited in the same fabrication step, thus covering the sides and top of the waveguide materials. Typical cladding materials have a low refractive index relative to waveguiding layers and are know to those skilled in the art.
The active layer 450 comprises an E-O material, such as films of the invention, and is structured in a M-Z modulator to include an input waveguide 452, a non-modulated branch 454, a modulated branch 456, and an output waveguide 458. The active layer 450 is typically poled by heating the entire device 400 while poling the area intermediate the two electrodes 420, 470. The active layer 450 is the waveguiding layer and has a refractive index greater than the surrounding cladding layers 430, 440, 460. The greater the difference in refractive index between the waveguiding and cladding layers, the more tightly the optical signal will be contained in the waveguide. Typically the refractive index difference will be as large as possible so as to reduce optical loss and to sufficiently optically insulate the optical signal from the signal-disrupting electrode materials. A top electrode 470 completes the device.
Operation of a typical M-Z modulator includes inputting an optical signal into the waveguide of the device 450, 452. Representative optical signals include lasers at telecommunication wavelengths (e.g., about 1300 nm and about 1550 nm). Methods for coupling light from the optical signal generator into the device structure are know to those skilled in the art and include butt-coupling and free-space coupling. After coupling light into the device, the optical signal enters the input waveguide 452 where it is split into two branches 454 and 456. If the device is a single-electrode M-Z modulator, as illustrated in FIG. 4, then the E-O effect is used to change the refractive index of the modulated branch 456 of the waveguide. The E-O effect is the result of the application of an electric voltage between the bottom electrode 420 and the top electrode 470 with an E-O material intermediate the electrodes. Because of the speed at which the E-O material can be affected (i.e., the refractive index changed), very high frequency electric signals applied to the electrodes will impart similar frequency signals on the affected E-O material in the modulated branch 456 of the waveguide. When no E-O effect is present (e.g., when there is no voltage across the electrodes 420, 470), constructive interference will occur upon recombination of the two signals in the output waveguide 458, as long as the two branches of the waveguide 454, 456 are of identical dimensions and composition. If the refractive index of the modulated branch 456 is affected via the E-O effect, the refractive index of the branch will increase or decrease. Change in the refractive index in the modulate branch 456 will result in a phase shift and varying degrees of constructive or destructive interference based on the amount of the refractive index shift. A typical M-Z modulator operates in two states, one with no voltage applied (maximum constructive interference), and a second with sufficient voltage applied so as to shift the phase of the modulated branch 456 optical signal π radians (Vπ), thus causing maximum destructive interference. The resulting output is a maximum optical signal with no voltage applied and a minimum optical signal with a voltage applied. Variations of the M-Z modulator are known to those skilled in the art.
In a representative application of a M-Z modulator, the voltage applied to the electrodes is an electrical data stream that is an analog signal, representing 1s and 0s, that is then converted to an optical signal by the M-Z modulator. Conversion is accomplished by defining the optical output of the M-Z modulator to correspond to the electrical input signals. For example, when the analog signal has no voltage (i.e., 0 V), this state may represent a 1, and a 0 would be represented by a voltage sufficient to affect the appropriate phase shift (typically Vπ) to create a different optical output than that representing a 1. The electrical input is a series of peaks and valleys representing the 1s and 0s of the data stream. The resulting optical signal output from the M-Z modulator output waveguide 458 is a blinking of the optical signal on (when no voltage is applied) and off (when Vπ is applied). The frequency of the output signal will match that of the input signal so long as the E-O material used is capable of sufficiently fast refractive index modulation. Because E-O chromophores change refractive index based on the rearrangement of electron density at a molecular level, the maximum speed of an E-O M-Z modulator is not currently known, but terahertz modulation should be possible given proper device design and material considerations.
The E-O material used as the waveguiding layer in M-Z devices will partially define the attributes of the device. The larger the E-O coefficient of the material, the smaller the Vπ required to drive the modulator. A reduction of Vπ to sub-1 V levels has been achieved and further reductions in Vπ will likely be accomplished through an increase in the E-O coefficient of the E-O materials used. Device engineering may further reduce the operating voltage and Vπ of M-Z modulators. By increasing the complexity of the device and adding a second top electrode 470 covering the portion of the waveguide layer depicted in FIG. 4 as being the non-modulated channel 454, both channels 454, 456 can be modulated, thus potentially reducing the Vπ of the device.
The use of organic polymers in integrated optics and optical communication systems containing optical fibers and routers has been previously described. The films of the invention may be used in place of currently used materials, such as lithium niobate, in most type of integrated optics devices, optical computing applications, and optical communication systems. For instance, the films may be fabricated into switches, modulators, waveguides, or other electro-optical devices.
For example, in optical communication systems devices fabricated from the films of the invention may be incorporated into routers for optical communication systems or waveguides for optical communication systems or for optical switching or computing applications. Because the films are generally less demanding than currently used materials, devices made from such films may be more highly integrated, as described in U.S. Pat. No. 6,049,641, which is incorporated herein by reference. Additionally, such films may be used in periodically poled applications as well as certain displays, as described in U.S. Pat. No. 5,911,018, which is incorporated herein by reference.
Techniques to prepare components of optical communication systems from optically transmissive materials have been previously described, and may be utilized to prepare such components from films provided by the present invention. Many articles and patents describe suitable techniques, and reference other articles and patents that describe suitable techniques, where the following articles and patents are exemplary:
Eldada, L. and L. Shacklette, “Advances in Polymer Integrated Optics,” IEEE Journal of Selected Topics in Quantum Electronics 6(1):54-68, January/February 2000; Wooten, E. L., et al. “A Review of Lithium Niobate Modulators for Fiber-Optic Communication Systems,” IEEE Journal of Selected Topics in Quantum Electronics 6 (1):69-82, January/February 2000; Heismann, F., et al. “Lithium Niobate Integrated Optics Selected Contemporary Devices and System Applications,” Optical Fiber Telecommunications III B, Academic, Kaminow and Koch (eds.), New York, 1997, pp. 377-462; Murphy, E., “Photonic Switching,” Optical Fiber Telecommunications III B, Academic, Kaminow and Koch (eds.), New York, 1997, pp. 463-501; E. Murphy, Integrated Optical Circuits and Components: Design and Applications, Marcel Dekker, New York, August 1999; Dalton, L., et al., “Polymeric Electro-Optic Modulators: From Chromophore Design to Integration with Semiconductor Very Large Scale Integration Electronics and Silica Fiber Optics,” Ind. Eng. Chem. Res. 38:8-33, 1999; Dalton, L., et al., “From Molecules to Opto-Chips: Organic Electro-Optic Materials,” J. Mater. Chem. 9:1905-1920, 1999; Liakatas, I. et al., “Importance of Intermolecular Interactions in the Nonlinear Optical Properties of Poled Polymers,” Applied Physics Letters 76(11): 1368-1370, Mar. 13, 2000; Cai. C., et al., “Donor-Acceptor-Substituted Phenylethenyl Bithiophenes: Highly Efficient and Stable Nonlinear Optical Chromophores,” Organic Letters 1(11):1847-1849, 1999; Razna, J., et al., “NLO Properties of Polymeric Langmuir-Blodgett Films of Sulfonamide-Substituted Azobenzenes,” J. of Materials Chemistry 9:1693-1698, 1999; Van den Broeck, K., et al., “Synthesis and Nonlinear Optical Properties of High Glass Transition Polyimides,” Macromol. Chem. Phys 200:2629-2635, 1999; Jiang, H., and A. K. Kakkar, “Functionalized Siloxane-Linked Polymers for Second-Order Nonlinear Optics,” Macromolecules 31:2508, 1998; Jen, A. K.-Y., “High-Performance Polyquinolines with Pendent High-Temperature Chromophores for Second-Order Nonlinear Optics,” Chem. Mater. 10:471-473, 1998; “Nonlinear Optics of Organic Molecules and Polymers,” Hari Singh Nalwa and Seizo Miyata (eds.), CRC Press, 1997; Cheng Zhang, Ph.D. Dissertation, University of Southern California, 1999; Galina Todorova, Ph.D. Dissertation, University of Southern California, 2000; U.S. Pat. Nos. 5,272,218; 5,276,745; 5,286,872; 5,288,816; 5,290,485; 5,290,630; 5,290,824; 5,291,574; 5,298,588; 5,310,918; 5,312,565; 5,322,986; 5,326,661; 5,334,333; 5,338,481; 5,352,566; 5,354,511; 5,359,072; 5,360,582; 5,371,173; 5,371,817; 5,374,734; 5,381,507; 5,383,050; 5,384,378; 5,384,883; 5,387,629; 5,395,556; 5,397,508; 5,397,642; 5,399,664; 5,403,936; 5,405,926; 5,406,406; 5,408,009; 5,410,630; 5,414,791; 5,418,871; 5,420,172; 5,443,895; 5,434,699; 5,442,089; 5,443,758; 5,445,854; 5,447,662; 5,460,907; 5,465,310; 5,466,397; 5,467,421; 5,483,005; 5,484,550; 5,484,821; 5,500,156; 5,501,821; 5,507,974; 5,514,799; 5,514,807; 5,517,350; 5,520,968; 5,521,277; 5,526,450; 5,532,320; 5,534,201; 5,534,613; 5,535,048; 5,536,866; 5,547,705; 5,547,763; 5,557,699; 5,561,733; 5,578,251; 5,588,083; 5,594,075; 5,604,038; 5,604,292; 5,605,726; 5,612,387; 5,622,654; 5,633,337; 5,637,717; 5,649,045; 5,663,308; 5,670,090; 5,670,091; 5,670,603; 5,676,884; 5,679,763; 5,688,906; 5,693,744; 5,707,544; 5,714,304; 5,718,845; 5,726,317; 5,729,641; 5,736,592; 5,738,806; 5,741,442; 5,745,613; 5,746,949; 5,759,447; 5,764,820; 5,770,121; 5,76,374; 5,776,375; 5,777,089; 5,783,306; 5,783,649; 5,800,733; 5,804,101; 5,807,974; 5,811,507; 5,830,988; 5,831,259; 5,834,100; 5,834,575; 5,837,783; 5,844,052; 5,847,032; 5,851,424; 5,851,427; 5,856,384; 5,861,976; 5,862,276; 5,872,882; 5,881,083; 5,882,785; 5,883,259; 5,889,131; 5,892,857; 5,901,259; 5,903,330; 5,908,916; 5,930,017; 5,930,412; 5,935,491; 5,937,115; 5,937,341; 5,940,417; 5,943,154; 5,943,464; 5,948,322; 5,948,915; 5,949,943; 5,953,469; 5,959,159; 5,959,756; 5,962,658; 5,963,683; 5,966,233; 5,970,185; 5,970,186; 5,982,958; 5,982,961; 5,985,084; 5,987,202; 5,993,700; 6,001,958; 6,005,058; 6,005,707; 6,013,748; 6,017,470; 6,020,457; 6,022,671; 6,025,453; 6,026,205; 6,033,773; 6,033,774; 6,037,105; 6,041,157; 6,045,888; 6,047,095; 6,048,928; 6,051,722; 6,061,481; 6,061,487; 6,067,186; 6,072,920; 6,081,632; 6,081,634; 6,081,794; 6,086,794; 6,090,322; and 6,091,879.
The foregoing references provide instruction and guidance to fabricate waveguides from materials generally of the types described herein using approaches such as direct photolithography, reactive ion etching, eximer laser ablation, molding, conventional mask photolithography, ablative laser writing, or embossing (e.g., soft embossing). The foregoing references also disclose electron donors and electron bridges that may be incorporated into the films of the invention.
Components of optical communication systems that may be fabricated, in whole or part, with the films according to the present invention include, without limitation, straight waveguides, bends, single-mode splitters, couplers (including directional couplers, MMI couplers, star couplers), routers, filters (including wavelength filters), switches, modulators (optical and electro-optical, e.g., birefringent modulator, the Mach-Zehnder interferometer, and directional and evanescent coupler), arrays (including long, high-density waveguide arrays), optical interconnects, optochips, single-mode DWDM components, photonic crystal devices, resonant devices (e.g., photonic crystal, ring, or disc resonators, and gratings. The films described herein may be used with, for example, wafer-level processing, as applied in, for example, vertical cavity surface emitting laser (VCSEL) and CMOS technologies.
In many applications, the films described herein may be used in lieu of lithium niobate, gallium arsenide, and other inorganic materials that currently find use as light-transmissive materials in optical communication systems.
The films described herein may be used in telecommunication, data communication, signal processing, information processing, and radar system devices and thus may be used in communication methods relying, at least in part, on the optical transmission of information. Thus, a method according to the present invention may include communicating by transmitting information with light, where the light is transmitted at least in part through a film of the invention or related macrostructure.
The films of the invention can be incorporated into various electro-optical devices. Accordingly, in another aspect, the invention provides electro-optic devices including the following:
an electro-optical device including a film according to the invention;
a waveguide including a film according to the invention;
an optical switch including a film according to the invention;
an optical modulator including a film according to the invention;
an optical coupler including a film according to the invention;
an optical router including a film according to the present invention;
a communications system including a film of the invention;
a method of data transmission including transmitting light through or via a film of the invention;
a method of telecommunication including transmitting light through or via a film of the invention;
a method of transmitting light including directing light through or via a film of the invention;
a method of routing light through an optical system including transmitting light through or via a film of the invention;
an interferometric optical modulator or switch, including: (1) an input waveguide; (2) an output waveguide; (3) a first leg having a first end and a second end, the first leg being coupled to the input waveguide at the first end and to the output waveguide at the second end; and 4) and a second leg having a first end and a second end, the second leg being coupled to the input waveguide at the first end and to the output waveguide at the second end, wherein at least one of the first and second legs includes a film of the invention;
an optical modulator or switch, including: (1) an input; (2) an output; (3) a first waveguide extending between the input and output; and (4) a second waveguide aligned to the first waveguide and positioned for evanescent coupling to the first waveguide; wherein at least one of the first and second legs includes a film of the invention, the modulator or switch may further including an electrode positioned to produce an electric field across the first or second waveguide; and
an optical router including a plurality of switches, wherein each switch includes: (1) an input; (2) an output; (3) a first waveguide extending between the input and output; and (4) a second waveguide aligned to the first waveguide and positioned for evanescent coupling to the first waveguide; wherein at least one of the first and second legs includes a film of the invention, the plurality of switches may optionally be arranged in an array of rows and columns.
The following example is provided for the purpose of illustrating, not limiting, the invention.
EXAMPLE
The Preparation of a Representative Crosslinked Polymer Film: Crosslinked Polymer Host with Nonlinear Optical Chromophore Guest
In this example, the preparation of a representative crosslinked polymer film of the invention including a crosslinked polymer host and a nonlinear optical chromophore guest is described. The film is made by crosslinking a mixture of a crosslinkable graft copolymer having a diene moiety (PMMA-co-AMA) and a crosslinking agent having two dienophiles (bismaleimide, BMI) in the presence of a nonlinear optically active chromophore (AJC146). The film is partially crosslinked during drying before electrostatic poling is used to align the guest chromophores, after which the film is fully crosslinked. A schematic illustration of the method is illustrated in FIG. 2, and FIG. 3 provides an illustration of a method for forming representative films of the invention. The crosslinkable graft copolymer was prepared by copolymerizing 9-anthrylmethyl methacrylate (AMA) and methylmethacrylate (MA).
The synthesis of 9-anthrylmethyl methacrylate (AMA). A solution of 9-anthracenemethanol (4.30 g, 0.021 mol) in 50 mL of THF and 7 mL of triethylamine was stirred at room temperature for 30 min. Methacryloyl chloride (4.39 g, 0.042 mol) in 5 mL of THF was slowly added to the solution. The reaction mixture was stirred for 12 hours. After the filtration of a precipitated solid, all the solvent was evaporated under reduced pressure. The crude product was redissolved with methylene chloride and washed with water, dilute HCl, NaHCO3, and brine water. The pure product was obtained by flash chromatography on silica gel with a gradient eluent of hexane/methylene chloride (2:1 to 1:4) and recrystallized with hexane/methylene chloride (4.00 g, 68%).
The synthesis of PMMA-co-AMA (AMA/MMA=12:88 by mole %). A solution of 3.07 g (30.71 mmol) of MMA, 1.21 g (4.19 mmol) of AMA, and 33 mg (0.2 mmol) of AIBN in 14 mL of THF was degassed using the freeze-pump-thaw procedure three times and filled with nitrogen. The solution was first heated at 55° C. for 2 hours, then 62° C. for 12 hours, and finally 65° C. for 5 hours. The viscous solution was poured into 500 mL methanol to precipitate the polymer. The polymer was redissolved in THF and reprecipitated twice into methanol to yield 3.8 g of the polymer. Yield: 89%. Mn=36,000, Mw=90,000, Mw/Mn=2.49.
The synthesis of PMMA-co-AMA (AMA/MMA=20:80 by mole %). A solution of 830 mg (8.3 mmol) of MMA, 573 mg (2.08 mmol) of AMA, and 10 mg (0.06 mmol) of AIBN in 4 mL of THF was degassed using the freeze-pump-thaw procedure three times and filled with nitrogen. The solution was first heated at 55° C. for 2 hours and then at 62° C. for 12 hours. The viscous solution was poured into 100 mL methanol to precipitate the polymer. The polymer was redissolved in THF and reprecipitated twice into methanol to yield 1.0 g of the polymer. Yield: 71.3%. Mn=40,000, Mw/Mn=2.22.
The preparation and poling of the crosslinked film. A mixture of 30 mg of PMMA-co-AMA 12, 2.5 mg of BMI, and 14 mg of AJC146 (30 wt % chromophore) was dissolved in 530 mg of distilled 1,1,2-trichloroethane (8 wt % total solids) for 6 hours. The homogeneous solution was filtered through 0.2 μm of poly(tetrafluoroethylene) (PTFE) filter and spin-coated onto ITO glass substrates. The film thickness was controlled to be about 1.0 μm with a 1200 rpm spin speed. The spin-coated films were dried under vacuum for 10 hours at 50° C. and were stored under vacuum at room temperature for further measurements. A thin layer of gold was then sputtered onto the films as the top electrode for poling.
The use of an un-optimized process is expected to give low E-O activity due to premature crosslinking of the polymer before applying the poling field to the chromophores. To minimize the detrimental effect of crosslinking, poling is performed before the polymer film becomes fully crosslinked. At higher temperature and longer vacuum drying times, the E-O activity of the polymers is significantly reduced due to crosslinking before reorientation of chromophores. For example, the r33 value of the representative film after being dried at 50° C. for 10 hours was 215 pm/V under a 125 V/μm poling field. However, after vacuum drying for 10 hours at 70° C. and for 24 hours at 50° C. with the same material composition and poling condition measured 127 and 145 pm/V, respectively. The electro-optic (E-O) coefficient values were measured using the reflection technique at 1310 nm light according to Teng, C. C.; Man, H. T., Appl. Phys. Lett. 56:1734, 1990.
The representative film was poled with the following profile: 75 V/μm at 50° C., 5° C./min ramping to 135° C. The poling voltage was slowly increased to 125 V/μm from about 105° C. to about 125° C. The voltage was maintained until 135° C. and also during cooling to room temperature.
Substituting the polarizable chromophore AJL28 (illustrated in FIG. 1) as a guest under similar conditions to those described in the above example, yields a film having an r33 value of about 300 pm/V.
While illustrative embodiments have been illustrated and described, it will be appreciated that various changes can be made therein without departing from the spirit and scope of the invention.

## Claims

1. A film having electro-optic activity, comprising a plurality of aligned, polarizable chromophore compounds and a host matrix, wherein the host matrix comprises passive crosslinked polymers, and wherein the passive crosslinked polymers comprise one or more 4+2 cycloaddition crosslinks, wherein each crosslink is formed by 4+2 cycloaddition between a passive crosslinkable polymer and a crosslinking agent that does not include a polarizable chromophore.

2. The film of claim 1, wherein the 4+2 cycloaddition crosslink is the product of the reaction of a diene and a dienophile.

3. The film of claim 2, wherein the diene is an anthracene.

4. The film of claim 2, wherein the dienophile is a maleimide.

5. The film of claim 1, wherein the chromophore compound is a nonlinear optically active compound.

6. The film of claim 1, wherein the crosslinked polymers are crosslinked polymethylmethacrylate-co-9-anthrylmethyl methacrylate copolymers.

7. The film of claim 1 having an r33 value from about 215 to about 300 pm/V.

8. The film of claim 1, wherein the chromophore compounds are present in an amount from about 5 to about 50 percent by weight based on the total weight of the host matrix.

9. An electro-optic device, comprising the film of claim 1.

10. The film of claim 1, wherein the crosslinkable polymer comprises a diene.

11. The film of claim 1, wherein the crosslinkable polymer comprises a dienophile.

12. The film of claim 1, wherein the crosslinking agent comprises a diene.

13. The film of claim 1, wherein the crosslinking agent comprises a dienophile.

14. The film of claim 1, wherein the crosslinking agent comprises two or more dienophiles.

15. The film of claim 1, wherein the crosslinking agent is a bismaleimide.

16. The film of claim 1, wherein the crosslinking agent is a trismaleimide.

17. A film having electro-optic activity, comprising a plurality of aligned, polarizable chromophore compounds and a host matrix, wherein the host matrix comprises passive crosslinked polymers, and wherein the passive crosslinked polymers comprise one or more 4+2 cycloaddition crosslinks, wherein each crosslink is formed by 4+2 cycloaddition between a passive crosslinkable polymer and a crosslinking agent selected from a bismaleimide or a trismaleimide.