NONLINEAR OPTICAL MATERIALS AND DEVICES

Abstract: An electrooptic or optical parametric device comprises a noncrystalline second order optically nonlinear element and means for providing an optical input to and an optical output from said element wherein said element comprises an or­ ganic molecule having second order optical susceptibility in­ corporated in a directionally oriented manner in an optically clear glassy polymer. When said device is employed in an electrooptic mode it includes means for applying an electric field and/or optical input to said element for altering an optical property thereof.

Description: Technical Field This invention relates to nonlinear optical elements comprising the features of the preamble of claim 1 and to nonlinear optical devices such as electrooptic modulators and switches, frequency converters and data processors and optically nonlinear materials useful in such devices. Background of the Invention Electrooptical modulators, switches and optical parametric devices based upon the nonlinear optical properties of materials are known in the art. Generally, these devices have utilized inorganic crystals, e.g., LiNbO₃ as the optically nonlinear media. More recently, organic crystalline materials, e.g., 2-methyl-4-nitroanaline, have been shown to have a figure of merit as an optically nonlinear active material which is greater than that of LiNbO₃. In addition, due to the electronic states associated with the effect, the organic crystalline materials not only have large intrinsic second order nonlinear optical susceptabilities, but potentially possess very fast switching times. Further, associated with such second order nonlinear optical effect is a linear electrooptical effect. One problem, however, in obtaining an optically nonlinear medium for device application of the type previously described is the difficulty in providing uniform crystalline structures, and thin films of such materials in a manner to be suitable for integrated devices. We have now developed electrooptic and optical parametric devices and optically nonlinear media used therein which do not use or require crystalline structures. ANGEWANDTE CHEMIE. INTERNATIONAL EDITION, vol. 23, 1984, p. 690-703, Verlag Chemie GmbH, Weinheim, DE; D.J. Williams "Organic polymeric and non-polymeric materials with large nonlinearities" discloses films consisting of a thermotropic nematic liquid crystalline coplolymer doped with pleochroic dye, which are subjected to a transverse electrical field and their linear and second non-linear optical properties are examined. Orthoscopic examination of the films established the nematic texture of the doped polymer and the ability to achieve dc field induced homogenous alignment. From linear dichroism measurements in the films an order parameter of 0.3 was obtained. Second harmonic generation measurements relative to quartz were made to establish the value of second-order nonlinear susceptibility and to probe the nature of the dc field induced alignment. Poling the films below T g leads to a second-order susceptibility of about 3 * 10⁻⁹ esu. Second harmonic generation measurements were made under various conditions. It is described in this document to use a nematic liquid crystal copolymer doped with a pleochroic dye. However, this material is not glassy and has a definite ordering with the nematic phase. Throughout the following description the term "glassy" in connection with polymer is meant in its commonly understood and generally used sense to designate an amorphous structure without long range three-dimensional order. Summary of the Invention A nonlinear optical element comprises an optically clear polymer host and organic dopant molecules having a nonzero second order optical susceptibility, being incorporated and directionally aligned in said polymer host; and said polymer host is a glassy polymer. Further, an optical device comprises the aforementioned nonlinear optical element and means for providing an optical input to and an output from said element. When said device is employed in an electrooptic mode it includes means for applying an electric field and/or optical input to said element for altering an optical property thereof. Brief Description of the Drawings FIG. 1 is an elevational partially cross-sectional view of an electrooptical directional coupler or switch, FIG. 2 is an elevational view of an integrated solid state laser tuner and frequency stabilizer, FIG. 3 is a diagrammatic representation of a device for generating second harmonic frequencies, FIG. 4 is a diagrammatic representation of an electrooptic phase/intensity modulator; and FIG. 5 is an elevational view of an electrooptical guided wave intensity modulator. Detailed Description The heart of any optically nonlinear device is the nonlinear optical medium employed therein. We have found that in order to take advantage of large microscopic susceptabilities of many non-centrosymmetrical organic molecules in macroscopic devices, one may construct a noncrystalline medium comprising a non-centrosymmetric organic molecule having a non-zero second order optical susceptability incorporated in an optically clear glassy polymer in an ordered or directionally aligned arrangement of the organic molecules. Such second order nonlinear optical media can be prepared directly on a desired substrate or can be made as a free film or tape. It may be noted that this optically nonlinear media can be utilized as an optical waveguide as well as in electrooptic devices. Generally, in electrooptic devices, here is electrical control of the direction, phase, frequency and/or amplitude of lightwave signals. In one class of optical parametric devices there is mixing of two optical input signals to generate two optical output signals whose frequencies are the sum and difference of the two input frequencies and whose amplitudes are related to the input amplitudes. In another class of optical parametric devices, one input beam is converted to one output beam whose frequency is twice that of the input beam. Further, the novel devices can be integrated with electronic devices on a semiconductor chip or laser or other solid state device to form a monolithic optical or electrooptical semiconductor device. Examples of such devices are described below. Referring to FIG. 1 there is shown an elevational partially cross-sectional representation of an electrooptical directional coupler or switch 1. In accordance with FIG. 1, the coupler 1 comprises a substrate 2, e.g., glass, quartz or Si, a pair of spaced channel waveguides 3 and 4 on one surface of the substrate 2 and a pair of electrodes 5 and 6, one electrode associated with and contiguous to each channel waveguides 3 and 4, respectively. There is a central region 7 and 8 of each channel waveguide 3 and 4, respectively, where they are parallel to each other and where the spacing between waveguides is smallest. Typical spacing in this region is from 5µm to 20µm. Further, the electrodes 5 and 6 are positioned adjacent to the waveguide in this narrowly spaced region so as to maximize the electric field developed across the waveguides upon application of a voltage of the electrodes. Alternatively, as shown by the dotted lines, one may employ a single top electrode over the waveguides and a bottom electrode below the waveguides to enhance the field for a given applied voltage. In addition, the device may contain a protective polymer overcoat 7, e.g., a clear epoxy or acrylate polymer, to protect the waveguides 3 and 4. The electrooptic waveguides 3 and 4 which are about 2 µm thick are comprised of an optical quality glassy polymer host having doped therein a directionally ordered array of non-centrosymmetric organic molecules which exhibit second order optical susceptability in response to an applied field. In operation of the device, light, preferably from a monochromatic single mode source, e.g., a laser, is inputted into one area of the upper channel waveguide 3, e.g., as designated by S₁. In the absence of any applied field, the electromagnetic field extends beyond the confines of the waveguide 3 a distance which is greater than the gap distance between the parallel portions of the upper and lower waveguides and penetrates the lower waveguide 4 and is propagated therethrough as well. If the length of the parallel portions of the waveguide are selected such that an antinode exists at the point of the lower waveguide 4 where the waveguides 3 and 4 start to deviate, the light (electromagnetic waves) will essentially be emitted from the lower waveguides at S₂. This is the crossover or switched configuration. Upon applying of an appropriate voltage by means of the electrodes across the parallel waveguides, the electrooptical effect produced thereby causes the light to be transmitted directly in the upper waveguide and exit as shown by S₃. The voltage causing the maximum straight-through transmission is given by where U is the applied voltage, λ is the wavelength, n the index of refraction of the waveguide, r the electrooptic coefficient of the waveguide, d the waveguide separation distance, L the length of the narrowly spaced parallel portions, and α the overlap integral between applied electric field and the optical field in the waveguide. FIG. 2 shows an integrated laser tuner and frequency stabilizer using the electrooptic medium described herein. Here, a junction or injection laser 20 is grown on a semiconductor substrate 21, e.g., a GaAs laser on a GaAs substrate. A 1-3µm thick electrooptic film 22 lies adjacent and contiguous with the laser junction 23 to provide a waveguide for the light emitted at the junction 23. The film 22 is provided with opposing electrodes 24 and 25, on one surface thereof, as shown, or on opposite surfaces, i.e., one electrode 24a between the film and the substrate and one electrode 25a on the top surface of the film so as to provide means for applying an electric field within the electrooptical film 22. Alternatively, electrode 25a can be a highly doped portion of the substrate 21. The electrooptic effect of the film under an applied field results in a tunable filter or frequency stabilizer for the laser output. FIG. 3 shows the optically onlinear medium used in an optical parametric device for second harmonic frequency generation. Here, an incident light beam 30 at frequency ω impinges upon the optically nonlinear film 31. Due to the nonlinear optical properties of the film 31, two colinear beams 32 and 33 are emitted, one at the same frequency, ω, and one at twice the frequency, 2ω. The emerging colinear beams 32 and 33 are passed through a prism 34 to spatially separate the two wavelengths 32 and 33. The beam 32 at 2ω is now available to be used. FIG. 4 shows the use of the electrooptic film in an electrooptic phase/intensity modulator. Here, incident light 40 having a polarization P₁ is passed through the electrooptic film 41 which is provided with transparent electrodes 42 and 43 on opposing surfaces of the film 41. Upon passing through the film, the natural bi-refringence of the film causes a change of polarization of the light to P₂. When a voltage is applied to the film by means of a voltage source 44 applied across the electrodes 42 and 43, an electric field is generated within the film 41. Through the linear electrooptical property of the film 41, the electric field causes a change in the film's index of refraction, thereby altering the bi-refringence. This, in turn causes the emitted light to have yet a different polarization, designated as P₃. Thus, a polarization modulation between the values P₂ and P₃ can be achieved by the periodic applications and/or removal of the voltage to the film 41. An intensity modulation can be achieved by placing a polarizer 45 at the output beam which is oriented to allow the passage of either P₂ or P₃, but not both. It should be noted that the nonlinear optical film of the devices of FIGS. 4 and 5, in practice, are preferably deposited on a substrate. FIG. 5 shows a guided wave electrooptic intensity modulator employing an electrooptic material as described herein. Here, a film 50 of the electrooptic material is formed on a conductive substrate 51 having an insulative coating 52. The film 50 has a Mach-Zehnder two-arm interferrometric waveguide structure. A top electrode 53 is placed on one arm 54 of the interferromitric waveguide structure. The substrate is kept at ground potential. As voltage is applied to and removed from across the arm 54 by means of top electrode 53 and conducting substrate 51, an electric field is produced in the arm 54 of the interferrometer. This field changes the index of refration of the material due to the linear electrooptic effect possessed by the film 50. This results in an effective change in optical path length in arm 54 of the interferrometer relative to the other arm which, in turn, produces either constructive or destructive interference of the light at the recombination point 55. As the voltage is modulated so as to alternate between constructive and destructive conditions, the output intensity exhibits a maximum and minimum value, respectively. The second order nonlinear optical medium useful for the above mentioned and other electrooptic and optical parametric devices comprises an optically clear glassy polymer having a no-centrosymmetric organic molecule which exhibits a non-zero second order optical susceptability in a ordered (directionally aligned) arrangement within said polymer. Since the magnitude of the effect is a linear function of the concentration of the organic molecule in the polymer, it is advantageous to utilize a system where the organic molecule is highly soluble within the glassy polymer host. While many polymers may be suitable hosts, e.g., polymers of acrylates, methacrylates, clear epoxies, styrene and polycarbonate, we have found thus far that polymethylmethacrylate is generally preferred as the polymeric host material for the classes of nonlinear organic molecules investigated. Examples of suitable non-centrosymmetric organic molecules which are dissolved in the polymer are represented by the formulas: where R¹ is a strong electron withdraing group as known in the art, e.g., NO₂, and SO₂ R and R² is an electron donating or netural group, e.g., where R x and/or R y are H or an alkyl group or derivative thereof such as -C₂H₅, -C₂H₄OH, C₃H₇, etc. There may also be ring substitutions of the compounds. It should be understood that these compounds are merely representative of suitable non-centrosymmetric organic compounds useful in the practice of the invention and are not limiting. In practice, one should incorporate the maximum amount of active nonlinear optic compound as can be dissolved in the glassy polymer matrix in order to maximize the bulk second order nonlinear optical effect. Hence, the particular polymer most suitable with any specific nonlinear optical compound may depend upon the solubility of the compound in the polymer which can easily be determined. A particularly suitable system appears to be the azo dye, disperse red 1 (R₁ is NO₂ and R₂ is dissolved in polymethylmethacrylate (PMMA) to a concentration of up to 18 weight percent. Other compounds which are expected to give similar results in PMMA or other acrylate based polymers, e.g., polyethylacrylate, polymethylacrylate and polyethylmethacrylate are those where R₁ is -NO₂ and R₂ is either NH₂ or NR 3 / 2 where R³ are alkyl groups such as CH₃ , C₂H₅, C₃H₇ or the like or one such alkyl group and a hydrogen atom. The azo dyes such as disperse orange 3 have also been found to be suitable in an epoxy host. In all cases, the active non-centrosymmetric organic material must be directionally oriented in the polymer matrix. This orientation is accomplished by poling the molecules in the polymer under the influence of an electric field under conditions where the polymer is fluid (e.g., above its glass transistion temperature or mixed with a solvent therefor). The field is retained until the polymer film hardens by reducing the temperature or evaporating the solvent. Upon hardening, the oriented active molecules remain in their ordered position in the polymer. Unoriented films do not exhibit the second order nonlinear optical properties of the oriented films due to the cancellation of the microscopic molecular effects on a macroscopic level caused by random orientation of the molecules. It should also be possible to achieve an ordered film under an electric field applied across the active molecule dissolved in a liquid monomer which is spread on a substrate to form a film and polymerized in situ. An example of the preparation of a suitable nonlinear optical film is as follows. The polymer, e.g., PMMA, is dissolved in a suitable solvent and filtered through a sub-micron sized filter. Suitable solvents for PMMA are chloroform, DMSO, methylene chloride, chlorobenzene, acetone, ethyl or methyl cellosolve and cellosolve acetate. The optically nonlinear material is dissolved in the polymer-solvent solution. For the dye, disperse red 1, the concentration of the dye in the polymer is preferably about 18%. The substrate upon which the optically nonlinear film is to be prepared is thoroughly cleaned, preferably in a dust free atmosphere. Typical substrates are glass, quartz, aluminum, silicon wafer, thermal oxide coated silicon wafers and conductive indium-tin oxide-coated glass. A suitable substrate cleaning procedure employs an immersion in a heated solution comprising H₂O, NH₄OH and H₂O₂ in a volume ratio of 10:2.5:2 followed by a rinse with conductivity grade water and drying in an inert atmosphere. The substrate is then coated with the solution of the nonlinear optical material in the polymer such as by means of spin coating a 1µm thick film on the substrate and removing the solvent by baking. Thicker films, e.g., up to 5µm are preferably prepared by multiple coatings followed by baking after each coating. For films in the 25µm to 200µm thick range multiple coatings of about 25µm per coating may be achieved by spray coating or doctor blading. It may be noted that by techniques well known in the art, high quality photoresist patterns can be applied to unmetallized films to form films having feature sizes of for example 4-50µm, which may be useful in some of the novel devices previously described. In order to pole or orient the active optically nonlinear molecules in the deposited film, it is preferred that the substrate have provided a conductor on the surface on which the optically nonlinear film or a buffer layer beneath the film is to be deposited. This can be a transparent tin oxide, indium oxide or indium tin-oxide conductor or a transparent or non-transparent metallic conductor deposited for example by sputtering. A top conductor is formed over the deposited film such as by sputtering a thin (100-1000 A.) gold layer on the deposited film. The film sandwiched between electrodes is then raised about 5°C-40°C above the glass-rubber transition temperature of the polymer by slow heating. For example, the preferred azo dye in PMMA is heated at a rate of 5-15°C/minute to a temperature of from 115°-130°C. After heating, a poling voltage which aligns the optically nonlinear molecules in the polymer, is applied across the film and maintained for from 1-10 minutes. The voltage applied depends upon the film thickness. A voltage which creates a field of at least about 1x10⁵V/cm is desirable. Subsequently, the film is slowly cooled at a rate of about 10°C/minute and annealed for 5-15 minutes at a temperature just below the glass transition temperature ( 90°C for the azo dye in PMMA). After annealing it is slowly cooled to room temperature at about 15°C/minute and the poling voltage is removed. The slow heating, cooling, and annealing is to prevent defects from arising, minimizing or eliminating strain and minimizing free volume in the film. The top electrode layer may then be removed by abrasion or other means or it may be left on. Also the film may be patterned as previously mentioned by standard photoresist - etch techniques. For use in a second harmonic generator, the film is typically applied to a transparent indium tin oxide conductor on a glass substrate and the top electrode is a transparent sputtered gold electrode. For use in a directional coupler, the film is typically deposited on a thermal oxide coated silicon wafer and its top surface is metallized by sputtering 2000-3000A. of Al on the film.

Claims: A nonlinear optical element comprising: an optically clear polymer host; and organic dopant molecules having a nonzero second order optical susceptibility, being incorporated and directionally aligned in said polymer host; characterized in that said polymer host is a glassy polymer. The optical element recited in claim 1, wherein said element is a film of said polymer. The optical element recited in claim 2, wherein said film is adherent upon an optically clear substrate. The optical element recited in claim 3, wherein the film is from 1 µm to 200 µm in thickness. The optical element recited in anyone of claims 1 to 4, wherein the organic compound is dissolved in said polymer to about the limit of its solubility therein. The optical element recited in anyone of claims 1 to 5, wherein the organic compound is represented by the formula wherein X represents an atom selected from nitrogen and carbon, R¹ is a strong electron withdrawing group and R² is an electron donating or neutral group. The optical element recited in claim 6, wherein R¹ is selected from a member of the group consisting of where R is an organic radical and R² is wherein R x and/or R y is selected from a member of the group consisting of hydrogen and an alkyl group. The optical element recited in claim 6, wherein the polymer is selected from a member of the group consisting of polymethacrylates, polyacrylates, epoxy, polystyrene and polycarbonate. The optical element recited in anyone of claims 1 to 8, wherein the organic molecule is disperse red 1 azo dye and the polymer is polymethylmethacrylate. The optical element recited in claim 2, including means for applying a voltage across said film for altering an optical property thereof. The optical element recited in claim 10, wherein said voltage means comprises at least one pair of spaced electrodes, at least one of said electrodes being on a surface of said film. An optical device comprising the optical element recited in anyone of claims 1 to 11 and means for providing an optical input to and an optical output from said element. An electrooptical directional coupler or switch comprising the optical element recited in claim 10, and consisting of a film on a substrate, said film being present on said substrate in the form of two separated arms having a closely spaced, parallel central region from which the arms diverge on each side of said region, the spacing between arms and arm lengths of said central region being such that light of a given wavelength passing through one arm can be coupled to the other arm and emitted therefrom in the absence of an applied field and such emission from said other arm can be reduced or eliminated upon the application of an electric field to said arms and including means for providing an optical input to one of said arms and means for detecting an optical output. The device recited in claim 13 wherein the means for applying an electric field comprises spaced electrodes said electrodes being in the same plane as and adjcent each of said arms in the central region thereof. The device recited in claim 13, wherein the means for applying an electric field comprises at least one spaced electrode pair consisting of an electrode below and an electrode over said film in the central region thereof. An integrated injection laser tuner and frequency stabilizer comprises a p-n junction laser grown on a semiconductor substrate, an optical waveguide on said substrate contiguous with and extending from the laser junction, said waveguide comprising the optical element recited in claim 10 and consisting of a film having the organic compound in the shape of a non-central symmetric molecule, and means for applying an electric field to said waveguide film for tuning or stabilizing the output of said laser. A second harmonic generator comprising means for passing light of one frequency through the optical element recited in anyone of claims 1 to 11, so as to produce a coincidental wave of a second frequency which is twice the original frequency and means for splitting the coincidental waves to allow one to extract said second frequency wave independent of the original frequency. The device recited in claim 17, wherein the means for splitting the coincidental beams is a prism. An electrooptical phase modulator comprising means for passing light of a first phase through an optical element recited in anyone of claims 1 to 11, means for applying an electric field to said element sufficient to cause a phase change in the incident light passing therethrough to create light of second phase. The modulator recited in claim 19, including a polarizer situated in the light path after said electrooptic element whcih allows light of either said first phase or said second phase, but not both, to pass therethrough. An electrooptic amplitude modulator comprising an interferometric waveguide including the optical element recited in anyone of claims 1 to 11 and means for applying an electric field to an arm of said waveguide to change the index of refraction of said arm, means for providing an optical input to said waveguide and means for detecting an optical output from said waveguide, the intensity of said output being dependent upon the field applied to said arm of said waveguide. The modulator recited in claim 21, wherein said interferometer is of the Mach-Zehnder type and wherein the waveguide is a thin film deposited on a conductive substrate having an insulating layer between said waveguide film and said conductive substrate and one arm of said film having an electrode thereover such that a voltage can be applied between the substrate and said electrode.

Inventors: LALAMA, SALVATORE JOSEPH, SINGER, KENNETH DAVID, SOHN, JOHN EDWIN
Applicants: AMERICAN TELEPHONE AND TELEGRAPH COMPANY
Application year: 1986
Main classification: G02F1
IPC codes: G02F1, C09K9, H01S3