Scope of the project

Synthesis and research of crystalline nanostructured materials as an innovative technological product

Project content

The problem to solve:

Optical and vibrational properties of materials for creating antennae, modulators and converters of the optical range, particularly, using nanotechnology.

Object and subject of research:

Crystalline nanostructured materials composed of dielectric nanoporous matrices filled with nanocrystallites with specific functional properties.
Nanoporous matrices were selected that meet the requirements for filling their structures with nanocrystallites from aqueous solutions. The following nanocrystallites KDP, ADP, Ba(NO₃)₂ were grown within the pores of the matrices, and the optimal conditions for the technology of obtaining nanocrystalline samples were worked out. X-ray structural and SEM studies showed that crystals ADP, KDP, Ba(NO₃)₂ and LiNbO₃ were synthesized in Al₂O₃, Si and SiО₂ matrices. New technological conditions for synthesis and new crystalline filler materials (KDP, ADP) provide a significant advantage over known materials in the efficiency of nonlinear optical conversion and in reducing the reflection coefficient over a wide frequency range.

The purpose and main objectives of the study:

The goal of the project is twofold.

• Firstly, the project is intended to study the physical peculiarities of the manifestation of dielectric, optical, and nonlinear-optical properties of crystalline compounds during the transition from bulk materials to two- and one-dimensional structures, as well as when combining such low-dimensional structures of one chemical composition with a material of another chemical composition in the form of a composite with nano- or micro-dimensional scale.
• Secondly, based on the research conducted, it is foreseen to solve applied problems in manufacturing of prototypes of possible devices for efficient control of electromagnetic radiation based on nanostructured materials using the electro-optic effect or nonlinear optical conversion of the radiation frequency in the optical range, particularly for telecommunication applications. It is also planned to verify the previous experimental data, according to which nanoscale composite materials based on a matrix of Al₂O₃ (anodic aluminum oxide - AAO) and crystal (NH₄H₂PO₄) (ADP) exhibit very low transmittance and reflectance coefficients, which can be directly used in creating a structure with an ultra-low reflectance coefficient as anti-radar material in the infrared range of the spectrum.

Main objectives of the project:

• Optimization of synthesis processes of nanostructured materials based on AAO, ATO (anodic titanium oxide), SiO₂ matrices and filling materials: KH₂PO₄ (KDP) crystals, ADP, etc.;
• Electron microscopy study on the surfaces of synthesized nanostructured materials and examining their pore content for uniformity of penetration of the incorporated material into the matrix volume;
• X-ray structural and spectroscopic (micro-Raman scattering) studies on nanostructured materials with detailed group theory analysis of Raman spectra;
• Study of reflection/transmission spectra in a wide range of 0.4-15 microns;
• Nonlinear-optical and parametric-optical studies on synthesized nanostructured materials;
• Research into the spatial and surface morphology of nanostructured materials in the form of nanotubes/nanorods with a view to their possible practical use as an innovative technological product, particularly, in telecommunication devices;
• Research of a structure with an ultra-low reflectance/transmittance coefficient based on a nanoporous matrix and a crystalline filling material and development of an engineering model and creation of a mock-up of a structure with an ultra-low reflectance coefficient.

Main results

1. A careful selection, characterization and determination of the best geometry of nanoporous matrices that meet the requirements for filling their structures with nanocrystallites from aqueous solutions were carried out. Nanocrystallites were grown from saturated aqueous solutions at different temperatures and the most optimal conditions for the technology of obtaining nanocrystalline samples from saturated aqueous solutions were worked out. X-ray diffraction and SEM studies confirmed the growth of crystals in the matrices.
2. Based on the analysis of Raman scattering of composite materials, the conclusions about the formation of the corresponding nanocrystals in the pores of the matrices have been confirmed. Group theory based and ab initio calculations of phonon spectra of filling crystals, dynamic and mechanical conditions of stability of crystal lattice of crystals have been described. Based on the modeling results, experimental data of Raman studies have been interpreted.
3. The global maxima of the electro-optic effect for crystalline materials that can be used to fill nanomatrices have been derived by the method of extreme surfaces, as well as the optimal geometries of vector phase synchronism for uniaxial nonlinear-optical crystals for cases of second harmonic generation, sum and difference frequency. The directions of the wave vectors of the input rays and the beam at the wavelength of the second harmonic have been determined, which ensure maximum efficiency of the processes. The manifestations of second harmonic generation in composite materials have been investigated and the conditions and materials with the highest generation efficiency have been established.
4. The reflection/transmission spectra of the nanocomposites obtained were measured and analyzed for different states of the matrix surface. Based on the studies carried out, a technology for obtaining structures with an ultra-low reflection coefficient of electromagnetic radiation in the wavelength range of 1.0÷10.0 μm has been developed.

Originality and innovative output

These studies made it possible to develop a technology for obtaining nanocomposites suitable for the creation of anti-reflective coatings over a wide spectral range.

Oral and poster presentations at international conferences based on the project outcome

1. Andrushchak N., Vynnyk D., Adamiv V., Haiduchok V., Strelchuk V., Nikolenko A., Andrushchak A. Optical and Electron Microscopy Studies of Al₂O₃ Nanomatrices with Embedded ADP and KB5 Nanocrystals // In 2022 IEEE 12th International Conference Nanomaterials: Applications & Properties (NAP). - 2022. Kraków, Poland. - NCI02-1. 10.1109/NAP55339.2022.9934289
2. Andrushchak N., Vynnyk D., Kopko B., Haiduchok V., Adamiv V., Andrushchak A. The Impact of Mechanical Treatment of the Al₂O₃ Nanomatrices Surface on their Optical Parameters with and without KDP Crystals Inclusion // Book of abstracts 2nd International Conference on Innovative Materials and NanoEngineering. - 2022. Dovgoluka, Ukraine. - Р. 2-2.
3. Shchur Ya., Bendak A., Kityk A., Andrushchak A. Peculiarities of Raman Mapping of Nanocomposite Materials. // Book of abstracts 2nd International Conference on Innovative Materials and NanoEngineering (IMNE`2022), November 11-13, 2022, Dovgoluka, Ukraine, Р. 2-3.
4. Shchur Ya., Strelchuk V., Nikolenko A., Kityk A., Beltramo G., Vitusevich S., Andrushchak N., Adamiv V., Teslyuk I., Andrushchak A. Lattice Dynamics of Nanosized KH₂PO₄ and Ba(NO₃)₂ Crystals Confined in Porous SiO₂ Matrix: Raman Spectroscopy and ab initio Lattice Dynamics Analysis. // Book of abstracts 2nd International Conference on Innovative Materials and NanoEngineering (IMNE`2022), November 11-13, 2022, Dovgoluka, Ukraine, Р. 3-1.
5. Shchur Ya., Kityk A., Bendak A., Andrushchak N., Beltramo G., Vitusevich S., Andrushchak A., Jedryka J., Slyvka Y. Raman Scattering and X-ray Diffraction Study of Benzil (C₆H₅CO)₂ Nanocrystals Embedded to Porous Silica Matrix. // Book of abstracts 2nd International Conference on Innovative Materials and NanoEngineering (IMNE`2022), November 11-13, 2022, Dovgoluka, Ukraine, Р. 3-3.
6. Kityk A. V., Karout H. E., Sahraoui B., Shchur Y., Andrushchak A., Wielgosz R., Kityk O., Jedryka J., Slyvka Y., Lelonek M., Goring P., Huber P. Silica-benzil and alumina-benzil crystalline nanocomposites: textural morphology and nonlinear optical characterization // Book of abstracts 3rd International Conference on Innovative Materials and NanoEngineering (IMNE`2023), November 10-13, 2023, Dovgoluka, Ukraine, Р. 61.
7. Yaremko O., Adamiv V., Teslyuk I., Shchur Y., Andrushchak A., Zhukovska D., Lelonek M. Preparation of Potassium Pentaborate and Lithium Niobate Crystalline Nanocomposites Based on Al₂O₃ and SiO₂ Nanoporous Matrices. Proceedings // 16th International Conference on Advanced Trends in Radioelectronics, Telecommunications and Computer Engineering. - 2022. Lviv.-Slavske, Ukraine. - P. 689-693. 10.1109/TCSET55632.2022.9766979
8. Shchur Ya., Adamiv V., Teslyuk I, Andrushchak A. Preparation of Bi₁₂GeO₂₀ nanocrystalline structures // International Conference on Innovative Materials and Nanoengineering (IMNE`2023). Conference Program and Book of Abstracts. - 2023. Dovgoluka, Ukraine. - P. 55.
9. Aamoum A., Taboukhat S., El Kouari Y., Zawadzka A., Andrushchak A., Sahraoui B. Optical Properties of Some Selected Organometallic Compounds // 2023 23rd International Conference on Transparent Optical Networks (ICTON), Bucharest, Romania, 2023, pp.1-4. 10.1109/ICTON59386.2023.10207187
10. Sahraoui B., Karout H. E., Kityk A. V., Shchur Y., Andrushchak A., Wielgosz R., Kityk O., Lelonek M., Goring P. Functionalised selected conjugated compounds for nonlinear optical applications // Book of abstracts 3rd International Conference on Innovative Materials and NanoEngineering (IMNE`2023), November 10-13, 2023, Dovgoluka, Ukraine, Р. 60.
11. Buryy O., Shulha D., Andrushchak A. Determination of Optimal Conditions of Second Harmonic, Sum and Difference Frequency Generation in Crystalline Materials by Extreme Surfaces Method // Book of abstracts 2nd International Conference on Innovative Materials and NanoEngineering (IMNE`2022), November 11-13, 2022, Dovgoluka, Ukraine, Р. 2-5.

Publications

Scientific papers published in the course of the project:

1. Yaremko O.M., Adamiv V.T., Teslyuk I.M., Zhukovska D., Wielgosz R., Strykhaluik B.M., Shchur Ya. Synthesis and Study of KH₂PO₄ Nanotubes (Nanorods) Embedded in Al₂O₃ Porous Matrix // Acta Phys. Pol. A - 2022. - V. 141(4). - P. 390-395. 10.12693/APhysPolA.141.390
2. Shchur Y., Beltramo G., Andrushchak A.S., Vitusevich S., Huber P., Adamiv V., Kityk A.V. On the issue of textured crystallization of Ba(NO 3 ) 2 in mesoporous SiO 2 : Raman spectroscopy and lattice dynamics analysis // Spectro-chimica Acta Part A: Molecular and Biomolecular Spectroscopy - 2022. - V. 275. - P. 121157. https://doi.org/10.1016/j.saa.2022.121-157
3. Karout H.E., Shchur Y., Andrushchak A., Sahraoui B., Wielgosz R., Kityk O., Jedryka J., Slyvka Y., Kityk A.V. Second harmonic generation on crystalline nanoclusters in functionalized silica-benzil composites: Effect of extreme nanoconfinement on conversion efficiency // Sci. Rep. - 2023. - V.13.- P.9943. https://doi.org/10.1038/s41598-023-37147-4
4. Shchur Ya., Bendak A., Beltramo G., Andrushchak A. S., Vitusevich S., Pustovyj D., Sahraoui B., Slyvka Yu., Kityk A. V. Nanoarhitectonics of Inorganic-Organic Silica-Benzil Composites: Synthesis, Nanocrystal Morphology and Micro-Raman Analysis // Nanomaterials. - 2023, V.13. - P.1913-1-15. https://doi.org/10.3390/nano13131913
5. Buryy O., Andrushchak N., Danylov A., Sahraoui B., Andrushchak A. Optimal Vector Phase Matching for Second Harmonic Generation in Orthorhombic Non-Linear Optical Crystals // Acta Physica Polonica A. - 2022. - V.141. - P. 365-370. 10.12693/APhysPolA.141.365
6. Buryy O.A., Demyanyshyn N.M. Mytsyk B.G., Andrushchak A.S., Sugak D.Yu. Acousto-optic interaction in LGS and CTGS crystals // OSA Continuum. - 2022. - V.1. - P. 1314-1323. https://doi.org/10.1364/OPTCON.450576

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