National Budget/Nanocomposite (from the Ministry of Education and Science of Ukraine)

Name

Modeling and creation of a new class of crystalline nanocomposites with controlled crystallization and their research in the optical and sub-terahertz wavebands.

Project content

Task of project:

The structure modeling and directed crystallization technology creation of solid materials in mesopores of nanoporous matrices are aimed at solving an important scientific and technical problem of materials science and nanophysics. In particular, manufacturing of a new class of crystalline nanocomposites with controlled crystallization in order to in order to increase the efficiency of their practical use as promising working elements of electro-, acoustic or nonlinear optical devices for infocommunication ones, including defensesystems, as well as optoelectronic sensitive elements of micro- and nanoelectronics.

Object and subject of research:

The object of study is nanoporous matrices with different geometry and pore structure, as well as anisotropic materials with different crystallization geometries in these mesopores. The subject of scientific and technical (experimental) development is modeling, refractive and induced properties of nanoporous matrices and crystal nanocomposites made on their basis with controlled crystallization.

The purpose and main objectives of the study:

The aim of the work is to model and create a new class of crystalline nanocomposites with controlled crystallization geometry and to perform experimental measurements of refractive and induced properties of fabricated nanostructures to assess the prospects of their practical use in a wide range of wavelengths. The main tasks of scientific work are: 1) to model and choose the structure and pore geometry of nanoporous matrices as the "host" of crystalline nanocomposites; 2) to modernize interferometric (based on Michelson and Mach-Zender interferometers) installations for refractive measurements in the optical and quasi-optical ranges; 3) to perform a set of experimental refractive measurements of selected nanoporous matrices in the visible and sub-terahertz wavebands; 4) to model and select the directions of crystallization (global anisotropy maxima) for the studied crystalline material (for example, the ADP groupcrystals) as a "guest" when creating a crystalline nanocomposite with controlled crystallization geometry; 5) to develop the technology of controlled growth of nanocrystallites in the pores of selected receiving matrices with the required geometry and structure of mesopores; 6) to evaluate the spatial anisotropy of refractive and induced optical properties of both the nanoporous structures and crystal nanocomposites based on them with controlled crystallization geometry and evaluate the prospects of their possible practical application in a wide range of wavelengths; 7) to evaluate the possibilities of practical use of manufactured laboratory prototypes of a new class of crystalline nanocomposites with controlled crystallization using ADP and KDP crystals as nanofillers as an example.

The main results

1. At the first stage the analysis of literature sources and methods of research of nanoporous matrices was carried out. In addition, a plan was created to modernize the experimental installations. Also, a literature review was conducted of methods and software for modeling the geometry of structures of nanoporous materials. Algorithms and mathematical models of crystal structures formation were considered and a comparative analysis of crystal and nanoporous structure formation was performed. Based on the analyzed data, a mathematical model was designed and the structure of the nanoporous matrix of anodized alumina was implemented by software, in which the design and analysis is based on the input parameters of the structure and geometric dimensions of the pores. Based on the results of the evaluation, the installations were improved: a) for measuring the refractive indices in the visible wavelength range, b) for measuring the refractive indices in the sub-THz (millimeter) wave range, and c) modified the software part of the the automated experiment control process.
2. At the second stage, a methodology for manufacturing a new class of crystalline nanocomposites with controlled crystallization was developed. To do this, a comparative analysis of existing technologies for growing nanocrystallites, the rate of their crystallization and compliance with appropriate growth conditions was performed. Based on these data, a set of rules and recommendations was formed that can be used to manufacture the appropriate crystalline nanocomposites based on selected nanoporous matrices. In addition, a set of crystalline materials for their growth in the pores of nanoporous matrices was proposed and the based on them possibilities for creating crystalline nanocomposites with controlled crystallization were evaluated. An algorithmic model for the analysis of interaction processes in nanoporous structures was also developed, which made it possible to derive the basic equations and calculate the effective refractive index of the designed crystalline nanocomposites.For this purpose, algorithms for the formation of regular microlevel cell models of the structure of composites based on the use of Bezier curves were described, and the corresponding numerical models and methods of their visualization were given. In addition, with the use of OpenCL parallel computing technology, the methodology of the existing software for 3D analysis of spatial anisotropy and finding the global maximum of induced optical effects was improved. As a result, the analysis rate for the selected material under the same specified conditions was reduced from 12 hours up to 20 minutes. Based on the results of X-ray diffraction analysis of the created nanocomposites and the results of studies of nonlinear optical properties of crystalline materials as fillers of nanoporous matrices and nanocomposites created on their basis, the presence of nanocrystallites in the pores of the studied Al2O3 nanomatrices was shown. The nonlinear optical effect in crystalline nanocomposites was studied on the basis of the second harmonic generationwith the help of the Maker band method, using picosecond pulses of laser radiation at a 1064 nm wavelength. The polarization-dependent effect of the second harmonic generation was observed mainly due to the anisotropy of the macroscopic structure of the KDP / Al2O3 nanocomposite. In addition, atomic force and conventional microscopy of the created nanocomposites was performed. According to the microscopy results,the surface morphology of the created nanostructures information was obtained. The surface quality of the samples is quite low and as a result high-quality polishing of the surface is required for further measurements, because the manufactured nanostructures are not suitable in this form for experimental measurements and development of devices for the optical wavelength range. Also the transmission spectra of the created crystalline nanostructures were measured. The analysis of the spectra shows that the transmission of pure Al2O3 nanostructures in the wavelength range of 0.3–3 ?m increases unexpectedly with decreasing nanopore diameter. In addition, the presence of crystallites in the nanopores leads to a significant increase in the transmission of the created structures Al2O3 + ADP and Al2O3 + KDP. The results of the refractive measurements in the visible range did not give the predicted result using the existing equipment, because the nanostructures are not sufficiently optically transparent and have significant scattering of laser radiation passing through them. In addition, experimental studies were performed in the sub-terahertz range (at a frequency of 33 GHz). In this range, the sensitivity of the devices does not allow to obtain a high-quality interference pattern and, accordingly, to determine the effective refractive index of nanocomposites.
3. At the third stage, the optical properties of the structures were studied based on the grown nanocomposites. To do this, the transmission and reflection spectra of Al2O3 matrices with ADP nanocrystallites were taken with a Shimadzu UV-3600 spectrophotometer.Also, with the Carry 5000 spectrophotometer the transmission spectra with diffuse scattering and diffuse scattering spectra were taken. From the above experimental studies it follows that the transmission and scattering of samples of Al2O3 matrices with ADP crystals in nanopores and without them largely depend on the properties of Al2O3 matrices and their manufacturing technology. However, analyzing the experimental results, the possibility of using the obtained structures with ADP nanocrystallites as filters for the corresponding frequency range, in particular for 0.8-2.6 ?m can be considered.

Originality and innovative aspects

• In comparison with the existing growth methods of water-soluble nanocrystallites and solid nanocrystallites in nanoporous matrices,with our proposed method of growing nanocrystallites from solution, controlled growth of nanocomposites in nanopores of matrices method was developed with growth manipulations by positioning nanoporous matrices at a predetermined angle in a specially designed holder.This positioning, in combination with a certain direction of crystallization, allows to reduce the cost of the hardware of the device for growing nanocomposites and in the future can provide the formation of nanocrystallites of a given crystallization in the nanopores of the studied matrices.
• In addition, we showed the possibility of modeling and more efficient selection of crystallization directions (i.e. global maximum anisotropy) for the electro-optical effect in the studied crystalline material when used as a "guest" to create a nanocomposite with controlled crystallization geometry, which significantly improves efficiency of the use of a new class of crystalline nanocomposites.
• The algorithmic model developed by us for the analysis and study of possible interactions in nanoporous structures, namely for search of an effective refractive index of the designed crystalline nanocomposites based on the used Bezier curves, has a number of advantages in comparison with existing similar approaches, namely: (1) Our model allows to visually show the distribution of radiation passing through the nanomatrix + nanocrystallites system, (2) to perform modeling to determine the effective refractive index of nanostructures in accordance with the pore diameter of the nanomatrix, different nanofillers and predicted pore unevenness.

According to the project materials the oral and poster presentations were made at international conferences:

• N. Andrushchak, D. Vynnyk, A. Andrushchak, V. Haiduchok, Y. Zhydachevskyy, M. Kushlyk, “Optical Properties of Nanoporous Al2O3 Matrices with Ammonium Dihydrogen Phosphate Crystals in Nanopores,” 2018 IEEE 8th International Conference on Nanomaterials: Applications & Properties, NAP 2018, September 9-14, Zatoka (Ukraine).
• N. Andrushchak, P. Goering, A. Andrushchak, “Nanoengineering of Anisotropic Materials for Creating the Active Optical Cells with Increased Energy Efficiency,” 2018 14th International Conference on Advanced Trends in Radioelectronics, Telecommunications and Computer Engineering (TCSET’2018), February 20-24, Lviv-Slavske (Ukraine). – pp. 484-487.
• I. Kityk, A. El-Naggar, A. Albassam, N. Andrushchak, D. Kulwas, P. Czaja, B. Sahraoui, “Coherent Laser Induced Synthesis of Rare Earth Doped Nanocrystallites of 50PbO–25Bi2O3–20Ga2O3–5BaO,” 2018 14th International Conference on Advanced Trends in Radioelectronics, Telecommunications and Computer Engineering, (TCSET’2018), February 20-24, Lviv-Slavske (Ukraine). – pp. 488-491.
• N. Andrushchak, Y. Matviychuk, A. Andrushchak, “Application of a principle of mathematical models reduction for optimal vector of induced optical effects in crystalline materials for optoelectronics,” Proceedings of the 2017 14th International Conference The Experience of Designing and Application of CAD Systems in Microelectronics, CADSM 2017, February 21-25, Polyana (Ukraine). – pp. 70-73.
• N. Jaworski, N. Andrushchak, “A method of nanoporous anodic aluminum oxide structure modeling based on Bezier curves generation,” 2017 14th International Conference The Experience of Designing and Application of CAD Systems in Microelectronics, CADSM 2017, February 21-25, Polyana (Ukraine). – pp. 63-66.
• N. Jaworski, N. Andrushchak, “A Numerical Model of Light Propagation in Porous Composite Structures”, International Conference on Oxide Materials for Electronic Engineering – fabrication, properties and applications, OMEE 2017, May 29 – June 2, Lviv (Ukraine). – p. 91.
• B. Kulyk, N. Andrushchak, B. Sahraoui, A. Andrushchak, “Exploration of Second Harmonic Generation in KDP-Based Crystalline Nanocomposites,” International Conference on Oxide Materials for Electronic Engineering – fabrication, properties and applications, OMEE 2017, May 29 – June 2, Lviv (Ukraine). – p. 92.
• B. Kulyk, N. Andrushchak, P. G?ring, A. Andrushchak, B. Sahraoui, “Nonlinear Optical Response of KDP/Al2O3 Crystalline Nanocomposite,” 2017 IEEE 7th International Conference on Nanomaterials: Applications & Properties, NAP 2017, September 10-15, Zatoka (Ukraine). – pp. 03NNSA26.
• N.A. Andrushchak, O.A. Buryy, V.T. Adamiv, I.M. Teslyuk, A.S. Andrushchak, A.V. Kityk “Development of Crystalline Nanocomposites with KDP crystals as Nanofiller,” International Conference “Nanomaterials: Applications and Properties” (NAP), 2016. – September 14-19, 2016, Lviv (Ukraine). – p. 02NNSA10-1-2.
• A.S. Andrushchak, O.A. Buryy, N.A. Andrushchak, O.M. Yaremko, A. Rusek, A.V. Kityk “Global maxima of linear electro-op tic effect for selected widely used crystalline materials,” International Conference on Advanced Optoelectronics and Lasers (CAOL), 2016. – September 12-15, 2016, Odesa (Ukraine). pp. 176-178.
• N.A Andrushchak, A.V. Kityk, A.S. Andrushchak. “Perspectives of Design of Crystalline Nanocomposites with Tailored Anisotropy as Active Elements in Optoelectronics,” Nanotechnology and Nanomaterials (NANO), 2016, August 24-27, Lviv (Ukraine). – p. 24.

Publications

Within the project the scientific and technical papers were published:

1. N. Andrushchak, I. Karbovnyk, R. Lys, “LabVIEW-based Automated Refractive Index Measurements of Optical Materials Using Red Laser, Measurement Science and Technology, 2018. https://doi.org/10.1177%2F2472630319891133
2. N. Andrushchak, B. Kulyk, P. Goring, A. Andrushchak, B. Sahraoui, “Study of Second Harmonic Generation in KDP/Al2O3 Crystalline Nanocomposite,” Acta Physica Polonica A, vol. 133, pp. 856-859, 2018 http://przyrbwn.icm.edu.pl/APP/SPIS/a133-4.html
3. A. Andrushchak, O. Buryy, N. Andrushchak, Z. Hotra, O. Sushynskyi, G. Singh, V. Janyani, I. Kityk, "General method of extreme surfaces for geometry optimization of the linear electro-optic effect on an example of LiNbO3:MgO crystals," Appl. Opt., vol. 56, Issue. 22, pp. 6255-6262, 2017. https://doi.org/10.1364/ao.56.006255
4. N. Andrushchak, N. Jaworski, M. Lobur, “Improvement of the Numerical Method for Effective Refractive Index Calculation of Porous Composite Materials Using Microlevel Models,” Acta Physica Polonica A, vol. 133, pp. 164-166, 2017. http://doi.org/10.12693/APhysPolA.133.164
5. O. Buryy, N. Andrushchak, A. Ratych, N. Demyanyshyn, B. Mytsyk, and A. Andrushchak, "Global maxima for the acousto-optic effect in SrB4O7 crystals," Appl. Opt., vol. 56, pp.1839-1845, 2017. https://doi.org/10.1364/AO.56.001839

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