CN100410707C - Steam meltaback preparation of low-consumption organic polymer array wave light-conducting grating - Google Patents

Steam meltaback preparation of low-consumption organic polymer array wave light-conducting grating Download PDF

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CN100410707C
CN100410707C CNB2005101190606A CN200510119060A CN100410707C CN 100410707 C CN100410707 C CN 100410707C CN B2005101190606 A CNB2005101190606 A CN B2005101190606A CN 200510119060 A CN200510119060 A CN 200510119060A CN 100410707 C CN100410707 C CN 100410707C
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organic polymer
waveguide
polymer waveguide
steam
general formula
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张大明
鄂书林
张海明
邓文渊
张希珍
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Changchun Institute of Optics Fine Mechanics and Physics of CAS
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Abstract

The invention relates to a preparation method of the organic polymer array waveguide grating. Spin coating the organic polymer waveguide lower envelope and the core layer material on the Si underlay and dry and solidify them. Vaporize or spurt the metal film, carry out photoetching and oxygen reactive ion etching and etch the organic polymer waveguide core layer outside the figure. Put it in the organic steam and control temperature and time to make the churlish part of the organic polymer waveguide core layer side wall dissolve gradually and become smooth. After corroding the metal layer, spin coating the organic polymer waveguide upper envelope material, dry and solidify them to get the organic polymer array waveguide grating wave length division multiplex or detaching multiplex device with the low loss. The invention adopts the steam round dissolution technique to reduce the churlish extent of the organic polymer waveguide grating side wall and decrease the dispersion loss led by the coarseness of the waveguide side wall. It produces the organic polymer array waveguide grating wave length division multiplex or detaching multiplex device with the low loss to make the total loss decrease by 5-10dB.

Description

The steam of low-loss organic polymer array waveguide optical grating returns molten preparation method
Technical field
The invention belongs to the preparation method of Wavelength division multiplexer/demultiplexer in the optical communication system, relate to a kind of organic polymer array waveguide optical grating.
Background technology
Wavelength-division multiplex (WDM) technology is a kind of effective ways that solve broadband, high capacity optical fiber network communication.Multiplexing demultiplexing device is the Primary Component of structure wavelength-division multiplex system.Practical now multiplexer comprises Fiber Bragg Grating FBG filtering type, multilayer film filtering type and arrayed waveguide grating type.Wherein, array waveguide grating is considered to the most rising a kind of novel light wavelength division multiplexing device that is applicable to the dense wavelength division multiplexing system.Array waveguide grating can be operated in high order diffraction, so its overall dimensions is very little but the wavelength resolution of good millimicron magnitude is arranged.Array waveguide grating not only can be used as multiplexer, demodulation multiplexer, lambda router, and have the wavelength interval little, be beneficial to integrated, the number of channel is many, it is low to crosstalk, output characteristics such as smooth, is the important component part of many functional modules in the fiber optic network.
At present, many researchers are putting forth effort to study silica-based organic polymer array waveguide grating device, advantages such as this device has that low price, technology are simple, the transparency is good, polarization-insensitive and Heat stability is good, make its with the competition of inorganic array waveguide grating device in be in an advantageous position.At present in some developed countries such as Japan, the U.S., Germany all in the research work of actively developing the organic polymer array waveguide grating device, and having obtained many important progress, some main indexes reach the level of inorganic array waveguide grating device just gradually.
The organic polymer array waveguide grating device mainly is method formation waveguide covering and the sandwich layer by spin coating, form the waveguide core of bar shaped or ridged again by traditional photoetching and reactive ion etching technology, method is simple, to instrument and equipment require lowly, thereby be subjected to general welcome.But, behind reactive ion etching process, the waveguide core sidewall is more coarse, does not have the smooth interface in the theory, and this coarse waveguide sidewalls is the main cause that causes light scattering loss in transmission course, and the existence of this scattering loss has increased the total losses of array waveguide grating device.
The roughness of polymer waveguide sandwich layer sidewall after reactive ion etching generally greater than 200nm, by the about 1.5-2.5dB/cm of it scattering loss that causes.
Experimental results show that, the unevenness of organic polymer material, the crack of film and bubble, micronic dust in the air, the levels of precision of reticle figure waveguide edge with a certain distance is arranged in theory, aluminium film not fine and close, it is not very smooth that the error of lithographic accuracy, development all can make waveguide edge, add that the relative inorganic thin film of organic polymer thin film is soft more, so after reactive ion etching, the bombardment of etching gas ion and side direction etching all cause the coarse of organic polymer waveguide core sidewall easily.
Summary of the invention
Because the background technology etching technics brings the coarse of organic polymer optical waveguide sidewall, make waveguide sidewalls have bigger scattering loss, thereby cause organic polymer array waveguide optical grating Wavelength division multiplexer/demultiplexer spare that bigger problems such as insertion loss are arranged, the objective of the invention is to reduce the scattering loss that light is caused by waveguide sidewalls in transmission course in order to address the above problem, reduce the insertion loss of Wavelength division multiplexer/demultiplexer spare, the steam that provides a kind of economy to prepare low-loss organic polymer array waveguide optical grating efficiently returns molten preparation method.
The steam that the present invention makes low-loss organic polymer array waveguide optical grating returns dissolution method, its processing step is as follows: dry and the heat cross-linking reaction after earlier applying organic polymer waveguide under-clad layer material with spin-coating method on the silicon substrate, spin coating organic polymer waveguide core material and drying with heat cross-linking reacts then; Evaporation or splash-proofing sputtering metal film and apply photoresist on metal film top and carry out photoetching on the organic polymer waveguide core material again, the light tight district that utilization is positioned at the photolithography plate on photoresist top carries out selectivity to ultraviolet light and blocks, remove photolithography plate after the exposure and develop, simultaneously with the array waveguide grating figure transfer on the photolithography plate on photoresist and metal film; Carry out the oxygen reactive ion etching then, simultaneously photoresist and metal film are carried out etching, after exposing metal film, continue the whole etchings of organic polymer waveguide sandwich layer are formed the organic polymer waveguide sandwich layer of array waveguide grating; The organic polymer waveguide sandwich layer of making is placed airtight saturated organic steam container, under the temperature of 50-70 degree, molten processing is returned at the concavo-convex position of organic polymer waveguide sandwich layer sidewall, time is 50-90 minute, the jog position is dissolved retraction gradually under the effect of steam, thereby forms smooth organic polymer waveguide sandwich layer sidewall; Remove metal film behind Hui Rong, spin coating organic polymer waveguide top covering material on the organic polymer waveguide sandwich layer promptly obtains low-loss organic polymer array waveguide optical grating after oven dry and the cross-linking reaction then; Described organic polymer waveguide under-clad layer material is identical with organic polymer waveguide top covering material and be: the fluorinated polyester of A, general formula (I) expression; The phenyl-pentafluoride ethene of B, general formula (V) expression and the multipolymer of glytidyl methacrylate; A kind of in the methyl methacrylate of C, general formula (VII) expression and these three kinds of materials of methyl-prop diluted acid epoxy methacrylate-trimethoxysilyl propylmethacrylate copolymer; Described organic polymer waveguide core material, be to add high index of refraction correctives (VI) on described organic polymer waveguide or in the under-clad layer material or regulate the proportioning of synthesizing " organic polymer waveguide clad material " reactant to constitute the organic polymer material of high index of refraction, and the refractive index of used organic polymer waveguide core material is between 1.46-1.60, under 1.55 mum wavelengths.
Advantage of the present invention:
Owing to adopt steam of the present invention to return molten technology, reduced the waveguide sidewalls roughness of organic polymer array waveguide optical grating, having reduced light effectively transmits in waveguide owing to the coarse scattering loss that causes of waveguide sidewalls, thereby can produce low-loss organic polymer array waveguide optical grating Wavelength division multiplexer/demultiplexer spare, make the total losses of array waveguide grating reduce 5-10dB.
The metal mask layer technology that the present invention uses not only can be protected the organic polymer waveguide sandwich layer when the oxygen reactive ion etching, make it to conform to design load, also returns the upper surface of protection organic polymer waveguide sandwich layer in the molten process by time molten processing at steam.
Array waveguide grating device is operated near the 1550nm, if when the roughness of sidewall reaches 150-200nm, is back the waveguide sidewalls of the organic polymer array waveguide optical grating before the molten processing as Fig. 3, and it is bigger in the scattering loss of waveguide sidewalls.The organic polymer array waveguide optical grating made of the present invention for example, the number of channel is 33 * 33, the centre wavelength of work is 1.55 μ m, channel spacing 0.8nm, it is 6-10dB by the coarse scattering loss that brings of waveguide sidewalls.Utilize steam of the present invention to return molten technology, by selecting for use appropriate solvent as boil-off gas, under the control of certain temperature and time, after the organic polymer waveguide sandwich layer of spin coating top covering did not return molten processing, corresponding scattering loss can be reduced in the 2-3dB.After utilizing the organic polymer array waveguide optical grating waveguide sidewalls Hui Rong that the present invention prepares electron micrograph as shown in Figure 4, the roughness that shows organic polymer waveguide core layer sidewall is reduced to about 20nm about the 200nm by Fig. 3.The invention solves the big problem of organic polymer waveguide etching rear wall roughness in the above-mentioned background technology, 0.3-0.5dB/cm is reduced in scattering loss.
Description of drawings
Fig. 1 is an organic polymer array waveguide optical grating planar structure synoptic diagram of the present invention
Fig. 2 a, Fig. 2 b, Fig. 2 c, Fig. 2 d are the process charts of preparation organic polymer array waveguide grating device of the present invention;
Fig. 3 is an electron micrograph before the organic polymer array waveguide optical grating waveguide sidewalls Hui Rong of the present invention;
Fig. 4 is an electron micrograph behind the organic polymer array waveguide optical grating waveguide sidewalls Hui Rong of the present invention.
Embodiment
The input waveguide of organic polymer array waveguide optical grating, output waveguide can design as required, and Waveguide array generally is made up of 100-500 bar optical waveguide, and concrete number can be determined according to actual materials used and process conditions.The optical principle of array waveguide grating is: the length difference of adjacent array waveguide is a constant, the multi-wavelength light that is coupled into input waveguide by optical fiber behind two rowland gardens power by the optical grating diffraction theoretical distribution, according to the formula of the mode profile of array waveguide grating far diffraction field, can obtain different wavelength output in corresponding output waveguide.
The steam that the present invention makes low-loss organic polymer array waveguide optical grating returns dissolution method, its processing step is as follows: dry and the heat cross-linking reaction after earlier applying organic polymer waveguide under-clad layer material 2 with spin-coating method on the silicon substrate 1, spin coating organic polymer waveguide core material 3 and drying with heat cross-linking reacts then; Evaporation or splash-proofing sputtering metal film 4 and apply photoresist 5 and carry out photoetching on organic polymer waveguide core material 3 again utilize 7 pairs of ultraviolet lights in light tight district 8 of photolithography plate 6 to carry out selectivity and block, shown in Fig. 2 a.Remove photolithography plate 6 after the exposure and develop, thus with the figure transfer on the photolithography plate on photoresist 5 and metal film 4.Carry out oxygen reactive ion etching 9 then, shown in Fig. 2 b.Photoresist 5 and metal film 4 are etched simultaneously during the oxygen reactive ion etching, because photoresist is thinner, so very fast photoresist layer is etched away, expose metal film 4.Because metal film 4 has good mask effect in oxygen reactive ion etching process, therefore the part of not covered continues to be etched, and the part of coverage is protected.After finishing, reactive ion etching forms the structure shown in Fig. 2 c.Wherein the sidewall of organic polymer waveguide sandwich layer 11 promptly is pending uneven surface.The organic polymer waveguide sandwich layer of making 11 is placed airtight saturated organic steam, and (50 degree-70 degree) return molten processing at a certain temperature, and the time is 50 minutes-90 minutes.In returning molten process, metal film 4 can continue to stop the Hui Rong of 10 pairs of organic polymer waveguide upper surfaces of steam, carry out Hui Rong and only organic polymer waveguide sandwich layer 11 sidewalls are had concavo-convex position, the jog position is dissolved retraction gradually under the effect of steam 10, thereby form the organic polymer waveguide sandwich layer sidewall of smoother, shown in Fig. 2 c; Remove metal film 4 behind Hui Rong, spin coating organic polymer waveguide top covering material 12 on organic polymer waveguide sandwich layer 11 promptly obtains low-loss organic polymer array waveguide optical grating after oven dry and the cross-linking reaction, shown in Fig. 2 d then.
The waveguide covering and the core material of organic polymer array waveguide optical grating of the present invention are organic polymer materials, all are solution state before spin coating, need filter through the filtrator below 0.4 micron and 0.4 micron; The organic polymer waveguide clad material adopts the multipolymer of fluorinated polymeric material such as fluorinated polyester, fluorinated polyether, fluorinated polyimide or fluorinated styrenes and glytidyl methacrylate, also can use not fluorine-containing organic polymer material; The organic polymer waveguide core material is the organic polymer material that the proportioning that adds the high index of refraction correctives in the above in the described organic polymer waveguide clad material or regulate synthetic organic polymer waveguide cladding materials reactant constitutes high index of refraction, the refractive index of used organic polymer waveguide core material is at (under 1.55 mum wavelengths) between the 1.46-1.60, to satisfy different array waveguide grating device demands.
The selected organic polymer material of the present invention can be following A, B, and three kinds of C:
A, organic polymer waveguide covering and waveguide core layer material are a kind of fluorinated polyesters, its molecular structural formula is shown in general formula (I):
Figure C20051011906000081
Above-mentioned fluorinated polyester by structural formula (II), (III) and (IV) different proportion of monomer form have different refractivity organic polymer as waveguide cladding materials and waveguide core layer material.The refractive index of organic polymer waveguide clad material is 1.46, and organic polymer waveguide sandwich layer refractive index is at (under 1.55 mum wavelengths) between 1.46~1.54.
B, organic polymer waveguide covering and waveguide core layer material can be the multipolymers of phenyl-pentafluoride ethene and glytidyl methacrylate, its molecular structural formula is shown in general formula (V), general formula (VI) is the high index of refraction correctives, the organic polymer waveguide clad material is made up of general formula (V), and refractive index is 1.47 (under 1.55 mum wavelengths).Add high index of refraction correctives (VI) in the organic polymer waveguide clad material, the content of control high index of refraction in whole material makes the refractive index of organic polymer waveguide core material at (under 1.55 mum wavelengths) between 1.47~1.55.
Figure C20051011906000091
C, can also use a kind of not fluorine-containing organic polymer material as waveguide cladding materials and waveguide core layer material, be methyl methacrylate and glytidyl methacrylate multipolymer (this material can adopt the conventional method copolyreaction to make from methyl methacrylate and two kinds of materials of glytidyl methacrylate), its molecular structural formula is shown in general formula (VII).The organic polymer waveguide clad material is made up of general formula (VII), and refractive index is 1.48 (under 1.55 mum wavelengths).In the organic polymer waveguide clad material, add high index of refraction correctives (VI) and control its content, make the refractive index of organic polymer waveguide core material at (under 1.55 mum wavelengths) between 1.48~1.58.
Figure C20051011906000092
The organic polymer waveguide clad material of above-mentioned selection and waveguide core layer material, the absorption loss of fluorinated polyester material is less than 0.5dB/cm when the logical optical wavelength of device is 1.55 μ m, and the absorption loss of fluorine material is not about 2dB/cm.Though its absorption loss was less when fluorinated polymeric material prepared as device, material cost is higher than not fluorine material.No matter adopt still fluorine material not of fluorine material, can adopt back molten technology to reduce the scattering loss of organic polymer waveguide sidewall, have ubiquity.
As Fig. 1 is the polymer arrayed waveguide grating structure of utilizing method of the present invention to make, by input waveguide 1-1, two Rowland circle 1-2,1-4, Waveguide array 1-3 and output waveguide 1-5 form, the two ends of Rowland circle 1-2 are connected with Waveguide array 1-3 with input waveguide 1-1 respectively, and the two ends of Rowland circle 1-4 are connected with output waveguide 1-5 with Waveguide array 1-3 respectively.
In sum, the organic polymer array waveguide grating device has that manufacture craft is simple, cost is low, birefringence is less, refractive index is easy to control and advantage such as polarization-insensitive, can adopt traditional photoetching technique and reactive ion etching (RIE) technology to realize technology.Because the randomness and the flexibility of organic polymer material inside, make that the organic polymer waveguide sidewall after the reactive ion etching is coarse easily, therefore the organic polymer waveguide after the etching is in suitable saturated solvent steam, under optimized time and temperature, return molten processing, obtain the smoother organic polymer waveguide sandwich layer of sidewall, and then prepare low-loss array waveguide grating device.This invention is suitable for producing low-cost, high-performance organic polymer array waveguide grating device, for the practicability of organic polymer array waveguide optical grating provides a reliable approach.
Embodiment 1, select above-mentioned organic polymer material C, its formulations prepared from solutions process is as follows: get methyl methacrylate and glytidyl methacrylate multipolymer as organic polymer waveguide under-clad layer material 2 (shown in general formula VII), after tested, the refractive index of this material at 1.55 μ m places is 1.483.With bisphenol A epoxide resin as high index of refraction correctives (shown in general formula VI), be incorporated in the organic polymer waveguide clad material, be formed with organic polymer waveguide core layer material 3, regulate the percentage composition of bisphenol A epoxide resin, control organic polymer waveguide sandwich layer refractive index is 1.495, and the organic polymer waveguide that makes formation is the single mode transport waveguide.In organic polymer waveguide covering and waveguide core layer material, add a certain amount of butyl acetate solvent and dilute, mix and stir, filter, regulate its concentration, make it and can slowly flow with 0.4 micron filtrator, standby.
The spin coating mode:
The organic polymer waveguide under-clad layer material 2 of organic polymer material C preparation is applied on the silicon substrate of handling 1, rotating speed rotation with 2500 rev/mins, rotational time is 30 seconds, dries then, obtains thickness and be 10 microns organic polymer waveguide under-clad layer 2; Again the rotating speed of organic polymer waveguide core material 3 with 3500 rev/mins is spun on the organic polymer waveguide clad material 2, the thickness that makes organic polymer waveguide core material 3 is in 6 micrometer ranges, the aluminium film 4 of oven dry back evaporation one deck 50nm, the spin coating photoresist 5 then, photoetching, development are carried out with array waveguide grating photolithography plate 6 in the baking back before the photoresist 5, with the array waveguide grating figure transfer on the photolithography plate to photoresist 5, by developing further the array waveguide grating figure transfer to aluminium film 4.
Reactive ion etching:
The sample of above preparation is positioned in the reactive ion etching machine, under the oxygen condition, carry out reactive ion etching 9, photoresist 5 at first is etched away, expose aluminium film 4, because during the reactive ion etching of aluminium film in oxygen atmosphere, aluminium meeting and oxygen reaction, form one deck aluminium oxide on the surface, stop 3 reactions of oxygen and the organic polymer core material below it, thereby play good mask effect, can guarantee the end surface shape of the organic polymer waveguide made.50 watts of the incident microwave powers of reactive ion etching 9, reflective power<1 watt-hour, etching time is 40-60 minute.
Steam Hui Rong
The sample of above preparation is positioned in the airtight butyl acetate saturated vapour, the aluminium mask 4 that attention covers in melt back on the organic polymer waveguide sandwich layer can not remove, otherwise originally level and smooth organic polymer waveguide sandwich layer upper surface is dissolved with the out-of-flatness that may become owing to returning.Under 50 degree, 90 minutes or 70 degree, 50 minutes condition, sample is returned molten processing.After returning cementing bundle and cooling, with sodium hydroxide solution erosion removal aluminium film 4, spin coating organic polymer top covering material 12 on sample again, the thickness of top covering is as the criterion to cover the organic polymer waveguide sandwich layer within 7 microns.So just prepare the low-loss organic polymer array waveguide grating device that adheres to specification.
Embodiment 2: select above-mentioned organic polymer material A, get fluorinated polyester compound (I) and be dissolved in N, in the N-2 NMF, being concentrated into concentration after 0.4 micron membranes filters is 15%, as the organic polymer waveguide clad material, standby.
Get the fluorinated polyester compound and be dissolved in N, in the N-2 NMF, after 0.4 micron membranes filters, be concentrated into concentration and be 15% as the organic polymer waveguide core material as the organic polymer waveguide core material, standby.
Spin coating mode, reactive ion etching, steam Hui Rong (selecting N for use, N-2 NMF steam) step are with embodiment 1.
Embodiment 3: select above-mentioned organic polymer material B, the solution (shown in general formula V) (copolymerization ratio of phenyl-pentafluoride ethene and glytidyl methacrylate is 6: 4) of getting the multipolymer of phenyl-pentafluoride ethene and glytidyl methacrylate is as the organic polymer waveguide clad material, and solvent is a butyl acetate solution., be incorporated in the organic polymer waveguide clad material as high index of refraction correctives (shown in general formula VI) with bisphenol A epoxide resin, be formed with organic polymer waveguide core layer materials for later use.
Spin coating mode, reactive ion etching, steam Hui Rong (selecting butyl acetate steam for use) step are with embodiment 1.

Claims (1)

1. the steam of low-loss organic polymer array waveguide optical grating returns molten preparation method, it is characterized in that: its processing step is as follows: dry and the heat cross-linking reaction after earlier applying organic polymer waveguide under-clad layer material with spin-coating method on the silicon substrate, spin coating organic polymer waveguide core material and drying with heat cross-linking reacts then; Evaporation or splash-proofing sputtering metal film and apply photoresist on metal film top and carry out photoetching on the organic polymer waveguide core material again, the light tight district that utilization is positioned at the photolithography plate on photoresist top carries out selectivity to ultraviolet light and blocks, remove photolithography plate after the exposure and develop, simultaneously with the array waveguide grating figure transfer on the photolithography plate on photoresist and metal film; Carry out the oxygen reactive ion etching then, simultaneously photoresist and metal film are carried out etching, after exposing metal film, continue the whole etchings of organic polymer waveguide sandwich layer are formed the organic polymer waveguide sandwich layer of array waveguide grating; The organic polymer waveguide sandwich layer of making is placed airtight saturated organic steam container, under the temperature of 50-70 degree, molten processing is returned at the concavo-convex position of organic polymer waveguide sandwich layer sidewall, time is 50-90 minute, the jog position is dissolved retraction gradually under the effect of steam, thereby forms smooth organic polymer waveguide sandwich layer sidewall; Remove metal film behind Hui Rong, spin coating organic polymer waveguide top covering material on the organic polymer waveguide sandwich layer promptly obtains low-loss organic polymer array waveguide optical grating after oven dry and the cross-linking reaction then; Described organic polymer waveguide under-clad layer material is identical with organic polymer waveguide top covering material and be: the fluorinated polyester of A, general formula (I) expression; The phenyl-pentafluoride ethene of B, general formula (V) expression and the multipolymer of glytidyl methacrylate; A kind of in the methyl methacrylate of C, general formula (VII) expression and these three kinds of materials of methyl-prop diluted acid epoxy methacrylate-trimethoxysilyl propylmethacrylate copolymer; Described organic polymer waveguide core material, be to add high index of refraction correctives (VI) on described organic polymer waveguide or in the under-clad layer material or regulate the proportioning of synthesizing " organic polymer waveguide clad material " reactant to constitute the organic polymer material of high index of refraction, and the refractive index of used organic polymer waveguide core material is between 1.46-1.60, under 1.55 mum wavelengths; Described general formula (I), general formula (V), general formula (VII), general formula (VI) chemical formula are:
Figure C2005101190600003C1
CNB2005101190606A 2005-12-08 2005-12-08 Steam meltaback preparation of low-consumption organic polymer array wave light-conducting grating Expired - Fee Related CN100410707C (en)

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TWI456276B (en) * 2011-11-11 2014-10-11 Univ Nat Formosa Method of fabrication for an asymmetric bragg coupler-based polymeric filter with a single-grating waveguide
CN103424376B (en) * 2013-08-02 2016-02-17 贵州大学 A kind of biochip based on grating guide mode resonance technology and preparation method thereof
CN105759349A (en) * 2015-07-03 2016-07-13 苏州峰通光电有限公司 Organic-inorganic hybrid integrated thermo-optical modulation type grating and preparation method thereof
CN113050222B (en) * 2021-04-16 2022-03-08 吉林大学 Reconfigurable polymer mode converter for mode division multiplexing system
CN115480347A (en) * 2021-06-15 2022-12-16 中国科学院长春光学精密机械与物理研究所 Method for improving verticality of array waveguide fiber and slab waveguide in wavelength division multiplexer

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