RU2683873C1 - Method of formation of polarization-sensitive material, polarization-sensitive material produced therewith and polarization-optical elements and devices, including specified polarization-sensitive material - Google Patents

Abstract

FIELD: optical physics.SUBSTANCE: present invention relates to optical physics, in particular, to a method for forming a polarization-sensitive material, capable of forming and/or transforming, in volume thereof and on surface thereof, the spatially modulated picture in the solid state, ordered anisotropic molecular structure in the form of a polarization-optical element. Claimed method of forming a polarization-sensitive material, capable in the solid state reversibly form and/or transform in volume thereof and on the surface a picture of a spatially modulated, ordered anisotropic molecular structure in the form of a polarization-optical element by acting polarized or unpolarized, but directed radiation to the polarization-sensitive component of the specified polarization-sensitive material. As a polarization-sensitive component, responsible for the formation in it of an anisotropic optical element, photochemically stable, anisotropic one- or two-photon absorbing, non-luminescent or weakly luminescent substance is used, which is a component of a polarization-sensitive material in the form of a component uniformly distributed at the molecular level in a homogeneous and isotropic low or high molecular weight matrix. Specified formed spatially modulated, ordered anisotropic molecular structure can be reversibly formed and/or transformed many times both in the case of a single, and in the case of a two-photon, through a real or virtual intermediate level, absorption of the proposed photochemically stable component of the polarization-sensitive material, which also includes other low molecular weight additives whose vibrational levels of the ground state are close or in resonance with the corresponding vibrational levels of molecules of a photochemically stable substance, providing an efficient process of anisotropic intermolecular vibrational cross-relaxation of the energy of an absorbed quantum in the nearest environment during irradiation of the MDL, in addition, the regulatory film-forming, viscous, anisotropic-optical, physico-chemical and mechanical properties of the formed material, depending on its specific application.EFFECT: technical result: development of a method for forming new polarization-sensitive solid-state photoanisotropic materials based on a previously unknown effect in non-luminescent or weakly luminescent, photochemically stable, anisotropically absorbing (dichroic) substances (pCSS) capable of reversibly forming and/or transforming spatially modulated, ordered molecular functional nano-, micro- or macro-pattern structures in accordance with the spatial distribution of polarization and energy characteristics of one- or two-photon absorbed activating radiation.28 cl, 9 dwg

Description

FIELD OF TECHNOLOGY

The present invention relates to optical physics, and in particular to a method of forming a polarization-sensitive material capable of reversibly forming and / or transforming in its bulk and on the surface a picture of a spatially modulated, ordered anisotropic molecular structure in the form of a polarizing optical element. The subject of the present invention can be used in specific systems of 3-dimensional optical elements, for example, such as anisotropic three-dimensional optical elements such as diffraction gratings, lenses, functional phase plates, as well as various structures with a complex three-dimensional configuration of anisotropic optical properties. As the latter, there can be polarized computer models transparent for measuring radiation of various products subjected to mechanical stresses and with which it is possible to carry out the same studies by photoelasticity as with real objects [J.W. Dally, Introduction to Photoelasticity, Exp. Mech 20, 409 (1980)].

The present invention also relates to three-dimensional systems of stereo imaging and polarization holography and three-dimensional systems of optical memory WORM (write only read many) or RW (rewritable) type.

Layers based on non-luminescent or weakly luminescent, photochemically stable, anisotropically absorbing (dichroic) substances with surface-ordered molecular structures can be used as photo-oriented layers for thermotropic and lyotropic liquid crystals (LC), as well as optically formed highly oriented matrices for special low-molecular active additives exhibiting high reaction selectivity and the effectiveness of the various photothermo- or simply chemically occurring processes depending on the degree of their picture orientation molecular ordering in the matrix, etc.

The mechanism of photoinduced optical anisotropy in such media was not previously known and is based on the reversible formation of a spatial pattern of orientational molecular ordering in them, the magnitude and direction of which are determined by the local spatial distribution of the polarization state (and the direction of propagation) of optical radiation absorbed by them one or two photons.

BACKGROUND

The first industrial applications of solid-state polarizing optical elements (POEs) and devices were realized more than 70 years ago, for example, in the form of light modulators using materials from natural electro-optical crystals with specified optical and geometric parameters as polarizing-optical materials (for example, see Handbook of Lasers, edited by Academician AM Prokhorov, in 2 volumes, vol. 2, Moscow: Sov. Radio, 1978, 400 pages), as well as in the form of Land’s film polarizers and phase plates with using one fundamentally stretched polymer films with the presence in them (or without them) of dissolved dichroic substances (for example, see W. Sherklif, Polarized light, preparation and use, translated from English, Moscow: MIR, 1965, 264 pp. .) or oriented solid-state layers of dyes formed from lyotropic liquid-crystalline properties exhibiting in certain solvents (for example, see JF Dreyer, US 2,400,877 A, IPC G02B 5/30, published May 28, 1946). Despite significant technological efforts, these work on POE (except for Land's film polarizers) were not widely used, mainly due to their limited functionality.

Significant progress in the development of POE has come with the discovery of lasers, holography, and optical memory. At the same time, to expand their functional capabilities, the role of the technological effect of optical, especially polarized radiation on the bulk and surface properties of solid-state, in particular organic, media in the form of so-called polarization-sensitive materials (PCM) has increased.

The development of such anisotropic bulk optical structures as, for example, a variety of fiber or integrated optical radiation input-output elements or photonic crystals includes the preparation of spatially periodic nano-, micro- and submicrostructures for use in the visible or near infrared wavelength range electromagnetic radiation.

The developers' desire to create technology for cheap and mass production of light-weight anisotropic optical and electro-optical elements and devices stimulates them to use new polarization-sensitive optical media and materials.

In the technology for the production of oriented molecular structures, both in volume and on the surface of solid optical films and bodies, optical methods are possible that allow the formation of reversible or irreversible orientational molecular structures in layers with a thickness of about several nanometers to several millimeters under the influence of optically active radiation, absorbed in the layer.

In general, the optical methods for the formation of such anisotropic molecular structures can be of two types: the “photothermal type of formation” (FTTF), the method adopted for the closest analogue of the method of forming the polarization-sensitive material claimed by the authors, and the “photon type of formation” (POTF), the method adopted for the prototype of the inventive method of forming a polarization-sensitive material.

When using non-magneto-optical media operating in the FTTF mode, a local powerful pulsed optical exposure to radiation with quantum energy hv leads to pulsed local melting (at temperature T1 for a time t ₁ ) of the medium and the transition from the amorphous phase state to the polycrystalline state when it is cooled [see, e.g. US Pat. No: 6,090,508; 5,666,344; 5,597,998] (Fig. 1b):

The process is reversible and a reverse transition is possible when exposed to the same radiation source with different parameters (kT ₂ , t ₂ ) of the pulse.

In the case of using magneto-optical media operating in the PTF mode in the presence of an external magnetic field H, the local pulsed optical effect leads to pulsed local melting of the medium followed by reversible orientational reorganization of its microdomains upon cooling [see, for example, US Pat. No, No: 5,187,703; 5,822,282; 6,061,307] (Fig. 1c).

The disadvantages of materials based on FTTF type are its applicability only to media with a very small layer thickness (of the order of 1 μm) and the difficulty of using large spatial sizes (areas) of picture-oriented molecular nano- or microstructures in the production technology.

einen neuen effekt der strahlung in lichtempfindlichen schichten. Verhandl. Deutsch. PhysiK. Ges., 21, 479-491, 615, 623 (1919)] (рис. 1d).Currently, the “Photon-type formation” (POTF) method of forming polarization-sensitive materials is described in a huge number of patents, which used a lot of photosensitive compositions based on a variety of monomolecular irreversible or reversible (photochromic) photochemical reactions of destruction or structuring under the action of polarized radiation . This method of passive photo selection is based on the Weigert effect), first discovered in 1919 [F. Weigert

einen neuen effekt der strahlung in lichtempfindlichen schichten. Verhandl. Deutsch. PhysiK. Ges., 21, 479-491, 615, 623 (1919)] (Fig. 1d).

The essence of the method of passive photo selection resulting from angular hole burning (ANB) is that the resonance absorption of optical radiation by a photochemically active molecule occurs with a maximum probability ε if the direction of the long axis of its dipole transition moment μqe at the wavelength of the activating radiation coincides with the direction of the electric vector of the light wave Ehv in accordance with equation (2):

where θ is the angle between Ehv and μge. With the perpendicular mutual direction of these vectors, the probability of light absorption is close to zero.

In this regard, in the absence of a sufficiently fast Brownian thermal rotation in disordered systems (with the initial disordered orientation of the molecules), various molecules absorb light with different probabilities, i.e. light selects molecules according to their orientation - photo selection. Molecules that absorbed light then enter into a photochemical reaction with a certain quantum yield and, thus, the initial disordered distribution of the molecules according to their spatial orientation is violated.

The result of the different probability of light absorption by variously oriented centers is the appearance during the reaction of the preferential orientation of both unreacted molecules of the starting material and the molecules of the product of the photochemical transformation and, as a result, the appearance of photoinduced optical anisotropy (dichroism of absorption and birefringence (DLF) Δn = no- ne) in an irradiated solid.

The molecular orientation order depends on the exposure energy, while the direction of the preferred molecular orientation is determined by the direction of the polarization vector and / or the direction of propagation of the activating radiation.

The method of passive photo selection allows one to use various irreversible or reversible (photochromic) monomolecular photochemical reactions for the artificial formation of orientationally ordered molecular structures (and, accordingly, anisotropy of optical properties) in a solid [V.A. Barachevsky, G.I. Pashkov, V.A. Tsekhomsky. Photochromism and its application // M .: "Chemistry", 280 p. (1977); Organic Photochromes, ed. A.V. Eltsova, L-d (1982); R.C. Bertelson, in: ʺPhotochromismʺ, ed. G.H. Brown; Wiley Interscience (1971), 853; G.H. Dorion, A.F. Weibe, in: hotPhotochromism - Optical and Photographic Applicationʺ, N.Y., Focal Press, (1970), 120; R.C. Bertelson, in: ʺPhotochromism: Techniques of Chemistryʺ, ed. G.H. Brown, N.Y .: Wiley Interscience, 3 (1971), 45; ʺOrganic Phorochromicsʺ, ed. by A.V. Eltsov, translaited from Russian by Y.E. Sviridov and translation, ed. by J. Whittall, Consultants Bureu, N.Y. 1990].

den photoanisotropen effect (Weigerteffekt) an farbstoffen 1 // Zeitschrift

wissenschaftliche photographie, photophysik und photochemie, Bd. 31, 153 (1932).], обнаружившего дихроичный эффект в более чем 450 (в основном красителях, введенных в коллодий и желатину) из 1700 различных обследованных им органических соединений.Light-induced optical anisotropy is a widespread physical phenomenon, as evidenced by the fundamental experimental work of Kondo (T. Kondo) [T. Kondo,

den photoanisotropen effect (Weigerteffekt) an farbstoffen 1 // Zeitschrift

wissenschaftliche photographie, photophysik und photochemie, Bd. 31, 153 (1932).], Which revealed a dichroic effect in more than 450 (mainly dyes introduced into collodion and gelatin) from 1700 different organic compounds examined by him.

This article is the closest in technical essence and practical implementation to the claimed in the present invention method for the artificial formation of picture-oriented ordered nano-, micro- and macromolecular structures in a solid, adopted as a prototype.

In the last two decades, research in the field of photoinduced optical anisotropy in condensed matter has become most widespread after one of the authors of the present invention discovered the effect of picture photo orientation of thermotropic and lyotropic liquid crystals on the surface of the PMF after irradiation with polarized or not even polarized, but directed radiation [see V.M. Kosenkov and others, 2nd All-Union Seminar "Optics of Liquid Crystals", Abstracts, Krasnoyarsk, September 17-21, 1990]. Abstracts of almost all patents (150) related to this area of application of polarization-sensitive materials published between 1990 and 2007 are given in [V.G. Chigrinov, V.M. Kozenkov, H.S. Kwok, Photoalignment of Liquid Crystalline Materials: Physics and Applications, 232 pp., Wiley, August 2008].

Photoinduced orientational ordering and optical anisotropy in such polarization-sensitive materials, like liquid crystals [V.G. Chigrinov, Liquid Crystal Devices. Physics an Applications, Artech House Boston - London, 1999], are defined as:

- order parameter S:

- dichroic ratio d:

- birefringence Δn:

и А11,

- показатели преломления п и оптические плотности А, измеряемые для компонент, ориентированных параллельно и перпендикулярно вектору поляризации активирующего света, соответственно.where, n11,

and A11,

- refractive indices n and optical densities A, measured for components oriented parallel and perpendicular to the polarization vector of the activating light, respectively.

In this case, the value of the order parameter S can vary from 0 (completely disordered structure) to 1 (fully ordered structure).

The magnitude of the phase delay δ is determined by the expression:

where: Δn and d are the birefringence and the thickness of the optically transparent

films, respectively; λ is the wavelength of the measuring light.

However, in reality, the maximum achievable values of the molecular order parameter S for the initially isotropic PSM formed on the basis of passive photochemical selection (reversible or irreversible photochemical reaction in polarized light) are quite small (usually less than 0.3). This is due to the fact that it is very sensitive to the chemical structure of photosensitive substances and the time (energy) of their exposure (Fig. 2, cr. 1, 2) and requires precise control of the irradiation mode.

In addition, the induced optical anisotropy decreases or completely disappears at a sufficiently high exposure energy, i.e. the molecular order depends critically on the energy exposure (Fig. 2, cr. 1, 1ʺ).

Moreover, as a rule, photo-induced anisotropy in these materials is thermally unstable and quickly disappears when heated.

A characteristic property of the method of forming orientationally ordered molecular nano-, micro-, and macrostructures with photoinduced anisotropy (for example, birefringence) in layers of all types of these photochemical materials is the partial reversibility of the process of forming optical anisotropy with the possibility of optical and / or thermal “erasure” and subsequent restoration of optical anisotropy with the same direction of the optical axis (see Fig. 2, curves 1 and 1 '1ʺ; 2 and 2', 2ʺ, respectively).

The reversibility of the photo-induced anisotropy process in a polarization-sensitive material (PCM), for example, allows the process of optical correction of the picture anisotropic nano-, micro- or macrostructure incorrectly recorded in the PCM layer. This simplifies the technological process of manufacturing such picture optically anisotropic structures.

However, a significant drawback of using such IFMs formed using photosensitive substances based on passive photochemical selection is their extremely limited reversibility. This can be seen from Fig. 2 (cr. 1ʺ), where it is shown that the form of kinetics of formation and the magnitude of optical anisotropy (for example, DLP) varies significantly with the cycles “optical guidance (cr. 1) - optical erasure (cr. 1 ') and optical recovery (cr. one)".

Thus, the disadvantages of the FTD method of forming picture-molecularly orientationally ordered nano-, micro- or macrostructures in photosensitive media based on passive photo-selection are:

1. Low optically formed orientational order (S <0.1-0.3),

2. The ambiguity of the dependence of the quantitative value of the formed orientational and optical anisotropy on the absorbed energy of photochemically active polarized radiation. This can be seen from the ones shown in Fig. 2 typical dependences of photoinduced DLP induction on exposure energy for photoanisotropic materials based on passive irreversible (cr. 1) and reversible (photochromic) (cr. 2) photochemical selection. During photolysis in such systems, the induced anisotropy passing through a maximum during long-term irradiation can tend to either some photostationary value Δn, as for photochromic media (cr. 2 ÷ 2ʺ), or to zero (cr. 1 ÷ 1ʺ), as for irreversible photochemical processes. In the latter case, with prolonged exposure, an isotropic layer of the photoproduct is formed.

3. Limited reversibility. It is due to a finite number of photochemically sensitive molecules in the medium for irreversible processes or photodegradation of photochromic molecules.

4. The variability of the shape of the absorption spectra and chemical properties in the initial and ordered states. For example, in fig. Figure 3 shows the absorption spectrum of a photosensitive substance from the class of phenoxynaphthacinquinones in a polymer matrix before (cr. 1) and after (cr. 2 and 3) irradiation with actinic radiation [V.M. Kosenkov et al., Vestnik MGOU, series Physics and Mathematics, 4, 115-122 (2011)].

In addition, the POTF method of forming picture-molecularly orientationally ordered nano-, micro-, or macrostructures in the PSM based on passive photo-selection has several other disadvantages, which are:

5. The absence of a threshold effect on the power density of the activating radiation during the formation of locally oriented molecular nano- and microstructures directly in the volume of the photoanisotropic PSM. For this reason, it is impossible to use single-photon photochemical reactions to form local spatially modulated orientational molecular nano- or microstructures in the bulk of the layer.

6. The presence of only one (disordered isotropic) thermodynamically stable state.

7. Lack of methods for fixing the orientational order (optical anisotropy) formed in the layer. This leads to its destruction when exposed to extraneous or read radiation absorbed by them. In addition, anisotropy induced by polarized light (orientational ordering) can relax as a result of rotational thermal diffusion of photoselected molecules and their photoproducts in the dark or as a result of chemical reversal for photochromic substances.

Disclosure of invention

The objective of the present invention is to develop a method for the formation of new polarization-sensitive solid-state photoanisotropic materials based on a previously unknown effect in non-luminescent or weakly luminescent, photochemically stable, anisotropically absorbing (dichroic) substances (PCF), capable of reversibly forming and / or transforming in its volume and on the surface, spatially modulated, ordered molecular functional nano-, micro- or macro-picture structures in accordance and with the spatial distribution of the polarization and energy characteristics of one- or two-photon absorbed activating radiation.

The problem is solved due to the fact that a method has been created for forming a tape-sensitive material capable of forming a polarizing optical element in its volume and surface in the form of a spatially modulated ordered anisotropic molecular structure by irradiation with polarized or non-polarized but directed radiation the specified polarization-sensitive material absorbed by the polarization-sensitive component that is part of this mat rial, characterized in that as a polarization-sensitive component responsible for the formation of an anisotropic optical element in it, instead of an anisotropic photochemically sensitive substance, it is proposed to use a photochemically stable, anisotropic one- or two-photon absorbing, non-luminescent or weakly luminescent substance, which is part of the polarization -sensitive material, for example, in the form of components uniformly distributed at the molecular level in a uniform and isotropic low - or a high molecular weight matrix, wherein the indicated spatially modulated ordered ordered anisotropic molecular structure is formed in which the orientational order and anisotropy of the optical properties (directions of the optical axis and absorption dichroism, birefringence, and phase delay) and other angular dependences of the physicochemical properties directly correlate with spatial distribution of a linear, elliptical or circular polarization state, energy characteristics and By propagation of the activation radiation, it can be reversibly formed and / or converted both in the case of one- and two-photon (through the real or virtual intermediate level) absorption of the proposed photochemically stable component of the polarization-sensitive material, which also includes other low molecular weight additives whose vibrational levels of the ground state are close to or in resonance with the corresponding vibrational levels of the PCF molecules Providing an effective process of anisotropy of intermolecular vibrational cross-relaxation of the energy of the absorbed quantum upon irradiation of the PMF and, in addition, the regulatory film-forming, viscous, anisotropic-optical, physicochemical and mechanical properties of the formed material, depending on its specific application.

Another subject of the invention is a method of forming a polarization-sensitive material capable of forming a polarization-optical element in its volume and on the surface, which, when irradiated with linearly, elliptically or circularly polarized or non-polarized radiation absorbed by a polarization-sensitive photochemically stable component of the material, exhibits anisotropy of its optical properties (absorption dichroism, birefringence and phase delay), leaving the spectral shape unchanged the absorption line of the photochemically stable component, regardless of the amount of absorbed energy, but always “clearing” for the polarization component, parallel to the polarization of the activating radiation and “darkening” for the orthogonal component.

Moreover, some possible changes in the absorption spectra are due to the manifestation of changes in the Van der Waals forces of intermolecular interaction when polarized or directed radiation affects polarization-sensitive material [Dubinin N.V., Yudin S.G., Blinov L.M. The quadratic Stark effect and the orientation of molecules in polar Langmuir multilayers // Optics and Spectroscopy, 1985, 59 (1), 92].

This is especially evident in the effect of the so-called “non-photochemical spectral dip” in media with inhomogeneously broadened absorption spectra at helium temperatures [E.I. Alshits, B.M. Kharlamov, Z.I. Persons, On the question of non-photochemical burning of spectral dips // Journal. Adj Srektrosk., XLV, 559 (1986)].

Another object of the present invention is a polarization-sensitive material in which the polarization-sensitive component is made of various classes of photochemically stable, anisotropically absorbing (dichroic) substances with absorption bands between 150 nm and 2000 nm in the UV, visible and / or IR spectral regions .

Moreover, classes of such anisotropic substances may include, for example:

- mono-, dis-, tris-, polyazo dyes, metal-complex or complex-forming azo dyes [see, for example, A.V. Ivashchenko, Dichroic azo dyes for liquid crystal displays. Chem. prom., Aniline-paint prom., NIITEKHIM, Cherkasy, 1987];

- anthraquinone dyes, mono- and polyoxy anthraquinones [see, for example, A.V. Ivashchenko, Dichroic anthraquinones for liquid crystal displays. Chem. prom., Aniline-paint prom., NIITEKHIM, Cherkasy, 1989];

- azo dyes with polar hydrophilic "heads" and long hydrocarbon lipophilic "tails" for Langmuir-Blodgett films

- mordant or acid azo dyes [B.I. Stepanov, Introduction to Chemistry and Technology of Organic Dyes, ed. "Chemistry", M. 1971]; as well as many other photochemically stable substances from the classes of anisotropic (dichroic) substances exhibiting the property of photoinduced optical anisotropy in solid-state layers with the participation of low molecular weight additives, the vibrational levels of the ground state of which are close to or in resonance with the corresponding vibrational levels of molecules of a photochemically stable substance, providing an efficient process anisotropy of intermolecular vibrational cross-relaxation of the energy of the absorbed quantum. In most cases, such molecular additives in relation to optically excited molecules can be the same, but not excited, anisotropic molecules located in the nearest neighbors of the former.

A polarization-sensitive material can (but not necessarily) be, for example, an initially isotropic, solid disordered polymer solution (matrix) with photochemically stable anisotropically absorbing, non-luminescent or weakly luminescent substances uniformly distributed in it at the molecular level.

In some cases, a polymer binder may be absent, and the glassy, isotropic unirradiated layer of a photochemically stable low or high molecular weight substance with various technological or other low molecular weight additives introduced into it (if necessary) at the molecular level acts as an isotropic matrix in this case, providing in addition, in particular, the effect of photoinduced optical anisotropy in the solid state of the PMF.

Photochemically stable anisotropic chromophores, for example, derivatives of azo dyes, can be introduced directly into the main chain of the polymer macromolecule or covalently linked to it in the side group. Including by means of a conformationally mobile, for example, an alkyl spacer, facilitating the process of photoinduced orientational ordering under the influence of polarized or not polarized, but directed radiation. Moreover, similar polymer structures can contain fragments that give them the properties of thermotropic liquid crystals in a certain temperature range or lyotropic liquid crystals in a certain concentration range.

Low or high molecular weight PCBs can themselves exhibit thermotropic liquid crystal properties in a certain temperature range or lyotropic liquid crystal properties in a certain concentration range of a solvent.

In addition, FHSV can be made in the form of bi- or multifunctional substances such as monomers or oligomers, which can be additionally introduced, for example, luminescent or photochromic fragments, as well as one or more fragments capable of dimerizing or forming under the action of photochemically active the relation to them of radiation (not absorbed by FHSW) is a spatial polymer network.

The above substances can independently form solid layers or can be added as additives to polymer matrices transparent to the radiation that activates them, and PCM solid layers based on them can be obtained by watering, centrifuging, or dipping a polymer solution followed by evaporation of the solvent. They can also be obtained by photo- or thermopolymerization of monomeric or oligomeric compositions with the addition of anisotropic absorbing substances (PCF), made without a polymer matrix in the form of Langmuir-Blodgett films or amorphous layers by centrifugation, dipping, printing or thermal spraying in vacuum.

To give the given volumetric forms to condensed media based on PCFB dissolved in monomeric or oligomeric matrices, the latter can be cured using heat or some other radiation with a wavelength outside the spectral region of the optical radiation absorbed by these dichroic substances.

As high molecular weight (polymer) matrices, photochemically stable or photosensitive polymers transparent in the spectral region of single and / or two-photon absorption of PCBs can be used. They serve to maintain or obtain the required shape and provide the necessary stiffness of the MFM. It is desirable that the vibrational levels of the ground electronic state of the polymer matrix are in resonance with the corresponding levels of dichroic PCBs, which are used as rod-shaped molecules with a pronounced anisotropy of the absorption oscillator at a wavelength of one or two photon absorption. This ensures a higher photostimulated degree of molecular orientational ordering both of the PCFB itself, and of polymer fragments and other molecules contained in the PCM and located in the immediate vicinity of the PCFB.

Such polymers can be well-known derivatives: polyimide, polyethylene, polystyrene, cellulose acetate, polycarbonate, polyesters, polyacrylonitriles, polyvinyl alcohol, polymethyl methacrylate, polyvinyl ethyl, polyvinyl butyral, polybutyl methacrylate, phenol formaldehyde resins, other polymers, polymers.

As low molecular weight additives, it is desirable to use photochemically stable anisotropic substances, transparent in the spectral region of absorption of PCBs, whose vibrational levels in the ground unexcited electronic state are in resonance or close to the corresponding electronic levels of PCBB.

To improve their orientational ordering, these additives can also be chemically bonded directly to the anisotropic absorbing substances of PCFB in the form of bi- or multifunctional monomeric or oligomeric substances.

All these substances should preferably have at least two substituents of the type —OH, —NH2, COOH, NHR (where R can be, for example, -

-С6Н4СН3, - (СН3) 2, СОСН3) and others, capable of forming at least two specific intermolecular donor-acceptor or hydrogen bonds between this substance and the macromolecule of the polymer matrix or between the dichroic molecules themselves with the formation of a spatial ordered network.

The proposed polarization-sensitive materials, in addition to the initial thermodynamically stable isotropic state with a random spatial orientation distribution of anisotropic photochemically stable molecules in it, provide, when they absorb actinic radiation, two more types of quasi-thermodynamically stable states with the orientation of the absorbing molecular oscillators in a plane perpendicular to the polarizing radiation vector circularly polarized along the propagation direction annogo or unpolarized radiation.

The inventive IFMs exhibit the effect of the formation of orientational molecular ordering in the two-photon cascade or cooperative absorption mode, which makes it possible, for example, to form a pattern of the distribution of the direction of the optical axis or the DLP along the depth of the volume IFM. Such structures cannot be obtained when forming in single-photon exposure mode.

Another option for the formation of orientational molecular ordering in the proposed materials in accordance with the present invention is a sensitized orientational ordering.

The advantages of polarization-sensitive photoanisotropic materials based on non-luminescent or weakly luminescent, photochemically stable, anisotropically absorbing (dichroic) substances are:

1. high value of the order parameter induced by the activating radiation (S ~ 0.8 ÷ 0.9),

2. high value of photoinduced DLP induced by activating radiation

(~ 0.2 ÷ 0.5),

3. the unambiguity of the dependence of the quantitative value of the formed orientation and optical anisotropy on the absorbed energy of the active polarized radiation,

4. the presence of three (one isotropic and two anisotropic) thermodynamically stable states,

5. the possibility of dark self-organization,

6. low dark relaxation (at least more than 25 years),

7. two threshold effects on the power density of the activating radiation,

8. almost unlimited reversibility and the possibility of adaptive reorientation,

9. High invariance of absorption spectra in the initial and oriented states.

The subject of the present invention is also the use of the claimed polarization-sensitive material:

- as a chemical and / or structural material in phototechnology for the production of a variety of pictorial two- and / or three-dimensional polarization-optical elements and devices of nano-, micro- and macro-optoelectronic equipment, as well as in instrumentation using such polarization-optical elements. The specified polarization-sensitive material can be used in the manufacture of optical anisotropic fiber and integrated optics such as anisotropic photonic crystals, bulk diffraction gratings, radiation input-output devices, lenses, polarization-selective light beam dividers, etc., in phototechnology for the production of photothermally stable adaptive internal thin-film phase plates and polaroids, as well as photo-orientants of liquid crystals.

- as an optically formed picture highly oriented matrix for special low molecular weight active additives exhibiting high selectivity and efficiency of thermo-, photo- or simply chemical processes occurring in them, depending on the degree of their ordering in the highly-oriented matrix.

- as polarization-sensitive photoanisotropic storage media in technical means of recording, storing, processing and displaying information, including in systems of two - (2D) and / or three - (3D) dimensional optical memory WORM and VR - type, in polarization computer, including conoscopic, holography, in means of protection against counterfeiting and identification of securities and other products for household and technical purposes, when creating new instruments and devices of measuring equipment for the study of mechanical stresses in various cing product photoelasticity method, etc.

BRIEF DESCRIPTION OF THE DRAWINGS

In FIG. one

optical methods for the formation of oriented molecular structures are presented:

a) photo orientation of photochemically stable anisotropic molecules,

b) phase changes (Prior Art),

c) magneto-optics (Prior Art),

d) passive photochemical angular selection (Weigert effect) (Prior Art).

In FIG. 2

the reversibility of the guidance process (cr. 1, 2 and 3), optical ʺ erasure ʺ (cr. 1 ′, 2 ’and 3)) and repeated pointing (cr. 1ʺ, 2ʺ and 3ʺ) of optical anisotropy in media based on photochemically sensitive (cr . 1, 2,) and photochemically stable (cr. 3) substances.

In FIG. 3

) и перпендикулярно (

) вектору поляризации Еехр активирующего излучения, соответственно.a typical form of absorption spectra of polarization-sensitive photoanisotropic media based on passive photochemical selection (Prior Art) (a) and photoorientation of photochemically stable anisotropic molecules (b) in the initial isotropic (cr. 1) and photoinduced anisotropic (cr. 2, 3) states is presented with the orientation of the polarization vector Emeas of the measuring radiation in parallel (

) and perpendicular (

) polarization vector exp of the activating radiation, respectively.

In FIG. four

The scheme of molecular reorientation in a polarization-sensitive material based on photochemically stable substances is presented:

- orientation "self-organization" of the unit cell (solvate) upon absorption of one quantum of optical radiation (a-c);

- reorientation with multiple absorption (d).

In FIG. 5 a-s

a schematic representation of the initial disordered (a) and two highly oriented (b and c), thermally stable states in amorphous layers of PCF is presented.

In FIG. 6a

a schematic representation of the principles of one- and two-photon formation of specified spatial configurations of anisotropic dielectric optical properties in the scope of the proposed polarization-sensitive materials.

In FIG. 7

A typical view of the kinetic curves of guidance, erasure, and dark relaxation of optical anisotropy δ in photoanisotropic media based on photochemically stable, anisotropic absorbing substances is presented. The arrows ↑ (up) and ↓ (down) denote the moments of turning on and off photoactivating radiation. Symbols A → B and A ← B denote moments when the polarization state of the activating radiation is switched to orthogonal. The signs "0", "1" and "-1" denote the initial and photoinduced quasithermodynamically stable orientational states, respectively.

In FIG. 8

The dependence of the photosensitivity of amorphous layers based on PCFs on the power density of activating radiation is shown.

In FIG. 9

two different images are shown reproduced in crossed polarizers from a “hologram” recorded by incoherent, non-monochrome radiation on a PCF based on PCF.

The essence of the invention, which consists in the description of features, technical elements and its advantages, is illustrated in some specific, but not limiting, claimed technical solutions, examples of the invention with reference to the accompanying drawings, in which:

SUMMARY OF THE INVENTION

Before describing a number of options and embodiments of the present invention, we present the terms used in this description.

By the term “anisotropic absorbing substance” is meant a compound with anisotropic geometry, for example, a rod or a disk, which exhibits absorption properties with different values along different axes. For example, dichroic lyotropic and thermotropic liquid crystalline compounds are anisotropic absorbing substances.

The term ʺ photochemically active (photochemically sensitive) substance means an anisotropic absorbing molecule that exhibits photo-induced optical anisotropy in the solid state or in a solid-state matrix as a result of a reversible or irreversible (photochromic) mono- or bimolecular photochemical reaction with a quantum yield of about 0.1 ÷ 1 as a result of which at least the absorption spectrum changes.

The term “passive photochemical selection method” means that an orientational molecular structure with photoinduced optical anisotropy in a photosensitive solid-state optical medium based on photochemically active (photochemically sensitive) substances occurs as a result of irreversible or reversible (photochromic) photochemical reactions in polarized light (Weigert effect (Weigert effect)).

The term “photochemically stable, anisotropically absorbing (dichroic), non-luminescent substances” (PCFS) means that a molecule that exhibits photo-induced optical anisotropy in the solid state or in a solid-state matrix without participating in any reversible or irreversible (photochromic) photochemical reaction without changes forms of spectral absorption bands in the process of anisotropy formation.

In the present invention, ʺ Х Х ʺ ʺ ʺ is understood to mean substances in which, when absorbing the energy of the orienting radiation, they do not produce any photochemical reactions accompanied by spectral changes. Of course, this definition is relative and depends on the specific conditions of use and the properties of polarization-sensitive photoanisotropic materials based on PCF. In the solid phase, the quantum yield associated with photochemical reactions in such substances is about 10 ^-1 ÷ 10 ^-8 or less. Moreover, during the time of optical formation in such an anisotropy layer, photochemical changes can be neglected.

The term “photostable molecule” further means that the quantum efficiency associated with the photochemical reactivity of a molecule is practically zero.

The term "polarization-sensitive material" (FMS), means that, as a rule, an initially isotropic solid-state medium based on "photochemically active (photochemically sensitive)", "photochemically stable anisotropically absorbing" or "photostable molecules" exhibits photo-induced anisotropy (dichroism of absorption and / or birefringence) in the solid state upon absorption of polarized or non-polarized but directed radiation.

Until now, only one (photochemical) FTF mechanism was well known for the long-lived effect of photoinduced optical anisotropy (dichroism of absorption and / or birefringence) in solid-state media based on PCM with “frozen” Brownian rotational molecular mobility. Optical anisotropy in such IFs is the result of passive photochemical spatially angular selection resulting from irreversible or reversible (photochromic) photochemical mono- or bimolecular photochemical reactions (Weigert effect) (Fig. 1d).

The mechanism of photoinduced optical anisotropy in the PMIs of the present invention based on photochemically stable, anisotropically absorbing (dichroic), non-luminescent or weakly luminescent substances (PCF) was previously unknown.

According to the authors of the present invention, it is based on a previously unknown photophysical mechanism of active molecular ordering and reorientation of such substances during one- or two-photon absorption of linearly, elliptically or circularly polarized or non-polarized, but directed optical radiation (Fig. 1a).

In this case, the maximum achievable orientational order parameter S in such IFMs based on pure PCFs without a polymer matrix and even in some cases in PCFW layers in a polymer matrix reaches S> 0.8-0.9, which significantly exceeds the value of the PCM order parameter based on photochemical angular selection ( S <0.3).

The authors of the present invention found that the orientational order parameter for such IFM reaches its maximum value asymptotically with increasing radiation dose (Fig. 2b, cr. 3,), even after optical “erasure” (3 ') and re-guidance (3ʺ), until melting point (~ 150-250 ° C), depending on the component composition of the PM.

FIG. 4a-d schematically illustrates the proposed process of photoinduced ordering and reorientation of molecules in the PMM based on photochemically stable, anisotropically absorbing (dichroic), non-luminescent substances, dissolved in, for example, a polymer matrix or without it.

[

С.J.F., Theory of Electric Polarization, Elsever, Amcterdam, 1952; 2^nd ed. Revised by Van Belle, О.C. Bordewijk, P. and Rip, A., Vol. 1 and 2, Elsever, Amsterdam, 1973]) в исходном состоянии (фиг. 4а) среда 40 изотропна и ее можно характеризовать множеством случайно ориентированных сольватов 41 диаметром от нескольких десятков до сотен А°, каждый из которых включает невозбужденную фотохимически стабильную дихроично поглощающую молекулу ФХСВ 42, окруженную, в общем случае, не поглощающими активирующее излучение фрагментами макромолекулярной матрицы, другими низкомолекулярными добавками или, например, молекулами того же вещества) 43. Такой сольват 41 можно охарактеризовать дипольным моментом перехода μge дихроичной молекулы 42 (однозначно связанным с ее постоянным или наведенным электрическим дипольным моментом), ориентированным под углом θо по отношению к некоторой оси координат Y. Квазистатическое (медленно, за десятки или сотни минут изменяющееся во времени за счет тепловых движений) поле Onsager (field Onsager) Ero ~10⁷÷10⁸ V/cm создается окружающими ФХСВ молекулами 43 и молекулой 42. Векторы μge и Ero первоначально (до облучения) ориентированны между собой под некоторым углом ϕо, статистическая величина которого во многом определяется предысторией приготовления образца 40.In accordance with Onsager-

[

C. JF, Theory of Electric Polarization, Elsever, Amcterdam, 1952; 2 ^nd ed. Revised by Van Belle, O.C. Bordewijk, P. and Rip, A., Vol. 1 and 2, Elsever, Amsterdam, 1973]) in the initial state (Fig. 4a), medium 40 is isotropic and can be characterized by many randomly oriented solvates 41 with diameters from several tens to hundreds of A °, each of which includes an unexcited photochemically stable dichroically absorbing molecule FHSW 42, surrounded, in the general case, by fragments of the macromolecular matrix not absorbing the activating radiation, other low molecular weight additives, or, for example, molecules of the same substance) 43. Such solvate 41 can be characterized by the dipole moment the transition volume μge of the dichroic molecule 42 (uniquely related to its constant or induced electric dipole moment) oriented at an angle θо with respect to some coordinate axis Y. Quasistatic (slowly, tens or hundreds of minutes changing in time due to thermal motions) Onsager field (field Onsager) Ero ~ ÷ July ¹⁰ August ¹⁰ V / cm is created FHSV surrounding molecules 43 and 42. vectors μge molecule and Ero initially (prior to irradiation) are oriented to each other at an angle φo, the statistical value of which is largely determined by pre ystoriey sample preparation 40.

Proposed formation mechanism

the photoinduced ordered molecular structure in such materials based on PCFB 40 (Fig. 4a-d) takes place as the process of active photo-reorientation and photoordering of PCBF molecules (42) and their immediate environment (43) in the nano-scale region 41) in the internal local electric reactive medium field Er during cross-vibrational relaxation of energy absorbed by a molecule of photochemically inactive photons of polarized Ehν, or unpolarized but directed radiation (Fig. 4b ÷ 4d).

In accordance with equation (2), when such a medium 40 is irradiated with many randomly oriented molecules 42 linearly polarized, for example, in the direction of the Y axis, by the radiation Ehν, its resonance absorption by the anisotropic molecule 42 occurs with a maximum probability when the angle θо is close to zero.

Moreover, in accordance with the Frank-Condon principle, the orientational molecular rearrangement of solvate 41 does not occur at the moment of transition of the molecule 42 to the excited state (Fig. 4a).

The mechanism underlying them combines three processes:

- “passive” onPhoton-mode fomingʺ photo-selection associated with absorption (formula (2)) of spatially oriented molecules 42 in a certain way with a dipole transition moment μge oriented at an angle θо with respect to the activating radiation Ehν, and the formation of an anisotropic ensemble of spatially inhomogeneous oriented excited molecules (Fig. 4a);

- “active”, due to photoordering of excited photo-selected molecules

chromophore 42 and their nearest neighbors 41, 43 under the influence of the Onsager field Ero (x, y), initially oriented at an angle ϕ0 relative to molecule 42, with their relative orientational rearrangement to positions 44 and 41 with parameters ϕ, θ ≠ ϕ0 , θ0 <90 ° and Er (x, y) ≠ Ero (x, y) (Fig. 4b);

- “statistical” photo-reorientation and ordering of photo-selected chromophore molecules 42 → 44 → 45 and their nearest neighbors 43 → 46 and 41 → 47 as a result of a single (for a picosecond pulse) or multiple (for continuous radiation) absorption and non-radiative energy deactivation quanta of activating studies on Wednesday (Fig. 4c) with the transition to the photo-stationary state 42 → 44 → 45 → 49, 43 → 46 → 50, 41 → 47 → 48 and ϕn → 0 °, θn → 90 ° and Ero (x, y ) → Ern (x, y) (Fig. 4d).

In this case, the role of the polarization of the activating radiation (or the direction of its propagation for circular or non-polarized but directed radiation), as in the “passive” method of photochemical selection, consists in the formation of an anisotropic ensemble of excited molecules of photochemically stable chromophores capable of subsequent orientational rearrangement and rotation by a certain angle Δθ from the initial spatial orientation θ0. For PCFS in a polymer matrix transparent to activating radiation, the Δθ value is, as a rule, small and amounts to fractions of a degree for a single absorption of light quanta of low-power radiation.

The direction and magnitude of such a change in the angle θ at each absorption event are random.

The “quantum yield" of such a rearrangement of the excited chromophore and its surroundings after deactivation no longer depends on the polarization of light, but is determined by the magnitude of the dissipated energy of the light quantum, the history of the formation of the nanostructure of the medium and the density of the molecular packing in the medium, the mechanism of intermolecular cross-vibrational relaxation, and constant dipole moments of the molecules and the polarizability of the elements of the solvate complex, as well as the presence of specific intermolecular interactions in it and the ambient temperature.

In contrast to photochemically active molecules, after absorption of a photon, the PCB molecules do not undergo chemical transformations and do not luminesce. As a result, they are able to change their orientation and, as a rule, during prolonged continuous irradiation during repeated repetition of such a process (in the case of continuous irradiation for several minutes) accumulate in the orientation of the dipole transition moments μge, which is unfavorable for the absorption of light in this spectral region, t .e. with θ → 90 °. The molecular ordering and orientation thus induced by optical radiation in the general case is accompanied by anisotropic changes in the optical (absorption dichroism and DLP) and other physical (e.g., mechanical, electrical, etc.) properties.

In addition, this process is accompanied by an increase in the solvate size 48 (47, 41) due to the involvement of partially reoriented and ordered peripheral molecules in its composition. An increase in the volume of solvate 48 (47, 41) and the mutual ordering of the molecules included in its composition lead to a significant slowdown of the Brownian thermal disordering of photoinduced anisotropy in the medium after the activation radiation is turned off. This is due to the increasing role of both steric obstacles and the anisotropy of the forces of intermolecular Van der Waals interactions in the solvate. This effect is not observed or is much less important in the case of passive photo-selection in media based on substances with high quantum yields of photochemical reactions.

The result of a long-lived orientational ordering and, accordingly, optical anisotropy induced in our FFM based on PFSS, the result of this experiment is largely related to the anisotropy of intermolecular energy transfer of electronic excitation through excited vibronic levels of the ground state. This process of vibrational cross-relaxation is resonant and orientational in nature. The effect of cross-vibrational relaxation is most pronounced when the vibrational levels of the ground state of PCFB molecules and solvate molecules (fragments of the polymer matrix and low molecular weight additives) are close or identical. An example is amorphous homogeneous in composition, for example, sprayed layers of some azo dyes or Langmuir-Blodgett films, when the photoinduced anisotropy effect (orientational order, dichoric ratio, and DLP) can reach maximum values comparable with LC structures.

In this case, the intrasolvation ordering tends to small values ϕn → 0 °, and θn → 90 °.

(Fig. 4d). In this case, the limit values of the photoinduced orientation

ordering (as in oriented layers of liquid crystals) S ~ 0.8 or more and, consequently, high values of optical anisotropy (Δn ~ 0.4 or more) even under prolonged exposure to low-power (of the order of units mW / cm ² ) radiation sources.

On the other hand, the absence of resonance in the vibrational spectra of the light-absorbing substance and solvate molecules and strong steric hindrances, for example, for the same PCBs in the polymer matrix, lead to small θn values and a significant decrease in the maximum attainable optical anisotropy values.

The polarization-sensitive materials proposed in this application based on this effect with photochemically stable anisotropic absorbing substances have a number of features and advantages compared to known materials based on photochemically sensitive substances.

The typical kinetics of optical anisotropy induction in these media is significantly

differs from a similar dependence for media based on passive angular photo-selection (Fig. 2, cr. 1 and 2). First of all, in the case of PCFs based on PCF during their irradiation

With polarized radiation, optical anisotropy (e.g., phase delay δ) reaches

maximum value asymptotically, and in the initial section, its fast

increase followed by a significant slowdown (Fig. 2, cr. 3). In applied

applications of such materials, this removes the question of the uniqueness of the dependence of the quantity

photoinduced optical anisotropy of the energy of absorbed radiation.

In PCM based on photochemically active substances, where during their exposure

всегда меньше (как на фиг. 3а, кр. 2, 3) (или больше) исходной оптической плотности Ао (рис. 3а). В предлагаемых ПЧМ на основе ФХСВ, как видно из рис. 3b, в процессе облучения всегда имеет место А

> Ао > А11, что также указывает на ориентационный механизм формирования оптической анизотропии в них.polarized radiation, both components of the optical density in the absorption band of the activating radiation A11 and A

always less (as in Fig. 3a, cr. 2, 3) (or more) of the initial optical density Ao (Fig. 3a). In the proposed FSMs based on FHSV, as can be seen from Fig. 3b, A always occurs during irradiation

>Ao> A11, which also indicates the orientational mechanism of the formation of optical anisotropy in them.

In the absence of a polymer matrix in such amorphous, initially isotropic films, the maximum attainable values of photoinduced orientational ordering and optical anisotropy are close to the corresponding values in liquid crystals. Thus, the orientational order parameter S and birefringence Δn can reach values up to

0.8 and 0.4 or more, depending on the anisotropic properties of these chromophores.

Indeed, as can be seen in Fig. 5a, in the initial thermodynamically stable state

amorphous layers of PCBs obtained, for example, by centrifugation, are isotropic and there is no orientational molecular ordering in them.

When the polarized radiation is exposed to these layers for a long time, the PCFB molecules are oriented so that their transition dipole moments at the activation wavelength μge are located mainly in the plane (ZY in Fig. 5b) perpendicular to the electric field vector of the light wave (X axis in Fig. 5b), without preferential direction

orientation in this plane (Z-Y plane in FIG. 5b).

A similar character of orientation takes place when exposed to circularly polarized

or directional, non-polarized radiation. However, the predominant axis

In this case, the photoinduced orientation of the PCFB molecules coincides with the direction of propagation of the radiation absorbed by the medium (Z axis in Fig. 5c).

From the absorption spectra in Fig. 3b, it is also seen that during the irradiation of films based on PCFB with polarized light, the shape of the absorption spectra for both components practically does not

is changing. Small spectral changes are associated with the formation of an ordered orientational structure in the layer and changes in the anisotropic intermolecular forces, for example,

Van der Waals forces of interaction. The cyclic “guidance-erasure” of photoinduced orientational ordering (optical anisotropy) (Fig. 2, curves 3, 3 'and 3ʺ) in such layers is limited only by photodegradation of the PCFW, the quantum yield of which, for example, for an azo dye (1) (see Table ) does not exceed 10 ^-5.

In accordance with the invention, the formation of orientational molecular

ordering in the FSMF-based FSMs described above can be performed both in the single-photon (hv) mode of absorption of activating radiation (Fig. 6a), and in the mode

real two-photon cascade (hv1 + hvv1) (Fig. 6b) or virtual cooperative (hv0v + hvv1) (Fig. 6c).

Cascade mode, in the general case, is carried out using two independent sources

radiation (Fig. 6b) (with different wavelengths λ1 and λ2), and, like single-photon, is based

on real sequential absorption of light quanta hv1 and hv2 first from the main E0, and then

from excited E1 singlet or triplet levels (Fig. 6b).

In a cooperative two-photon mode (Fig. 6c), in the general case also carried out with

using two independent sources with different wavelengths λ3 and λ4, the energies of the light quanta of each of them hv0v and hvv1 are such that they do not lead to any changes in the medium. However, if the sum of the energies of these two quanta is in resonance with a certain frequency

single-photon absorption of an anisotropic center with a quantum energy hv = Е1-Е0, the latter can

go to the excited state E1 through the virtual level Ev. As a result in the process

nonradiative energy degradation of two absorbed light quanta occurs

Orientational restructuring and ordering of both the center itself and its immediate environment.

Direction of propagation of radiation of two independent sources at two-photon

the formation of orientationally ordered molecular structures in media based on PCF

can be both collinear, and at an angle to each other. In the first case

their polarization vectors must be parallel. In the second case, the polarization vectors should be mainly perpendicular to the plane defined by their directions

distribution. The most acceptable two-photon cooperative process with one linearly or circularly polarized beam in a collinear mode. The efficiency of two-photon recording with different generation frequencies with spaced apart propagation directions of the beams deteriorates when using circularly polarized or non-polarized radiation.

Another option for the formation of orientational molecular ordering in

the proposed environments in accordance with the present invention is sensitized

orientational ordering. In this case, anisotropically absorbing, photochemically stable, and luminescent substances are used as a one- or two-photon absorber. They carry out anisotropic energy transfer of the photon absorbed by them to a photochemically stable non-luminescent and non-absorbing anisotropic substance of this initial radiation. It, in turn, together with the solvate shell undergoes orientational restructuring as a result of a nonradiative transition to the ground state.

In FIG. Figure 7 shows a typical kinetic curve for the guidance, erasure, and dark relaxation of optical anisotropy (phase delay) δ in an FSM based on PCF without matrix. As seen in FIG. 7, in the initial thermodynamically stable state, the amorphous layer is isotropic and there is no orientational molecular ordering in it, as shown in FIG. 5a. Such a state can be interpreted as a state corresponding to a logical zero “0” from the point of view of the applicability of such a frequency converter in an optical memory system. At short irradiation times (small doses of absorbed energy (small number of absorbed quanta)) (eq. 1), switching off the activating radiation leads to a rapid decay of the induced optical anisotropy due to Brownian rotational diffusion. This process of dark relaxation in the initial section has only a dynamic component (cr. 1 '). With an increase in the dose of absorbed energy, along with the dynamic component, a quasistatic component also appears (cr. 2 '). Its share grows up to a complete stop of the relaxation process (cr. 3 ') near exposures corresponding to saturation of orientational ordering. Further irradiation of the layer by polarized radiation leads to a certain photostationary value of the phase delay δphst.

Subsequent shutdown of the activating radiation leads even to some further

molecular self-ordering (cr. 4 ') with the achievement of a new, more ordered state with the value δdarkst> δphst. The rate of such anomalous dark relaxation "upward" increases with heating of the layer (cr. 5 '). This photostimulated dark state δdarkst can be interpreted as a new quasithermodynamically stable state of the medium corresponding to logical unit “1”. It is stable up to temperatures close to the melting point or thermal degradation of PCF. However, repeated irradiation of the layer with the same source with the same polarization is accompanied by a decrease in δdarkst to the previous photostationary value δphst (edge 6). But it is again accompanied by an abnormal upward relaxation when it is again turned off (cr. 7 ').

Under these conditions, reversing the short-time polarization of the activating radiation to orthogonal (A → B) leads to a partial “erasure” of the induced birefringence (curve 8), but its shutdown is accompanied by a dark restoration of the previously induced value (curve 9 '). Repeated, longer irradiation of the film by radiation with orthogonal polarization (A → B) (curve 10) again leads to a decrease in the DLP. Further irradiation can lead to the formation of the same highly oriented state, but with the opposite sign. By analogy with the previous one, it can be represented as yet another quasithermodynamically stable state corresponding to the logical unit “-1”.

It should be noted that the effect of dark relaxation “upward” is observed even before reaching the photostationary state δphst. It is observed immediately after the density of the energy of the activating radiation absorbed by the layer reaches a critical value at which the dark relaxation of the induced anisotropy stops, as shown in cr. 3 '. Such an effect of dark self-amplification is shown schematically in cr. eleven'. It has been experimentally observed many times in many environments based on FHSV.

Thus, the proposed polarization sensitive materials (FFM), in addition to the initial thermodynamically stable isotropic state with a random spatial orientational distribution of anisotropic photochemically stable molecules in them (Fig. 5a), provide 2 more types of sets of quasithermodynamically stable states, schematically shown in Fig. 5:

- anisotropic states with the orientation of the absorbing molecular oscillators μge in

a plane perpendicular to the polarization vector of the activating radiation (Fig. 5b) and

- anisotropic states with the orientation of the absorbing molecular oscillators μge along

directions of propagation of circularly polarized or non-polarized radiation (Fig. 5c).

The specific angular orientation of these optically formed ordered molecular

structures is determined by the angular orientation of the polarization vector and the direction of propagation of the activating radiation in the medium.

Due to the presence of reverse dark relaxation in the FMS based on FHSV (Fig. 7, cr. 1 'and 2'), they

, определяемое в основном величиной внутренней вязкости среды η и окружающей температуры t° меньше времени

между последовательными актами поглощения квантов света одной и той же дихроичной молекулой при воздействии на среду непрерывным источником излучения.inherent threshold effect on the minimum power density of the activating radiation of the order of tens of μW / cm ² (Fig. 8). The threshold power value decreases with increasing ambient temperature. The action of activating radiation with such and a lower density does not lead to the formation of orientationally ordered molecular structures even after prolonged exposure. This situation occurs at powers when the rotational molecular relaxation time

, determined mainly by the value of the internal viscosity of the medium η and the ambient temperature t ° less time

between successive acts of absorption of light quanta by the same dichroic molecule when a continuous radiation source is exposed to the medium.

When pulsed by a polarized or not polarized, but directed

radiation with a duration of not more than several tens of nsec and radiation energy densities

~ MW / cm ² amorphous layers of dichroic dyes without a matrix exhibit a second threshold

nonlinear effect. With such parameters of the exciting pulses, the limiting

photoinduced anisotropy in such layers is achieved by a single absorption of a quantum of light by molecules during the duration of the exciting pulse (the “large jump” effect is Δθ ~ 90 °).

In this case, the sensitivity (i.e., the reciprocal of the energy density necessary for

saturation) increases tenfold (Fig. 8) compared with the excitation mode

of these layers with low-power continuous radiation or pulsed with a pulse duration of more than hundreds of nsec and a pulse frequency of the order of ten kHz.

This effect is observed at optical power densities of only

slightly smaller than necessary for thermooptical melting of these layers (Fig. 8).

The presence of a second threshold in a certain range of power density and pulse duration of exciting radiation is due to the fact that in this mode, approximately 50% of all layer molecules oriented mainly parallel to the electric field vector of exciting radiation are in the excited state.

The subsequent intermolecular cross-relaxation and energy degradation of simultaneously absorbed light quanta for a short period of time (nanosecond duration) transfers all the molecules of the layer to a thermodynamically nonequilibrium highly ordered state of premelting under the action of a highly oriented internal reactive field ER created by the remaining “cold” unexcited molecules.

Rapid cooling of the layer preserves this molecular structure.

Thus, by analogy with the otherPhotothermal-mode formingʺ method of the reversible phase transition (1), in the present invention, we propose the hotPhoton-mode formingʺ method of the reversible phase transition “disordered amorphous structure - orientationally ordered structure”:

IFM based on such PCBs absorbing in the spectral region from 150 nm to 2000 nm

can be selected from classes including:

Moreover, classes of such anisotropic substances may include, for example:

- mono-, dis-, tris-, polyazo dyes, metal-complex or complex-forming azo dyes [see, for example, A.V. Ivashchenko, Dichroic azo dyes for liquid crystal displays. Chem. prom., Aniline-paint prom., NIITEKHIM, Cherkasy, 1987];

- anthraquinone dyes, mono- and polyoxy anthraquinones [see, for example, A.V. Ivashchenko, Dichroic anthraquinones for liquid crystal displays. Chem. prom., Aniline-paint prom., NIITEKHIM, Cherkasy, 1989];

- azo dyes with polar hydrophilic "heads" and long hydrocarbon lipophilic "tails" for Langmuir-Blodgett films

- mordant azo dyes [B.I. Stepanov, Introduction to Chemistry and Technology of Organic Dyes, ed. "Chemistry", M. 1971]

As well as many other photochemically stable substances from other classes of anisotropic (dichroic) substances exhibiting the property of photoinduced optical anisotropy with the participation of low molecular weight additives, the vibrational levels of the ground state of which are close to or in resonance with the corresponding vibrational levels of the molecules of the photochemically stable substance, providing an effective process of anisotropy of intermolecular vibrational vibrational cross-relaxation energy of an absorbed quantum.

As dichroic substances, substances from the class of azobenzenes, mono- and bisazo dyes are most preferred.

Such substances can also be used such substances as 2-methyltetrahydrofuran dissolved in a low molecular weight matrix exhibiting orientational rearrangement at helium temperatures and responsible for the non-photochemical burning of spectral dips in Shpolsky matrices [see, for example, E.I. Alshits, B.M. Kharlamov, Z.I. Persons, On the question of non-photochemical burning of spectral dips // Journal. Adj Srektrosk., XLV, 559 (1986)].

The table shows the structural formulas of a number of photochemically stable azo dyes and other substances exhibiting a reversible effect of orientational ordering and used as examples in this application.

FHSB can have two or more groups of the type —OH, —NH2, —COOH, NHR (where R can be —C6H4CH3, - (CH3) 2, COCH3) and others capable of forming specific intermolecular donor – acceptor or hydrogen bonds between the PCFB or PCFB molecules and the molecules of the solid-state matrix. These bonds provide long-term stability of photoinduced anisotropy.

In addition, FHSWs are also carried out in the form of bi- or multifunctional substances such as monomers or oligomers, which are additionally composed of fragments, for example, luminescent or photochromic. FHSV, for example, derivatives of azo dyes can be introduced directly into the main chain of macromolecules or linked through alkyl spacers in the side chain, which do not interfere with the effect of photoinduced anisotropy.

Polymer structures can contain fragments that give them the properties of thermotropic and lyotropic FAs.

For the fixation of photoinduced anisotropy, PFHS can have two or more polymerization-capable groups. Examples of such groups are (meth) acryloyl group, and (meth) acryloxy group, a (meth) acrylamide group, a vinyl group, a vinyloxy group, an azide group, a chloromethyl group, an epoxy group, a (meth) acryloyl group, a (meth) acryloyloxy group, a (meth) acrylamide group, a vinyl group.

Some examples of polymer matrices can be well-known derivatives: polyimide, polyethylene, polystyrene, cellulose acetate, polycarbonate, polyesters, polyacrylonitriles, polyvinyl alcohol, polymethyl methacrylate, polyvinyl ethyl, polyvinyl butyral, polybutyl methacrylate, phenol and polymeric formaldehydes.

The objective of the present invention is the use of IFM based on PFSS and one- and two-photon methods of phototechnology for the production of transparent or colored in the visible or near infrared region of the spectrum of molecular orientationally ordered structures in a solid, for example, in the form of static or adaptive picture 3-dimensional, for example periodic micro- and / or submicrodielectric structures, such as three-dimensional, in particular periodic, micro- or submicrodielectric structures, such as photonic crystals or fiber and flax-optical elements in a solid with a predetermined in accordance with the computer program anisotropic spatial distribution, in particular the optical properties in different sections of the two-dimensional volumetric body. They can also be used in the production of specific optical elements, for example, such as anisotropic three-dimensional optical elements such as diffraction gratings, lenses, phase plates, and also various structures with a complex volumetric configuration profile of anisotropic optical properties.

As the latter, there can be polarized computer volumetric or conoscopic holograms or computer anisotropic models transparent for measuring radiation of various products subjected to mechanical stresses and with which it is possible to carry out the same studies by photoelasticity as with real objects [Frocht MM, Proc. Intern. Sympos. on Stress Wave Propagation in Materials, 1960; J.W. Dally, Introduction to Photoelasticity, Exp. Mech 20, 409 (1980)].

The volumetric forms of such stressed solid models, in particular, can be preliminarily

were obtained by traditional stereolithography using initially liquid photopolymerizable compositions with FHSW incorporated into them, in which an anisotropic-stressed structure can be additionally formed by spatial scanning over the volume of the cured model of a focused laser beam, the polarization and energy characteristics of which are set by a computer program. The possibility of multiple formation of various anisotropic-stressed structures in such initially isotropic models from cured photopolymer compositions makes them especially economically attractive for this application.

Such media can also be used as artificially created highly oriented molecular matrices that provide unique selectivity and efficiency of thermo-, photo- or simply chemical processes of any molecular active additives introduced and oriented in them, similar to similar processes in “self-ordered” biological systems .

They can be used as means of protection when creating visually or machine-readable signs of authenticity and identification of various household and industrial products, such as banknotes, credit cards, etc.

The following are examples of the formation, irradiation, and application of the proposed PMFs based on FHSV.

EXAMPLE 1

As a PCM, a sample was formed based on 4- (4-nitrophenyl) -4 ¹ - (4-N, N-dioctylaminophenylazo) azobenzene azo dye (1) as PCF:

For this, a block (2.5 × 2.0 cm ² × 2 mm) of poly (methyl methacrylate) with azo dye (1) (0.05 wt.%) As a monolithic volume PCM was prepared as follows. The glass ampoule was purged with argon for four minutes, after which 0.0141 g of azobisisobutyronitrile, 0.007 g of azo dye (1), and 14.1 g (14.94 ml) of purified and freshly distilled methyl methacrylate were placed in it. After additional purging of this solution with argon for four minutes, the ampoules were sealed. Then it was placed in a water bath, followed by a gradual increase in temperature to 80 ° C and holding at this temperature for 1.5 hours. After this, the sealed ampoule was transferred to a water bath with a temperature of 25 ÷ 30 ° C and kept there for three days, followed by two hours of heating at 100 ° C.

The ampoule with the polymerized bulb was broken and the above specimen of a photoanisotropic material about 2 mm thick was cut out and polished from the latter. The sample was quite intensively absorbed in the region of ~ 540 nm and was transparent at the wavelength of the Ti-sapphire laser (860 nm) and the He-Ne laser (632.8 nm).

In accordance with the invention, the sample was used in a simplified version of the optical unit of the volumetric memory system for two-photon recording and single-photon reading of information.

It includes a recording source based on a Ti: sapphire laser with an argon laser as a pump source, the radiation of which was directed by a lens into a given microregion of a given volume recording medium. The size of the focused spot varied from 1.4 to 3 μm.

Since the laser generation wavelength (860 nm) lies in the transparency region of the used IFM, an unfocused beam does not have any effect on it. However, the sum of two photons is equivalent to one quantum with a wavelength of 430 nm, which was within the absorption band of the dye (1).

As a result of two-photon absorption, the irradiated microregions proposed in this

the invention of the recording medium becomes optically anisotropic, in particular, birefringent in the field of transparency at a wavelength of 632.8 nm. This was a consequence of the orientational ordering of dichroic molecules of a photochemically stable dye (1) in a plane perpendicular to the direction of the polarization vector of the recording radiation.

In addition, the two-photon recording process made it possible to form bulk anisotropic optical elements in which the DLP value was picture-modulated along the depth of the PSM.

EXAMPLE 2

A thick (~ 100 μm) film of the copolymer butyl methacrylate amide of methacrylic acid and acrylonitrile with azo dye (1) (1 wt%), obtained by pouring a polymer solution onto a substrate and subsequent evaporation of the solvent, was used as a bulk FFM. Two-photon recording and single-photon reading were carried out as in example 1.

EXAMPLE 3

We used the photoanisotropic PSM described in Example 2. It was used to study the stress states of a transparent deformed model. Using polarized incoherent radiation from a DRSh-250 mercury lamp (436 nm), an image of a stressed part was recorded on the material. The resulting image was a “hologram” of a deformed object recorded in non-monochromatic, incoherent light. It was also read in incoherent light in crossed polarizers. Photos of images reconstructed from such a “hologram” are shown in FIG. 9 obtained with two positions of crossed polarizers.

EXAMPLE 4

A homogeneous polymer block was used as a bulk PMF, in which an initially liquid, UV-curable (photopolymerizable) composition based on α, ω- (meth) acrylic- (bis-propylene glycol) -2,4-tolueneurethane of the chemical formula was used as a polymer matrix CH2 = C (CH3) -COO- (CH2-CH2O) 3-OC-C (CH3) = CH2) and diacetyl of the chemical formula (CH3-CO-CO-CH3) as a photoinitiator. The concentration of the anisotropic dye (1) in the photopolymerizable composition was about 0.03 weight. % To obtain a homogeneous solid polymer block, a photopolymerizable dye composition was placed in a 2.5 mm thick quartz cuvette and exposed to unfiltered polarized radiation from a 250 W mercury lamp for 5 minutes until it completely hardened. The moment of transition of the UV curable composition to a solid state was monitored at a wavelength of 632.8 nm by the absence of dark relaxation of birefringence induced in the cured block upon the occurrence of sufficient viscosity in it. After that, he underwent temperature annealing to transfer it to an isotropic state.

Two-photon recording and single-photon reading were carried out as in example 1.

EXAMPLE 6

A multilayer carrier consisting of separate thin photoanisotropic layers separated by transparent polymer films with a thickness of about 50 μm was used as a three-dimensional PSM. The separation layers are made of UV cured photopolymerizable composition without photoanisotropic dye, used in example 2 as a polymer matrix. Each of the recording layers with a thickness of about 150 nm was obtained by thermal spraying of the dye (1V)

in vacuum (deposition temperature - about 150 ° C) on the corresponding separation layer with their subsequent gluing together using a water-soluble photopolymerizable composition that does not dissolve the recording layer.

Received PMM was used as in example 1.

EXAMPLE 7

Similar to example 5, but each of the recording layers of the multilayer media

The information was obtained by sequentially depositing a thin layer of a photochemically stable dichroic dye of the formula (1) onto a photocured separating layer from a 0.5% (by weight) solution in dichloroethane (rotation speed 3000 rpm, application time 45 sec) .

Information was recorded in a single-photon mode using focused radiation from an argon laser (λ = 514 nm, continuous power ~ 5 W, recording time ~ 0.2 μs).

Due to the quasi-linearity of the photophysical process of photo-orientation (the strong dependence of the dark relaxation time on the absorbed energy during exposure in Fig. 8), the undesirable “background orientation molecular ordering induced in layers outside the focus plane (before and after the information layer in which the recording was made) gradually disappeared with time at room temperature with a simultaneous increase in the orientational order in the recorded microregions (increasing the brightness of the recorded spot at observation in crossed polarizers).

This process was accelerated by heating the carrier to temperatures close to the melting point of the dichroic dye (~ 136 ° C).

Example 8

Similar to example 6, but as a photochemically stable dichroic substance

We used a liquid crystal polymer with an azo dye in the side chain (11), the structural formula of which is given in the table.

While the present invention provides some preferred options for its implementation, specialists in this field it is clear that various changes in form and detail can be made without departing from the essence and scope of the present invention.

Example 9

The monomolecular layer of a pure yellow etch dye (111) obtained by drawing a glass substrate from a 1% aqueous dye solution (111) was used as a photo-orientation of Merck thermotropic LC by the method described in [V.G. Chigrinov, V.M. Kozenkov, H.S. Kwok, Photoalignment of Liquid Crystalline Materials: Physics and Applications, 232 pp., Wiley, August 2008].

Example 9

A thin (about 0.3 μm) dye layer (1) obtained by thermal evaporation in vacuo was used as a photo-orientant of lyotropic LC firms NIOPiK (Russia) and Corning (USA) also according to the method described in [V.G. Chigrinov, V.M. Kozenkov, H.S. Kwok, Photoalignment of Liquid Crystalline Materials: Physics and Applications, 232 pp., Wiley, August 2008].

Example 10

As an FCM based on PCF, layers of azo dye (1V) were used,

obtained by the Langmuir-Blodgett method. The PMF solid film was used in experiments on reverse image recording.

Example 11

Samples of TOSP color glasses manufactured by the domestic industry (GOST 17622-72) based on PMMA with photochemically stable dyes (usually azo dyes) and a plasticizer (dibutyl phthalate) introduced into the composition of the polymerization mixture were used as FFMs. The glass thickness was 5 mm. Softening point - not less than 90 ° С. They are used in instrument and mechanical engineering for the manufacture of various technical products.

However, the authors of the present invention have discovered the effect of photoinduced anisotropy (birefringence (birefringence) and absorption dichroism (DC)) and should be taken into account during their operation, since optical anisotropy can be induced only by polarized, but also non-polarized, directed radiation of natural origin.

The table shows the structural formulas of azobenzene-containing liquid crystalline polymers with azo dyes in the V-1X side chain, in which the effect of photoinduced optical anisotropy was also previously detected, the mechanism of this phenomenon being explained by photochemical angular selection as a result of the repeated trans-cis-trans photoisomerization reaction upon repeated absorption of quanta the lights are the same during irradiation with azobenzene fragments present as side fragments in the polymer chain.

The same applies to the metal-derived salts of azo dyes described in the patent of the Republic of Belarus, [No. 17225 (2013), authors V.U. Agabekov et al., “4,4'-Bis [1- (4-hydroxy-3-carboxy-6-methyl) phenylazo] diphenyl and its metal derivatives of salts as a photoorienting thin-film material”].

At the same time, it is well known that such transcis-photoisomerization of azo dye molecules is accompanied by significant spectral changes during the irradiation of the photochromic layer, including azo compounds [V.A. Barachevsky, G.I. Lashkov, V.A. Tsekhomsky. Photochromism and its application // M .: "Chemistry", 280 p. (1977); Organic Photochromes, ed. A.V. Yeltsova, L-d (1982)]. This is shown in fig. 3a for the photochromic substance phenoxynaphthacinquinone. However, such spectral changes were not seen in any of these samples of V-1X substances. Moreover, when irradiated with polarized radiation in the absorption band of polymer azo dyes, as for the FHSW claimed by the authors of the present invention, absorption dichroism is induced. Wherein:

1. the shape of the absorption spectrum always remains unchanged, regardless of the amount of absorbed energy and

2. there is always a “clarification" of the polarization component parallel to the polarization of the activating radiation and "dimming" for the orthogonal component (see Fig. 3b).

This indicates that high molecular weight substances V-1X, as well as metal derivatives of azo dyes, belong to the class of PCHS claimed in the present invention, exhibiting reversible photoinduced anisotropy and suitable for producing polarization-sensitive materials and polarization-optical elements from them, respectively.

The given examples confirm the fulfillment of the task.

INDUSTRIAL APPLICABILITY

The method and material proposed in the claimed invention can be used as a chemical and / or structural material in phototechnology for the production of a variety of picture two- and / or three-dimensional polarization-optical elements and devices of nano-, micro- and macro-optoelectronic devices, in instrumentation using such polarization optical elements.

It can be used in the manufacture of optical anisotropic fiber and integrated optics such as anisotropic photonic crystals, volume diffraction gratings, radiation input-output devices, lenses, polarization-selective light beam dividers, etc., in phototechnology for the production of photothermally stable adaptive internal thin-film phase plates and polaroids, as well as photo-orientants of liquid crystals.

It is promising in the manufacture of an optically formed picture highly oriented matrix for special low molecular weight active additives that exhibit high selectivity and efficiency of thermo-photo or simply chemical processes occurring in them, depending on the degree of their ordering in the highly oriented matrix.

As a polarization-sensitive photoanisotropic information carrier, it can be used in technical means of recording, storing, processing and displaying information, including in systems of two- (2D) and / or three- (3D) dimensional optical memory WORM and VR-type in polarizing computer, including conoscopic, holography, in means of protection against counterfeiting and identification of securities and other household and technical products, when creating new instruments and devices of measuring equipment for the study of mechanical their stresses in various products by photoelasticity, etc.

The list of abbreviations used in the order of their mention in the application text:

2D - two-dimensional optical memory,

3D - three-dimensional optical memory,

WORM - write only read many optical memory,

RV - rewritable optical memory,

POE - polarization-optical element,

PMM - polarization sensitive material

LCD - liquid crystal,

FTTF - photothermal type of formation,

FOTF - photo-optical type of formation,

DLP - birefringence,

FFM - polarization sensitive material,

FHSV - photochemically stable substance,

UV - ultraviolet radiation,

IR - infrared radiation,

FAM - photoanisotropic material.

Claims (39)

1. A method of forming a polarization-sensitive material capable of in the solid state to form in its volume and surface a polarization-optical element in the form of a picture of a spatially modulated, ordered anisotropic molecular structure by irradiation with polarized or non-polarized, but directed radiation of the specified polarization-sensitive material, absorbed by the polarization-sensitive component that is part of this material, characterized in that as a polarization-sensitive component responsible for the formation of an anisotropic optical element in it, a photochemically stable, anisotropic one- or two-photon absorbing, non-luminescent or weakly luminescent substance is used, which is part of the polarization-sensitive material in the form of components uniformly distributed at the molecular level in homogeneous and isotropic low or high molecular weight matrix, and the specified specified spatially modulated, ordered anise an otropic molecular structure in which the orientation direction, orientational order, and anisotropy of optical properties, namely, the absorption dichroism, birefringence, and phase delay, directly correlate with the spatial distribution of the linear, elliptical, or circular polarization states, energy characteristics, and the direction of propagation of activating radiation, can repeatedly reversibly formed and / or transformed both in the case of one- and two-photon, h a real or virtual intermediate level, the absorption of the proposed photochemically stable component of a polarization-sensitive material, which also includes other low molecular weight additives, the vibrational levels of the ground state of which are close to or in resonance with the corresponding vibrational levels of the molecules of the photochemically stable substance, providing an effective anisotropic intermolecular process vibrational cross-relaxation energy of an absorbed quantum in the nearest surrounded during irradiation of the PMF and, in addition, regulating film-forming, viscous, anisotropic-optical, physicochemical and mechanical properties of the formed material, depending on its specific application. 2. The method according to claim 1, in which the irradiation of a polarization-sensitive material with radiation absorbed by its polarization-sensitive component leads to the formation of a polarization-optical element in the bulk and on the surface of the material, exhibiting anisotropy of its optical properties, such as the orientation of the optical axis and the magnitude of absorption dichroism, birefringence, and phase delay, without changing the shape of the absorption spectra of the polarization-sensitive component itself, regardless of the amount of absorbed energy and, always “clarifying” for the polarization component parallel to the polarization of the activating radiation, and “darkening” for the orthogonal component. 3. The method according to claim 1, wherein the photoinduced anisotropy in the polarization-sensitive material reaches its maximum photostationary value asymptotically. 4. The method according to PP. 1 and 3, in which the orientational order parameter of photochemically stable molecules in a polarization-sensitive material can reach values greater than 0.8, and photo-induced birefringence more than 0.4. 5. The method according to p. 1, in which, when pulsed by radiation lasting no more than a few tens of nanoseconds and a power density of the order of MW / cm ^2, amorphous layers of photochemically stable substances without a matrix spend tens of times less inducing optical anisotropy in them than when exposed continuous radiation with a power density of the order of ten mW / cm ² . 6. The method of claim 1, wherein heating the irradiated layer of the polarization sensitive material to a temperature several degrees lower than the melting temperature of the polarization sensitive component leads to an increase in the degree of molecular ordering and optical anisotropy induced therein. 7. The method according to claim 1, in which the polarization-sensitive material provides one initial thermodynamically stable isotropic state with a randomly spatial orientation distribution of photochemically stable molecules and two quasi-thermodynamically stable states with the orientation of the dipole moments of the transition of molecules in a plane perpendicular to the polarization vector linearly or elliptically polarized activating radiation or along the direction of propagation of circularly polarized or non-polarized vannogo radiation. 8. The method according to p. 1, in which the reversible formation and / or transformation of the specified spatially modulated, ordered anisotropic molecular structure is carried out by periodic optical irradiation by reversing the spatial local or across the entire surface of the structure by changing the orientation of the polarization vector of the energy of the irradiating radiation to orthogonal. 9. The method according to p. 1, in which the provision of a variety of structures with a complex volumetric configuration of the properties of optical anisotropy (the direction of the polarization axis, dichroism of absorption and birefringence) along the thickness of the polarization-optical element formed in the polarization-optical material is carried out by locally changing the direction of the vector polarization and power density of focused two-photon absorbed radiation along the depth of a layer of polarization-sensitive material. 10. The method according to p. 1, providing the formation of polarization-optical elements and devices operating using the effect of non-photochemical orientation burning spectral dips in Shpolsky matrices at temperatures close to the temperature of liquid helium. 11. Polarization-sensitive material referred to in paragraphs. 1-10 and capable of forming a polarizing optical element in its bulk and on the surface in the form of a spatially modulated, ordered anisotropic molecular structure by irradiation with polarized or non-polarized but directed radiation that is one or two photon absorbed by a polarization-sensitive component, part of the specified polarization-sensitive material, containing in the general case also: - a monomeric, oligomeric or polymer matrix for dissolving in it a photochemically stable substance and transparent at a wavelength of activating radiation and - special low molecular weight additives that regulate film-forming, viscous and other physicochemical properties. 12. The material according to claim 11, in which the presence or absence in its composition of a monomeric, oligomeric or polymer matrix is determined by its specific application as a polarizing optical element or device. 13. The material according to paragraphs. 11 and 12, in which photochemically stable, anisotropically absorbing dichroic, non-luminescent or weakly luminescent substances are selected from classes of substances exhibiting absorption bands between 150 nm and 2000 nm in the UV, visible and / or IR spectral range. 14. The material of claim 13, wherein the classes of anisotropic substances include, for example: - mono-, dis-, tris-, polyazo dyes, metal-complex or complex-forming azo dyes; - quinone dyes; - anthraquinone dyes; - azo dyes with polar hydrophilic "heads" and long hydrocarbon lipophilic "tails" for Langmuir-Blodgett films; - mordant and acid azo dyes; - high molecular weight polymeric substances with azobenzene substituents in the side chain; - azobenzene-containing liquid crystal polymers. 15. The material according to claim 11, in which the photochemically stable substances are presented in the form of covalently bound bi- or multifunctional molecules, which in addition to the dichroic chromophore also include, for example, luminescent or photochromic fragments or one or more photosensitive fragments that contribute to the photochemical formation of spatial nets when irradiated with radiation absorbed by this fragment, but not absorbed by a photochemically stable substance. 16. The material according to claim 11, in which photochemically stable substances exhibit thermotropic liquid crystal properties in a certain temperature range. 17. The material according to claim 11, in which photochemically stable substances exhibit lyotropic liquid crystal properties in a certain concentration range of the solvent. 18. The material according to claim 11, in which photochemically stable substances are introduced into the main chain of the macromolecule or covalently linked to it in the side group via, for example, an alkyl spacer. 19. The material of claim 11, wherein the well-known derivatives of polyimide, polyethylene, polystyrene, cellulose acetate, polycarbonate, polyesters, polyacrylonitriles, polyvinyl alcohol, polymethyl methacrylate, polyvinyl ethyl, polyvinyl butyral, polybutyl methacrylate, polybutyl methacrylate, and other polymers. 20. The material of claim 11, wherein the well-known derivatives of photosensitive polymers such as polyvinyl cinnamate or polyimide are used as the polymer matrix. 21. The material according to p. 11, in which the film-forming polymers are selected from the conditions that their vibrational levels in the ground unexcited electronic state are in resonance or close to the corresponding vibrational levels of photochemically stable substances. 22. The material according to claim 11, the component composition of which includes low molecular weight additives, the vibrational levels of which in the main unexcited electronic state are in resonance or close to the corresponding vibrational levels of photochemically stable substances. 23. The material according to claim 11, in which the photochemically stable substances, or chromophores, and polymer matrices have at least two substituents of the OH, COOH, NHR type (where R can be, for example, -C6H4CH3, - ( CH3) 2, COSH3) and others capable of forming at least two specific intermolecular donor-acceptor or hydrogen bonds between the dichroic substance and the macromolecule of the polymer matrix or between the dichroic molecules themselves with the formation of a spatial orientationally ordered network. 24. The material according to claim 11, in which the polymer binder is absent, and the glassy, isotropic unirradiated layer of a photochemically stable low or high molecular weight substance with various technological or other low molecular weight additives introduced into it at the molecular level acts as an isotropic matrix in this case the effect of photoinduced optical anisotropy in the solid state of a polarization-sensitive material. 25. The material according to claim 11, where active special additives are used as special low molecular weight additives, exhibiting high selectivity and the effectiveness of the thermo-, photo- or simply chemical processes in them, depending on the degree of their ordering in a highly oriented matrix. 26. The use of polarization-sensitive material based on photochemically stable substances according to paragraphs. 1-25 as a chemical and / or structural material in phototechnology for the production of a variety of picture two- and / or three-dimensional polarization-optical elements and devices of nano-, micro- or macro-optoelectronic technology. 27. The use of polarization-sensitive material according to paragraphs. 1-25 as an optically formed picture highly oriented matrix for special low molecular weight active additives that exhibit high selectivity and efficiency of thermo-, photo- or simply chemical processes occurring in them, depending on the degree of their ordering in the highly-oriented matrix. 28. The use of polarization-sensitive material according to paragraphs. 1-25 as a photoanisotropic medium in the technical means of recording, storing, processing and displaying information.

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