EP1632520A1 - Matériau filmogène et préparation de structures à relief de surface et optiquement anisotropiques par irradiation du film formé à partir de ce matériau filmogène - Google Patents

Matériau filmogène et préparation de structures à relief de surface et optiquement anisotropiques par irradiation du film formé à partir de ce matériau filmogène Download PDF

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EP1632520A1
EP1632520A1 EP04020997A EP04020997A EP1632520A1 EP 1632520 A1 EP1632520 A1 EP 1632520A1 EP 04020997 A EP04020997 A EP 04020997A EP 04020997 A EP04020997 A EP 04020997A EP 1632520 A1 EP1632520 A1 EP 1632520A1
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Prior art keywords
film
material according
induced
relief structure
irradiation
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EP04020997A
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German (de)
English (en)
Inventor
Joachim Stumpe
Leonid Goldenberg
Olga Kulikovska
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Priority to EP04020997A priority Critical patent/EP1632520A1/fr
Priority to KR1020077007638A priority patent/KR20070102983A/ko
Priority to EP05784051A priority patent/EP1794236B1/fr
Priority to AT05784051T priority patent/ATE419308T1/de
Priority to PCT/EP2005/009346 priority patent/WO2006024500A1/fr
Priority to CN2005800296512A priority patent/CN101031619B/zh
Priority to ES05784051T priority patent/ES2318529T3/es
Priority to US11/574,672 priority patent/US8026021B2/en
Priority to DE602005012128T priority patent/DE602005012128D1/de
Priority to TW094129590A priority patent/TW200619235A/zh
Priority to JP2007528769A priority patent/JP2008511702A/ja
Publication of EP1632520A1 publication Critical patent/EP1632520A1/fr
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
    • G03C1/73—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds

Definitions

  • the present invention relates generally to a new type of film forming material having unique photochemical properties.
  • Non-scattering, optically clear films formed from the new materials can be easily prepared. They allow light-induced generation of optical anisotropy (photo-induced dichroism and birefringence) therein and of topological surface structures, e.g. such as surface relief gratings (SRG).
  • SRG surface relief gratings
  • the material comprises a complex prepared from at least two components: 1) an anionic or cationic polyelectrolyte and 2) an oppositely charged cationic or anionic photosensitive low molecular weight compound having the ability to undergo E/Z isomerisation or to participate in a light induced cycloaddition or in a photoinduced rearrangement reaction or another reaction capable of generating optical anisotropy in the material upon irradiation.
  • the material based on this complex readily forms films, preferably on solid substrates or between two such substrates from water/alcoholic or organic solvents.
  • amorphous and liquid crystalline polymers containing azobenzene or other photoactive moieties such as stilbenes, cinnamates, coumarins in side chains or main chains can be used for the induction of anisotropy by photoorientation (K.lchimura, Chem. Rev. 2000, 100, 1847; A. Natansohn et al., Chem. Rev. 2002, 102, 4139; V. Shibaev et al., Prog. Polym. Sci. 28 (2003) 729 ⁇ 836; X. Jiang, et al., WO 98/36298).
  • Azobenzene derivatives are also known for their ability to form SRG when being exposed to gradient light field (A. Natansohn et al., Chem. Rev. 2002, 102, 4139).
  • azobenzene containing materials were used for optical anisotropy and/or SRG generation.
  • guest-host systems this was attained by mixing of photochromic azobenzene derivatives, e.g. 4-[4-N-n-hexyl-N-methylamino-phenylazo]-benzoic acid or modified Direct Red 1 azodye with readily available polymer PMMA as a matrix (J. Si et al., APPL. PHYS. LETT. 80, 2000, 359; C. Fiorini et al., Synthetic Metals 115 (2000), 121-125).
  • LBL layer-by-layer
  • a substrate is alternately immersed for about 10-20 min in an aqueous solution of a cationic polyelectrolyte, such as poly-DADMAC, and an anionic azobenzene containing compound, respectively.
  • a cationic polyelectrolyte such as poly-DADMAC
  • an anionic azobenzene containing compound respectively.
  • Each immersion results in the formation of a monolayer on the substrate surface with typical thickness of about 1 nm.
  • Numerous repetition of this procedure results in a multilayer film.
  • About 150 layers are required to obtain a reasonable thickness of the resulting layer.
  • Films up to 700 layers can be produced.
  • SRGs with an amplitude of up to 120-140 nm can be generated, wherein a photoinduced orientation of the azobenzene moieties can be observed.
  • the procedure is tedious and time consuming.
  • rather thick films are necessary for the inscription of deep SRG, and such films are difficult to obtain.
  • compositions may form films, which allow introduction of optical anisotropy and/or the generation of surface relief structures therein.
  • Such compositions may form films, which allow introduction of optical anisotropy and/or the generation of surface relief structures therein.
  • the inventors found a novel, photoactive, film forming material combining high efficiency of the induction of optical anisotropy as well as of surface relief structures with the simplicity of material preparation.
  • the material consists of a complex prepared from at least two components: 1. an anionic or cationic polyelectrolyte and 2. a opposite charged cationic or anionic photosensitive compound, in general a low molecular weight molecule. Further components such as plasticizers, conventional organic oligomers or polymers, other photosensitive compounds, dyes, or liquid crystalline compounds can be added to modify formulation properties, and the properties of the films (flexibility of the film, hydrophilic/hydrophobic properties and the like).
  • the invented materials readily form films on solid substrates from water/alcoholic or organic solvents. Optical anisotropy and/or surface relief structures can be induced in these films upon irradiation with light.
  • the photosensitive compound suitable for the present invention is an ionic compound which is capable to undergo a photoreaction, and mainly selected from photoisomerization, photocycloaddition reactions and photoinduced rearrangements. If it is capable to undergo a photoisomerization, it is of formula I or II [R-P-R'] n+ n/x A x- (I) or n/x A x+ [R-P-R'] n- (II) wherein P is a group which is capable of photo-induced E/Z isomerization , and R and R' are independently selected from optionally substituted and/or functionalized aryl-containing groups at least one of which is positively or negatively charged, A is a cation or anion which is oppositely charged, n is preferably 1 or 2, more preferably 1, but may in specific cases be higher (3 or 4), and x is 1 or 2.
  • the invention is not restricted to compounds of formulae I or II containing one or more azo groups.
  • the ionic compound is capable to undergo a photocycloaddition or photoinduced rearrangement, it is of formula III or IV: [R 1 -Q-R 1' ] n+ n/x A x- (III) [R 1 -Q-R 1' ] n+ n/x A x- (IV) wherein Q is a group capable of participating in a photocycloaddition, preferably a (2+2) addition or a (4+4) addition, or capable of participating in a photoinduced rearrangement, preferably the rearrangement of spiropyranes to merocyanines, or the so called Photo-Fries reaction, and R 1 and R 1' are independently selected from optionally substituted or functionalized groups which have electron-accepting properties or comprise at least one aryl moiety or such (a) group(s) which together with Q form an aryl ring or heteroaryl ring. At least one of R 1 and R 1' is positively or negatively charged, or the ring structure and/or a substitu
  • Q is part of a conjugated p ⁇ -electron system.
  • Examples for respective compounds are cinnamates, imines, stilbenes, chalcones, or p-phenylene diacrylic esters or amides, wherein at least one of R 1 and R 1' is an optionally substituted or functionalized phenyl or other aryl or heteroaryl ring and the other is also an optionally substituted or functionalized phenyl or other aryl or heteroaryl ring or a carboxylic ester or carbonamide group or a phenyl carbonyl residue. All the said groups or residues may be substituted or functionalized, and at least one of R 1 and R 1' must carry at least one positive or negative charge.
  • R 1 and R 1 ' are in such cases fused to form a ring structure, together with Q.
  • One or more atoms of this ring structure or, alternatively, a substituent attached thereto may carry the respective at least one positive or negative charge. Again, such compounds, if carrying at least one positive or negative charge, will fall under the scope of the present invention.
  • Q may comprise more atoms in its backbone and may e.g. be an aromatic C 6 ring which can be fused within an aromatic system or may carry suitable residues at least one of which carries the respective charge(s).
  • One example is an anthracene derivative. Anthracenes are known to undergo a (4+4) cycloaddition whereby carbon atoms 9 and 10 will form bridges to a neighbour atom, resulting in formation of a sandwich-like dimer structure.
  • compounds (I) to (IV) may carry more than one group P or Q, respectively.
  • the said compounds are intended to include bisazobenzenes or trisazobenzenes as well as diacrylic ester compounds, e.g. p-phenylene-diacrylic esters.
  • R, R', R 1 and/or R 1' is an aryl group, it may be or may comprise a homocyclic or heterocyclic ring.
  • this ring may be fused to an aromatic system, e.g. a naphthalene or anthracene system. Further, the ring can be substituted or functionalized by one or more substituents.
  • substituted shall mean any other substituent.
  • the compounds as defined above may be used in any kind of salts as available, e.g. ammonium or sodium salts, chlorides, sulfates and the like, or they may be acidic or basic compounds e.g. carboxylic acids, sulfonic acids, amines, or a hydroxy group carrying compounds, and the like, which are capable of reacting with an oppositely charged polyelectrolyte to yield a respective ionic complex. As outlined above, they can be positively or negatively charged, with one or more charges.
  • salts e.g. ammonium or sodium salts, chlorides, sulfates and the like
  • they may be acidic or basic compounds e.g. carboxylic acids, sulfonic acids, amines, or a hydroxy group carrying compounds, and the like, which are capable of reacting with an oppositely charged polyelectrolyte to yield a respective ionic complex.
  • they can be positively or negatively charged, with one or more charges.
  • the polyelectrolyte to be used carries charges which are opposite to those of the photosensitive compound, i.e. is a polycation or polyanion.
  • the ionic strength of its cations or anions may be strong or weak.
  • the polyelectrolyte may be of natural origin, or may be synthetically prepared. Examples are polyethyleneimine, poly(allylamine hydrochloride), poly(dimethyldiallylammonium chloride), carageenans, polyacrylic acid, sulfonated cellulose, polystyrenesulfonate, Nafion, sol-gel products of alkoxysilanes functionalised with a proton acceptor (e.g. amino-group) to yield ammonium groups or to yield carboxylate groups.
  • a proton acceptor e.g. amino-group
  • the polyelectrolyte can be described as having formula mx/n Z n+ [B x- ] m or mx/n Z n- [B x+ ] m wherein m is the number of monomer-units in the polyelectrolyte and x is the number of the charge each of the monomer-unit carries.
  • Z is a cation or anion carrying n charges which are opposite to those of the polymer-moiety.
  • Z can be the same as A as defined for formulae I to IV and m may be in the order of from 2 to 1000 or even more, while n and x are as defined for formulae I to IV.
  • At least one polyelectrolyte as defined above and at least one photosensitive compound as defined above are each dissolved in a suitable solvent. Since both components are ionic, they are usually soluble in protic and polar solvents, in most cases in water or a lower alcohol or a mixture of both. The mixtures are preferably considerably concentrated, often until saturation.
  • the ratio of photosensitive compound to polyelectrolyte should preferably be not less than 0.5:1, in relation to the number of charges. This means that per each charge of the polyelectrolyte, at least 0.5 charges of a photosensitive compound should be present. The remaining charges of the polyelectrolyte can be compensated by additives, e.g.
  • ionic oligomers or additional ionic dyes or the like as required and/or desired.
  • An excess of photosensitive compound is not critical, i.e. the ratio can be 1:1 or even higher in order to achieve higher dye loading (and to improve consequently the effectivity of the material).
  • This complex may be described to consist of one or more of the following:
  • the said photosensitive compound it is alternatively possible to mix the said photosensitive compound with a non-ionic polymer, the polymer having groups within each monomeric unit which only upon addition of protons (acid) or a Lewis base become ionic and charged so that the polymer is converted into a polyelectrolyte.
  • non-ionic polymers are polymers comprising a Lewis base in each of their monomer units which may accept a proton or acid groups from which a proton can be taken. In such cases, a respective Lewis base or proton donor compound is added after mixing, in order to obtain the desired, inventive complex.
  • the complex precipitates at least partly, it can be taken up and redissolved in a less polar solvent, e.g. in water/alcohol mixtures containing more alcohol, in a longer chain alcohol, in a mixture of alcohol with another solvent, e.g. an aprotic solvent, or in an acetone or an ether like tetrahydrofuran, if desired. Further, it is possible to exchange any of the solvents of the initial solutions against another, more desired solvent, e.g. by evaporating the first solvent and taking up the complex with another solvent or solvent mixture.
  • a less polar solvent e.g. in water/alcohol mixtures containing more alcohol, in a longer chain alcohol, in a mixture of alcohol with another solvent, e.g. an aprotic solvent, or in an acetone or an ether like tetrahydrofuran, if desired.
  • Additives may be incorporated at any stage prior to forming the films, as appropriate. They may either be added to any of the solutions prior to the preparation of the complex, or may be added to the complex in any stage. Additives may be, for example, organic polymers, compounds having film forming abilities, plasticizers, liquid crystals and/or photosensitive compounds differing from the photosensitive compounds having formulae (I) to (IV).
  • the complex according to the present invention is rather stable, due to its ionic character. Specifically, it will be resistant against the influence of heat in a much larger extent than comparable materials which are not of ionic nature. Such materials will in general soften at lower temperatures.
  • the materials of the present invention comprise the inventive complex, together with one or more additional components which may undergo or provide cross-linking of the film, preferably after structurization.
  • additional components may be selected from additional organic monomers which are capable to bind to specific groups of the polyelectrolyte, forming bridges and/or an organic network.
  • this component is selected from monomeric photosensitive molecules which are capable to undergo photopolymerisation or photocross-linking.
  • the conditions of photopolymerisation or cross-linking should be such that a wavelength is used which is different from that used for "recording" (SRG formation) as mentioned above.
  • this component is susceptible to thermal curing or polymerizes/provides bridges or a cross-linking network upon thermal treatment.
  • any of the conventional film forming techniques like spin-coating or casting, doctor's blading and the like can be used to prepare homogeneous films on a substrate in merely one step.
  • ink-jet printing to produce patterned films is also readily available using e.g. water/alcoholic media. After the film has been deposited on the substrate or the respective basic layer, it is allowed to dry, preferably at room temperature, for example in air.
  • the thickness of the films may vary in a broad range, depending on the desired application. For example, it may vary between 10 nm and 50 ⁇ m, typically between 200 nm and 5 ⁇ m. If desired, additional layers may be deposited, either between the substrate and the film of the inventive photosensitive material and/or as one or more covering layers on the upper surface of the film.
  • the photoactive material according to the invention is light-sensitive, due to the presence of groups in the complex which may either undergo light-induced E/Z isomerization and/or photocycloaddition reactions, or light induced rearrangement reactions.
  • groups in the complex which may either undergo light-induced E/Z isomerization and/or photocycloaddition reactions, or light induced rearrangement reactions.
  • optical anisotropy is induced within films made from this material.
  • the optical anisotropy may be stable, unstable or erasable in dependence on the material composition, treatment and irradiation conditions, as outlined below. Under inhomogeneous irradiation, both a modulation of optical anisotropy and a deformation of film surface may be achieved.
  • the latter process is as effective or even more effective as reported for azobenzene containing functionalized polymers that have been known as the most effective for the surface relief gratings formation.
  • the material of the present invention is a viable alternative to the covalently bonded polymer systems used until now.
  • the properties of the proposed material may be optically modified in different ways. If irradiated homogeneously with polarized light, the film becomes anisotropic, that means, birefringence and/or dichroism are induced. This is due to aphotoorientation process in the steady state of the photoisomerisation in the material upon polarized irradiation. For example, if the material contains groups which undergo E/Z isomerization, light irradiation will result in an orientation of such groups. In case of photocycloadditions or other photoreactions, an angular-selective photo-decomposition or angular-selective formation of photoproducts will be observed.
  • optical anisotropy induced in such a way may relax back, be erased thermally or by irradiation with light, or may be stable.
  • the induced orientation based on the E/Z isomerization may be stable, may undergo relaxation, or may be erased thermally or photochemically.
  • the optical anisotropy of azobenzene systems is only temporary induced (while surface relief gratings formed therewith are long-term stable, see below).
  • optical anisotropy and surface gratings due to photocycloaddition will remain stable since the reaction is not reversible.
  • Stability of optical anisotropy may also be achieved by using a material which allows further curing or crosslinking, e.g. by building up an organic network within the film.
  • light induced optical anisotropy may be "frozen” in the material when the material is cured after inducing said anisotropy.
  • the velocity of the induction and relaxation processes may be controlled through adjusting the temperature and/or the parameters of irradiating/erasing light.
  • a variety of thin film polarization elements like polarizer or retarder may be created that may be permanent or optically switchable.
  • the light-induced change of birefringence or dichroism in this material may be also effectively used for optical data storage and, if reversible, for optical processing.
  • a film is irradiated with an inhomogeneous light field, i.e. a light field wherein the intensity or/and polarization of irradiating light is spatially modulated
  • the induced anisotropy is correspondingly modulated through the film.
  • irradiation through a mask In this way, pixel thin film polarization elements may be fabricated.
  • Another example is irradiation with an interference pattern, i.e. holographic irradiation. In this way, a variety of holographic optical elements operating in transmission or reflection modes (like polarization beam splitter or polarization discriminator) may be realized.
  • surface relief structures may be generated on the free surface of films made from the material of the present invention by inhomogeneous irradiation with polarized light (holographic, mask or near-field exposure).
  • Surface relief structures may be a result of a photo-induced mass transport upon an E/Z photoisomerization reaction or upon photocycloaddition or photoinduced rearrangement reaction (e.g. caused by shrinkage due to ring formation).
  • a film made of the material of the present invention is irradiated inhomogeneously, formation of surface relief structures (surface relief gratings, SRGs) can be observed along with the generation of inhomogeneous optical anisotropy.
  • SRGs surface relief gratings
  • formation of SRGs can, if required or desired, be suppressed by irradiating a film between two substrates.
  • reversibility and irreversibility of surface relief structures the same applies as outlined above for the occurrence of optical anisotropy.
  • the lateral size of generated relief structures ranges from tens of nanometers (in the case of irradiation with near-field) to tens of microns provided by holographic irradiation. It is being demonstrated here that the efficiency of the relief formation is comparable to the values reported for the azobenzene functionalized polymers (modulation depth of 2 ⁇ m was achieved).
  • Atomic force microscopy (AFM) images of SRG written in the materials of the present invention and, for comparison, in side chain azobenzene polymers of the prior art are shown in Fig. 1.
  • the final relief structure may be "frozen” or fixed, for example, thermally or by flood exposure (exposure of the whole film) in order to obtain crosslinking or the like. and to avoid destruction of the resulting relief.
  • relief holographic elements like diffraction grating, beam coupler, beam multiplexer, splitter or deflector, Fresnel lens and the like may be created.
  • Applications of structured films are not restricted to optical elements only.
  • One step all-optical structured surfaces may be used as templates for self-organisation of particles, as command surface for alignment of liquid crystals, as surface with modified wetting/dewetting properties or as antireflective layers.
  • surface relief structures may be replicated using a wide variety of different materials. Replication may be performed once or manifold. A replica may again serve as template for replication.
  • Materials which are useful for replication are known in the art. Examples are polysiloxanes, e.g. polydimethylsiloxane. Such materials may be prepared as resins having sufficiently low viscosity to fill the fine structures of the SRG and may be dried or cured after replication to yield a stable material.
  • Other examples are polyacrylate resins, polyurethanes, ene-thiol compositions or a metal, e.g. via electrochemical deposition from a metal solution.
  • the initial surface relief structure can be washed out from the replica, if desired, using an appropriate solvent.
  • the materials of the present invention have, inter alia, the following advantages: they can be manufactured from readily available non-expensive commercial materials, namely commercially available polyelectrolytes and photochromic derivatives with ionic groups. There is a great flexibility in their preparation, as well as in the composition of the materials and systems (multi-component systems). It is possible to use environmental friendly water/alcoholic media as solvents. Since the complexes and formulations are prepared in protic solvents like water and/or alcoholic media, films can easily be prepared on polymeric or other (e.g. inorganic) substrates or combined with other polymer layers which are not stable in organic solvents usually used for polymer film manufacturing, but would allow to form another layer from water/alcoholic media.
  • Ink-jet printing will be also readily available with water/alcoholic solvents.
  • the initial photosensitive film with the photo-induced structure can be washed out by solvents.
  • Anisotropic films and surface relief structures can be produced using the new material without expensive synthesis and purification of photochromic polymers wherein the photochromic unit must be covalently attached to the polymer backbone.
  • the film and products made from this film e.g. SRGs, are thermally stable, at least until about 150-200°C.
  • the material of the present invention may be used in a wide variety of technical fields, and specifically in the field of technical and other optics, data storage and telecommunication.
  • the material may be used as a photosensitive medium, optical element, functional surface and/or template.
  • Said elements may e.g. be diffractive elements, polarization elements, focusing elements or combinations of such elements. If the light-induced properties thereof are reversible, they can be used as or in elements for optical or optical/thermal switching. In such cases, the material is preferably prepared by a method as claimed in claim 27 or 28.
  • the light-induced properties are reversible, it may be used as a medium for real-time holography or optical information processing.
  • the photosensitive medium can be a medium for irreversible or reversible optical data storage. If the data storage is reversible, written information can subsequently be eliminated by irradiation or heating, if desired, whereafter another writing cycle is possible.
  • the material is used as a template, wherein the template surface is a surface for replication to another material or the command surface for aligning of liquid crystals, self-organization of particles. The surface may determine the chemical, mechanical and/or optical properties of the material, preferably selected from wetting/dewetting, hardness, reflectance and scattering.
  • Alizarin Yellow GG (5-(3-Nitrophenylazo)salicylic acid sodium salt, Aldrich) was dissolved in 20 ml of distilled water, 40 ⁇ l of 30% aqueous solution polyethyleneimine was added. The deposit was separated by filtration (30mg after drying) and dissolved in 1 ml of THF, while the mother solution was discarded. A film of about 2 ⁇ m thickness was fabricated from the THF solution by casting onto the glass substrate in a close chamber at room temperature. After drying at room temperature in air for 5 h, the film was irradiated with the interference pattern formed by two linearly orthogonally polarized beams with polarisation planes at ⁇ 45° to the incidence plane.
  • the irradiation wavelength was 488 nm, and the angle between beams was about of 12° resulting in a period of 2.3 ⁇ m.
  • the intensities of interfering beams were equal to 250 mW/cm 2 , the irradiation time was 40 min.
  • the 1 st order diffraction efficiency measured during the recording is shown in Fig. 2.
  • 1 st order diffraction efficiency at the end of recording was measured to be 16.5%.
  • the induced surface relief was investigated by means of AFM and revealed a SRG with amplitude of ca. 350 nm. The measured topography and the related cross-section are shown in Fig. 1.
  • the film from the material of the Example 1a was irradiated with the interference pattern formed by two linearly orthogonally polarized beams with polarisation planes at ⁇ 45° to the incidence plane.
  • the irradiation wavelength was 488 nm, and the angle between beams was about of 12° resulting in a period of 2.3 ⁇ m.
  • the intensities of interfering beams were equal to 250 mW/cm 2 , the irradiation time was 40 min.
  • For the erasing of grating one of the recording beams was used.
  • the polarisation of the erasing light was linear with polarisation plane at 45° to the grating grooves and the intensity of light was 250 mW/cm 2 .
  • the 0 th and 1 st order diffraction efficiencies measured during the recording and erasing of the grating are shown in Fig. 3.
  • Example 1a The film with the inscribed grating as in Example 1a was step-wise heated to a final temperature of 150°. Until 150° the grating was stable. At this temperature thermal erasing evident by decreasing 1 st order diffraction efficiency and by increasing 0 order diffraction efficiency started. The erasing was followed for 60 min (Fig. 4).
  • FIG. 1a A grating as in Example 1a was rewritten into the film of Example 2.
  • Figure 5 presents the diffraction efficiency measured during recording of the first grating, erasing with linearly polarized light and the recording of second grating onto the same spot of the film. The second recording has been done with a higher intensity thus resulting in a much faster formation of a grating.
  • a film of about 2 ⁇ m thickness was prepared as in Example 1b. Two gratings were successively inscribed into the same spot on a film. Between the two recording steps the film was rotated at 90° around the normal to the film plane. As a result a 2-dimensional structure was inscribed that is a combination of two linear gratings inscribed in the single steps.
  • the AFM topology image of induced structure is shown in Figure 6.
  • the gratings were recorded into the films of the material of the Example 1a.
  • the period of the gratings, recording intensities and irradiation times were kept constant for all gratings.
  • the polarisation of the recording beams was varied: i) linear parallel ss; ii) linear parallel pp; iii) linear orthogonal ⁇ 45°; iv) linear orthogonal 0°, 90°; v) circular parallel; vi) circular orthogonal.
  • the obtained diffraction efficiencies and the relief modulation depths are shown in Table 1. It is well seen that the linear orthogonal ⁇ 45° polarisation configuration is the most effective one.
  • a film of the material of Example 1a was exposed to the linearly polarized light of the wavelength of 488 nm.
  • the induction and the relaxation of the optical anisotropy were detected in real time by means of a probe beam of a He-Ne laser operating at a wavelength of 633 nm.
  • the probe light was linearly polarized at 45° to the polarisation plane of the irradiating beam.
  • the transmitted probe beam was split into two orthogonally polarized beams by means of a Wollaston-prism.
  • the intensities of both orthogonal polarisation components i.e. the component with the polarisation of the incident probe beam and a new component with orthogonal polarisation rising due to the induced birefringence, were measured.
  • Figure 7a represents the time behaviour of the induced optical anisotropy. Fifteen induction/relaxation cycles are shown, whereas during the first cycle the saturation and the complete relaxation of the signal were reached. It is seen that at the applied intensity and the wavelength of irradiation the induction time is of about 3 min. The time constant of dark relaxation is estimated to be of 8 min. The anisotropy was almost completely erased and then induced again. No fatigue is noticed after 30 induction/erasure cycles.
  • a film of the material of Example 1 was alternatively exposed to linearly polarized light with orthogonal polarisation planes.
  • the wavelength of the irradiation was 488 nm.
  • the induction of the optical anisotropy was detected as in Example 7a.
  • Figure 8a represents the switching of the induced optical anisotropy and
  • Figure 8b shows the switching dynamics. It is seen that the induced optical anisotropy is completely switched between two states by the irradiation with properly polarized light.
  • the surface relief structure as in Example 1a was replicated into polydimethylsiloxane (PDMS) by pouring a mixture of Sylgard silicone elastomer 184 and curing agent (10: 1) on the top of the SRG and allowing it to be hardened for 3 h at 60 C.
  • PDMS polydimethylsiloxane
  • the comparison of grating and replica is shown in the Fig. 9.
  • the original grating had amplitude of ca. 700-800 nm, replica has the same relief shape and amplitude of 400-500 nm.
  • Norland optical adhesive NOA65 (Norland corporation) was poured onto the surface of SRG obtained as in Example 1a and immediately irradiated for 30 sec. with UV light to harden. Separation of NOA layer from SRG yields the replica of grating in NOA material.
  • Example 9b was repeated, however, instead of NOA65, a two component adhesive (curing time approx. 5 min at 60°C) was used. After pouring the adhesive mixture onto the grating and hardening it for about 10 min at 60°C the replica was easily separated from the grating.
  • a surface relief grating as obtained in any of examples 1 was soaked in 1.2 mg/ml solution of SnCl 2 (activation solution) for 30 min. and then electroless plated with Ag by pouring onto the surface of the grating the following solution: 120 mg AgNO 3 200 ⁇ l 30% NH 3 solution, 80 mg NaOH in 20 ml of water. After washing with water, the Ag covered grating was used as cathode in Ni electrochemical plating in the following Ni plating bath: 50 ml water, 6.4 g NiSO 4 , 2.4 g Na 2 SO 4 x10H 2 O, 1 g MgSO 4 , 2 g H 3 BO 3 , 0.25 g Nacl.
  • Plating condition were Ni sacrificial anode, current density 20 mA/cm 2 , stirring.

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EP04020997A 2004-09-03 2004-09-03 Matériau filmogène et préparation de structures à relief de surface et optiquement anisotropiques par irradiation du film formé à partir de ce matériau filmogène Withdrawn EP1632520A1 (fr)

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EP04020997A EP1632520A1 (fr) 2004-09-03 2004-09-03 Matériau filmogène et préparation de structures à relief de surface et optiquement anisotropiques par irradiation du film formé à partir de ce matériau filmogène
KR1020077007638A KR20070102983A (ko) 2004-09-03 2005-08-30 필름 형성 물질 및 상기 물질에 대한 조사에 의한 표면양각 및 광학 이방성 구조의 제조
EP05784051A EP1794236B1 (fr) 2004-09-03 2005-08-30 Matiere filmogene et preparation de structures a relief de surface et optiquement anisotropiques par l'irradiation d'un film de ladite matiere
AT05784051T ATE419308T1 (de) 2004-09-03 2005-08-30 Filmbildendes material und herstellung von oberflächenreliefstrukturen und optisch anisotropen strukturen durch bestrahlung eines films aus dem material
PCT/EP2005/009346 WO2006024500A1 (fr) 2004-09-03 2005-08-30 Matiere filmogene et preparation de structures a relief de surface et optiquement anisotropiques par l'irradiation d'un film de ladite matiere
CN2005800296512A CN101031619B (zh) 2004-09-03 2005-08-30 成膜材料以及通过辐照所述材料的膜制备表面起伏和光学异向性结构
ES05784051T ES2318529T3 (es) 2004-09-03 2005-08-30 Material de formacion de pelicula y preparacion de un relieve superficial y estructuras opticamente anisotropicas irradiando una pelicula de dicho material.
US11/574,672 US8026021B2 (en) 2004-09-03 2005-08-30 Film forming material and preparation of surface relief and optically anisotropic structures by irradiating a film of the said material
DE602005012128T DE602005012128D1 (de) 2004-09-03 2005-08-30 Filmbildendes material und herstellung von oberfläturen durch bestrahlung eines films aus dem material
TW094129590A TW200619235A (en) 2004-09-03 2005-08-30 Film forming material and preparation of surface relief and optically anisotropic structures by irradiating a film of the said material
JP2007528769A JP2008511702A (ja) 2004-09-03 2005-08-30 薄膜形成物質及びこの物質で形成された薄膜を照射することによる表面レリーフの形成と光学的異方性構造の形成

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US10345093B2 (en) * 2015-12-11 2019-07-09 University Of Helsinki Arrangement and method of determining properties of a surface and subsurface structures

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US20030141441A1 (en) * 2002-01-30 2003-07-31 Fuji Xerox Co., Ltd. Optical encoder and scale for encoder

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