Photopolymerization process and related devices

• US 3,993,485 A
• Filed: 05/27/1975
• Issued: 11/23/1976
• Est. Priority Date: 05/27/1975
• Status: Expired due to Term

• Current Assignee: Bell Telephone Laboratories, Inc. (Nokia Corporation)
• Original Assignee: Bell Telephone Laboratories, Inc. (Nokia Corporation)
• Inventors: Chandross, Edwin Arthur, Weber, Heinz Paul, Tomlinson, Walter John III
• Primary Examiner(s): Welsh, John D.
• Application Number:
  US05/580,929
• Time in Patent Office: 546 Days
• Field of Search: 96/27 H, 96/35.1, 96/115 P, 350/3.5, 350/96 WG
• US Class Current: 385/141
• CPC Class Codes: G02B 6/02033 Core or cladding made from organic material, e.g. polymeric material G02B1/04 takes precedence
• CPC Class Codes: G02B 6/021 characterised by the core or cladding or coating, e.g. materials, radial refractive index profiles, cladding shape
• CPC Class Codes: G02B 6/02123 characterised by the method of manufacture of the grating photolithography G03F7/0005
• CPC Class Codes: G02B 6/032 with non solid core or cladding G02B6/02295 takes precedence
• CPC Class Codes: G03F 7/001 Phase modulating patterns, e.g. refractive index patterns
• CPC Class Codes: H01S 3/0635 provided with a periodic structure, e.g. using distributed feed-back, grating couplers controlling, e.g. modulating distributed feed-back lasers H01S3/102
• CPC Class Codes: Y10S 430/146 Laser beam

Abstract

A photopolymerization process is adapted for the production of various optical devices by means of a modified process which serves to increase the index change obtainable in a variable pattern of index of refraction. The process comprises the steps of flowing into place in a supporting structure a mixture of two components of differing reactivity and polarizability, partially polymerizing the mixture, writing a pattern of varying index of refraction in the partially polymerized mixture by further polymerizing it by suitable optical radiation in a corresponding pattern, and fixing the mixture against subsequent changes in polymerization. Typical components used in the process include a mixture of the monomers cyclohexyl methacrylate and N-vinylcarbazole together with benzoin methyl ether as a photosensitive initiator of polymerization, which proceeds by free radical reactions. In the limit of our technique, one of the components can have zero reactivity. This photopolymerization process is applicable to production of volume gratings in closed cavities having parts with constricted clearances therebetween, in which application it is impossible to evaporate unreacted components after the mixture has been flowed into place. The volume gratings are useful in distributed feedback lasers, in frequency sensitive optical filters and in channel-dropping arrangements for optical communication systems. Submerging the apparatus in which polymerization is to occur in an index-matching fluid between flat glass plates is an aid to producing uniform volume gratings in a cylindrical device.

Claims

1. A process comprising the steps of positioning in a supporting structure a mixture of at least two components of respectively differing photopolymerization reactivities and respectively differing optical polarizabilities, partially polymerizing the mixture, writing a pattern in the partially polymerized mixture by exposing it to optical radiation in a corresponding pattern and of a wavelength suitable for the photopolymerization, and fixing the mixture against the subsequent changes in polymerization.

2. A process according to claim 1 in which the positioning step comprises positioning a mixture of at least two components, a first component of which mixture is a monomer having a relatively high photopolymerization reactivity and a relatively high optical polarizability in the polymerized state, and a second component of the mixture is characterized by a substantially lower photopolymerization reactivity than said first component and a substantially lower optical polarizability than said first component, the writing step inducing a two-way diffusion of said components in the presence of the pattern of optical radiation, the writing step being continued long enough to promote diffusions of substantial portions of unpolymerized monomer from the low intensity light regions toward the high intensity light regions where they are subsequently polymerized and to induce diffusion of the second less reactive component from the high intensity light regions toward the low intensity light regions, the fixing step subsequently stabilizing the results of said two-way diffusion.

3. A process according to claim 1 in which the positioning step comprises positioning a mixture of at least two components, a first component of which mixture is a monomer having a relatively high photopolymerization reactivity and a relatively low optical polarizability in the polymerized state, a second component of which mixture is characterized by a substantially lower photopolymerization reactivity than said first component and a substantially higher optical polarizability than the polymerized form of said first component, said writing step being continued long enough to promote a diffusion of the unpolymerized monomer of said first component into regions of relatively high optical radiation intensity from regions of relatively low optical radiation intensity and to promote diffusion of the second component from the regions of relatively high optical radiation intensity toward the regions of relatively low optical radiation intensity, whereby the regions of the highest index of refraction coincide with the regions of relatively lowest optical radiation intensity during the writing step, the fixing step subsequently stabilizing the results of said two-way diffusion.

4. A process according to claim 1 in which the second component of the mixture has essentially negligible photopolymerization reactivity, and the fixing step polymerizes sufficient residual monomer portions of the first component about the concentrations of said second component to maintain the latter in their positions attained during the writing step.

5. A process according to claim 1 in which the two components of the mixture are initially substantially liquid components, the positioning step comprising flowing said components into position in a relatively restricted space of the supporting structure, the initial polymerizing step comprises increasing the viscosity of the mixture sufficiently to prevent flow of said mixture from said restricted space, the writing step promotes the two-way diffusion of the components from distances on the order no greater than the smallest dimension to be resolved in the pattern, and the fixing step includes photopolymerizing at least one component of the mixture to produce a solid matrix of both components retaining the results of the two-way diffusion of the writing step.

6. A process comprising mixing cyclohexyl methacrylate and a substantially comparable molecular proportion of N-vinylcarbazole and a substantially smaller proportion of benzoin methyl ether as a photosensitive initiator, flowing said mixture into position in a supporting structure, initially photopolymerizing partially to increase its viscosity to prevent flow along said supporting structure, writing a pattern of index of refraction into said mixture by exposing it to optical radiation adapted to promote further polymerizing of the cyclohexyl methacrylate, whereby a two-way diffusion of the monomer cyclohexyl methacrylate and N-vinylcarbazole occur, said methacrylate toward regions of highest optical intensity and said N-vinylcarbazole toward regions of lowest optical intensity, and fixing the patterns resulting from the two-way diffusion by a final exposure to uniform optical radiation selected to complete the polymerization of said mixture.

7. A process comprising mixing cyclohexyl methacrylate with a substantial but lesser portion of dimethyl suberate and still lesser proportions of ethylene glycol dimethacrylate and benzoin methyl ether as crosslinking monomer and photopolymerization initiator respectively, flowing said mixture into position in a supporting structure, initially the polymerizing of said mixture to increase its velocity and prevent flow along said supporting structure, writing a pattern of index of refraction into said mixture by exposing it to optical radiation selected to polymerize the polymerizable portions of said mixture whereby a two-way diffusion of the cyclohexyl methacrylate and dimethyl suberate is promoted, the former toward the regions of highest radiation intensity and the latter away from regions of highest radiation intensity, and fixing the mixture to preserve the index of refraction pattern resulting from the two-way diffusion by exposing it to optical radiation selected to complete the photopolymerization of the mixture.

8. A process comprising the steps of mixing butyl methacrylate with a substantially comparable molecular proportion of ethylene glycol dimethacrylate as a crosslinking monomer and 1-phenylnaphthalene as a liquid optical inert ingredient of relatively low viscosity and a substantially lesser proportion of benzoin methyl ether as a photosensitive polymerizing initiator, flowing said mixture into place in a supporting structure, initially photopolymerizing said mixture to increase its viscosity to prevent its flow along said supporting structure, writing an index of refraction pattern in said mixture by exposing it to a pattern of optical radiation selected to photopolymerize the monomer portion of butyl methacrylate and ethylene glycol dimethacrylate, thereby promoting a diffusion of the methacrylates toward the regions of highest optical radiation intensity and a diffusion of the 1-phenylnaphthalene away from the regions of highest optical intensity, and fixing the index of refraction pattern resulting from the two-way diffusion of exposing the mixture to optical radiation selected to complete the photopolymerization.