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Project titleDevelopment of plasmonic nanostructures based on aluminum and platinum nanoparticles using the aerosol printing method for efficient enhancement of ultraviolet radiation

Research area 09 - ENGINEERING SCIENCES, 09-710 - New materials for nano-electronic devices

Keywordsaluminum and platinum nanoparticles, plasmonic-enhanced luminescence , nanoplasmonics, ultraviolet light, gas discharge, aerosol printing

Annotation
The aim of the project is to solve the problem of the formation of plasmonic nanostructures using aerosol printing with "dry" gas-discharge nanoparticles of aluminum and platinum as a source in order to produce pasmon structures that can multiply enhance the luminescence of zinc aluminate (ultraviolet phosphor) in the ultraviolet region in the range of wavelength from 200 to 315 nm. And then to study the interaction between ultraviolet radiation with zinc aluminate films with deposited plasmonic structures with different surface density and packing of nanoparticles. Within the framework of the project, for the first time, the influence of the parameters of a pulse-periodic gas discharge on the dimensional and optical properties of aluminum and platinum nanoparticles will be investigated, including the process of laser and thermal modification of aerosol in a gas flow. Scientific and technical foundations for creating plasmonic nanostructures on the surface of a clean substrate and zinc aluminate films by aerosol printing methods with various patterns of nanoparticles on the surface, particle packing density in order to create "hot spots" capable of multiplying the electromagnetic field will be developed. Methods for stabilization of liquid dispersions of zinc aluminate and their mixtures with aluminum nanoparticles synthesized in a gas discharge will also be developed. For the first time, the processes of enhancement/ quenching of luminescence in solutions of mixtures of aluminum nanoparticles and zinc aluminate will be investigated in order to create homogeneous film structures from liquid dispersions by various methods. Then, simulated and experimental data about enhancement factor of cathodoluminescence and photoluminescence in the bactericidal ultraviolet range in zinc aluminate films depending on the film thickness will be obtained via parameters of the obtained nanostructure, size and morphology of aluminum and platinum nanoparticles, and preparation conditions. The research results have a real possibility of practical application in the production of cathodoluminescence and luminescent lamps of the bactericidal range of radiation, increasing the conversion efficiency of ultraviolet radiation in solar batteries, in gas, chemical and biological sensors.

Expected results
1. Dependences of the dimensional parameters, morphology, phase composition, and optical properties of aluminum and platinum nanoparticles on the synthesis conditions in a gas discharge: the composition of the atmosphere, the diameter and bevel angle of the electrodes. 2. Relationship of morphology, shape and optical properties of aluminum and platinum nanoparticles and parameters of laser modification of nanoparticles, namely, laser wavelength (from the series 355, 527 and 1053 nm), energy density, repetition rate and number of pulses. Dependences of the optical properties and sizes of metal nanoparticles on the temperature of additional aerosol sintering in a gas flow. 3. Technological basics for creating plasmonic structures based on metal nanoparticles on a quartz substrate and zinc aluminate films by aerosol printing methods with different surface densities and patterns (lines, grids, etc.), allowing to create a nanostructure that multiply increases the intensity of the electromagnetic field. Dependences of the optical properties of nanostructures on the surface density of particles and patterns. 4. Methods of manufacturing stable liquid dispersions of zinc aluminate particles with different size parameters using ultrasonic dispersion and accelerated sedimentation in a centrifugal field. Techniques for obtaining homogeneous zinc aluminate films from liquid dispersions by various methods, for example, immersion, electrophoretic deposition, centrifugation, aerosol printing. 5. Dependences of the luminescent properties of zinc aluminate films on the surface microstructure, film thickness and production method. 6. Simulated dependences of the surface plasmon resonance of an ensemble of aluminum and platinum nanoparticles, as well as the factor of enhancing the luminescence of zinc aluminate on the size of metal nanoparticles, their mutual arrangement and surface density. 7. Methods for making stable suspensions of mixtures of zinc aluminate and aluminum particles. Technological basics for creating homogeneous films of zinc aluminate and metal nanoparticles from liquid dispersions of mixtures by various methods, for example, immersion, electrostatic deposition, centrifugation, aerosol printing. 8. Dependences of the gain / quenching of the luminescence of zinc aluminate in liquid dispersions on the size of nanoparticles of aluminum and zinc aluminate and their mutual concentration. 9. Relationship between the luminescence properties of zinc aluminate films in the presence of aluminum nanoparticles made from liquid dispersions of mixtures, and the thickness, microstructure of the films, surface concentration of metal nanoparticles. 10. Dependences of the spectral-luminescent and cathodoluminescent properties of zinc aluminate films with applied plasmonic structures and without them on the method of obtaining films and structures, film thickness, pattern, size and surface concentration of aluminum and platinum nanoparticles. The optimal conditions for the creation of film plasmon nanostructures based on aluminum and platinum nanoparticles will be determined, which will make it possible to multiply amplify ultraviolet radiation in the range from 200 to 315 nm. The planned scientific results correspond to the world level of research, meet the requirements of a promising direction in photonics and solar energy - the creation of new manufacturing methods and materials for multiple plasmon amplification of electromagnetic radiation in the ultraviolet range from 200 to 315 nm. The development of new principles for the creation of plasmonic structures by aerosol printing methods and the study of the effect of aluminum and platinum nanoparticles on the spectral and luminescent properties of the UV phosphor zinc aluminate involves obtaining new fundamental and applied knowledge on (1) the synthesis of metal nanoparticles in a repetitively pulsed gas discharge with various optical properties. , (2) the features of the deposition of metal nanoparticles on substrates and the fabrication of nanostructures with different surface density of nanoparticles, (3) the dependences of the cathode and photoluminescent properties of the phosphor on the surface concentration, location and size of aluminum and platinum nanoparticles, (4) stabilization of liquid dispersions of zinc aluminate nanoparticles and their mixtures with nanoparticles, features of the interaction of ultraviolet radiation in solutions of plasmon particles and phosphor. The research results have a real possibility of early practical use in economics in the production of cathode and luminescent lamps of the bactericidal range of radiation, increasing the conversion efficiency of ultraviolet radiation in solar batteries, in gas, chemical and biological sensors. 1. Dependences of the dimensional parameters, morphology, phase composition, and optical properties of aluminum and platinum nanoparticles on the synthesis conditions in a gas discharge: the composition of the atmosphere, the diameter and bevel angle of the electrodes. 2. Relationship of morphology, shape and optical properties of aluminum and platinum nanoparticles and parameters of laser modification of nanoparticles, namely, laser wavelength (from the series 355, 527 and 1053 nm), energy density, repetition rate and number of pulses. Dependences of the optical properties and sizes of metal nanoparticles on the temperature of additional aerosol sintering in a gas flow. 3. Technological basics for creating plasmonic structures based on metal nanoparticles on a quartz substrate and zinc aluminate films by aerosol printing methods with different surface densities and patterns (lines, grids, etc.), allowing to create a nanostructure that multiply increases the intensity of the electromagnetic field. Dependences of the optical properties of nanostructures on the surface density of particles and patterns. 4. Methods of manufacturing stable liquid dispersions of zinc aluminate particles with different size parameters using ultrasonic dispersion and accelerated sedimentation in a centrifugal field. Techniques for obtaining homogeneous zinc aluminate films from liquid dispersions by various methods, for example, immersion, electrophoretic deposition, centrifugation, aerosol printing. 5. Dependences of the luminescent properties of zinc aluminate films on the surface microstructure, film thickness and production method. 6. Simulated dependences of the surface plasmon resonance of an ensemble of aluminum and platinum nanoparticles, as well as the factor of enhancing the luminescence of zinc aluminate on the size of metal nanoparticles, their mutual arrangement and surface density. 7. Methods for making stable suspensions of mixtures of zinc aluminate and aluminum particles. Technological basics for creating homogeneous films of zinc aluminate and metal nanoparticles from liquid dispersions of mixtures by various methods, for example, immersion, electrostatic deposition, centrifugation, aerosol printing. 8. Dependences of the gain / quenching of the luminescence of zinc aluminate in liquid dispersions on the size of nanoparticles of aluminum and zinc aluminate and their mutual concentration. 9. Relationship between the luminescence properties of zinc aluminate films in the presence of aluminum nanoparticles made from liquid dispersions of mixtures, and the thickness, microstructure of the films, surface concentration of metal nanoparticles. 10. Dependences of the spectral-luminescent and cathodoluminescent properties of zinc aluminate films with applied plasmonic structures and without them on the method of obtaining films and structures, film thickness, pattern, size and surface concentration of aluminum and platinum nanoparticles. The optimal conditions for the creation of film plasmon nanostructures based on aluminum and platinum nanoparticles will be determined, which will make it possible to multiply amplify ultraviolet radiation in the range from 200 to 315 nm. The planned scientific results correspond to the world level of research, meet the requirements of a promising direction in photonics and solar energy - the creation of new manufacturing methods and materials for multiple plasmon amplification of electromagnetic radiation in the ultraviolet range from 200 to 315 nm. The development of new principles for the creation of plasmonic structures by aerosol printing methods and the study of the effect of aluminum and platinum nanoparticles on the spectral and luminescent properties of the UV phosphor zinc aluminate involves obtaining new fundamental and applied knowledge on (1) the synthesis of metal nanoparticles in a repetitively pulsed gas discharge with various optical properties. , (2) the features of the deposition of metal nanoparticles on substrates and the fabrication of nanostructures with different surface density of nanoparticles, (3) the dependences of the cathode and photoluminescent properties of the phosphor on the surface concentration, location and size of aluminum and platinum nanoparticles, (4) stabilization of liquid dispersions of zinc aluminate nanoparticles and their mixtures with nanoparticles, features of the interaction of ultraviolet radiation in solutions of plasmon particles and phosphor. The research results have a real possibility of early practical use in economics in the production of cathode and luminescent lamps of the bactericidal range of radiation, increasing the conversion efficiency of ultraviolet radiation in solar batteries, in gas, chemical and biological sensors.

Annotation of the results obtained in 2022
1. In the course of the work, the processes of synthesis of aerosol aluminum nanoparticles in spark discharge in an argon atmosphere were investigated, depending on the diameter and angle of the bevel of the electrodes, additional laser modification (with wavelengths of 527 and 1053 nm), morphology, dimensional parameters and optical properties of nanoparticles were studied. It was found that the diameter of the electrodes significantly affects the synthesis and the average size of the primary nanoparticles. It is revealed that at the wavelengths of 527 and 1053 nm with a given power, a partial modification of the morphology of aluminum particles occurs. It is shown that all the obtained aluminum nanoparticles have a peak of plasmon absorption in the ultraviolet region in the range from 205 to 260 nm. 2. Technological bases for forming film nanostructures from spark discharge aluminum nanoparticles on the surface of quartz glass with different patterns (lines, grid, uniform distribution) and concentration of "hot spots" by aerosol printing methods have been developed, the microstructure of the surface and optical properties of aluminum films have been studied. It is revealed that an increase in the gas flow velocity, the number of layers and a decrease in the velocity of the substrate relative to the nozzle leads to an increase in the width of the line obtained from spark discharge aluminum particles. Samples of aluminum nanostructures with different patterns on the surface were obtained: a set of lines, a grid, homogeneous films with different relative surface densities of nanoparticles. 3. Methods have been developed for the manufacture and stabilization of suspensions of zinc aluminate particles in isopropyl solution with a concentration of nanoparticles from 0.1 to 10 g/l with various sizes by ultrasonic processing and sedimentation in a centrifugal field. The optical and dimensional properties of the obtained dispersions are investigated. It is shown that the suspensions have aggregative stability for 14 days and are characterized by intense photoluminescence in the ultraviolet region in the range of 304 – 360 nm. 4. Homogeneous film structures of zinc aluminate were made from suspensions by microplotter printing, drop and dip-coating methods, thickness, surface microstructure and spectral properties of the obtained films were investigated. It is shown that the uniformity and microstructure of films, as well as the intensity of photoluminescence of zinc aluminate in films, significantly depends on the method of their formation. 5. Within the framework of the Mi formalism, the extinction spectra of aluminum nanoparticles and the photoluminescence enhancement factor of ultraviolet phosphor in the presence of aluminum nanoparticles of various sizes and the distance between the emitter and the nanoparticle were calculated. Optimal conditions for the location and size of aluminum and zinc aluminate nanoparticles have been established to achieve maximum luminescence amplification. 6. Methods of sequential layer-by-layer deposition of aluminum and zinc aluminate nanoparticles on quartz glass by microplotter printing methods, as well as a combination of dry aerosol and microplotter printing methods have been developed. Optimal parameters of dry aerosol printing have been determined, including gas flow, the velocity of the substrate relative to the nozzle, and the focal length. Plasmonic nanostructures of aluminum nanoparticles with different patterns have been obtained, which make it possible to enhance the luminescence of ultraviolet phosphors.

Publications

1. A.A.Lizunova, D. Malo, D.V. Guzatov, I.S. Vlasov, E.I. Kameneva, I.A. Shuklov, M.N. Urazov, A.A. Ramanenka, V.V. Ivanov Plasmon-Enhanced Ultraviolet Luminescence in Colloid Solutions and Nanostructures Based on Aluminum and ZnO Nanoparticles Nanomaterials, MDPI, Nanomaterials 2022, 12, 4051. https:// doi.org/10.3390/nano12224051 (year - 2022) https://doi.org/10.3390/nano12224051

2. D.Malo, A.A.Lizunova, M.Nouraldeen, V.I.Borisov, V.V.Ivanov ALUMINUM NANOSTRUCTURES PRODUCED BY AEROSOL DRY PRINTING FOR ULTRAVIOLET PHOTOLUMINESCENCE ENHANCEMENT Научно-технические ведомости СПбГПУ. Физико-математические науки, - (year - 2022)

Annotation of the results obtained in 2023
Ultraviolet photoluminescence at a wavelength of 377 nm was studied for zinc oxide films of various thicknesses formed by microplotter printing from liquid dispersions, pure ones and deposited on plasmonic structures based on agglomerates of aluminum nanoparticles synthesized in a gas discharge with average sizes of primary particles from 15 to 30 nm. Aluminum nanostructures were produced by dry aerosol printing with different surface densities of nanoparticles and patterns on quartz glass (E.I. Kameneva, A.A. Lizunova, E.M. Filalova, D. Malo, D.V. Kornyushin, V.V. Ivanov. Technology of manufacturing thin-film aluminum nanostructures by dry aerosol printing , https://spb.hse.ru/mirror/pubs/share/874927492). It has been established that the effects of plasmonic enhancement of zinc oxide luminescence manifest themselves more significantly (with an enhancement factor of up to 5) in thin films of UV phosphor (less than 10 nm) with the use of plasmonic structures of aluminum nanoparticles with a low optical density of less than 0.1, the size of the metal particles and the order of formation aluminum and zinc oxide films also affect the plasmon-enhancement factor. A method has been developed for obtaining solutions of zinc aluminate in isopropyl alcohol with citric acid, stable for a month, in a mixture with aluminum nanoparticles of low concentration less than 0.2 g/l, obtained in a gas discharge. Cathodoluminescence in the range of 240-260 nm in thin films of zinc aluminate and powders in the presence of aluminum nanoparticles was studied. The quenching of cathodoluminescence in zinc aluminate powders and a slight enhancement in films in the presence of aluminum nanoparticles were shown. The photoluminescence of zinc oxide in liquid mixtures with aluminum nanoparticles of various sizes and concentrations was studied. An increase in the luminescence of ZnO at a wavelength of 377 nm was shown to be up to 2.4 times in the presence of aluminum nanoparticles with a size of 20-26 nm, obtained in a gas discharge (D. Malo, A. A. Lizunova, O. V. Vershinina, E. M. Filalova, V. V. Ivanov. Ultraviolet photoluminescence enhancement of zinc oxide nanocrystals in colloidal mixtures with spark discharge aluminum nanoparticles, https://spb.hse.ru/mirror/pubs/share/874927492). The influence of the parameters of additional laser modification in a gas flow (wavelengths of 355, 527 and 1053 nm and radiation power) on the dimensional and optical properties of aluminum and platinum nanoparticles synthesized in a gas discharge was studied. It has been shown that the maximum power (250 mW) of an ultraviolet laser with radiation at a wavelength of 355 nm in the range of gas flows from 50 to 600 ml/min is not enough to completely modify aluminum and platinum nanoparticles synthesized in a gas discharge and transform the morphology from submicron agglomerates to individual large metal nanoparticles. The dependence of the dispersed composition of nanoparticles after thermal treatment on the gas flow has been studied. Platinum particles with sizes from 6 to 105 nm and a plasmonic absorption peak in the mid-ultraviolet region from 265 to 280 nm were obtained (O. V. Vershinina, E. M. Filalova, A. A. Lizunova, E. S. Khramov, V. V. Ivanov. The effect of laser radiation on properties of platinum nanoparticles produced in a gas discharge, https://spb.hse.ru/mirror/pubs/share/874927492). The extinction spectra of platinum nanoparticles were modeled using the Mie theory. Calculations of the field enhancement factor on monodisperse and polydisperse platinum nanoparticles with particle size distributions similar to those obtained experimentally in a gas discharge were studied for various emitter wavelengths in the ultraviolet region and distances between the surface of the platinum nanoparticle and the phosphor.

Publications

1. A. A. Lizunova, V. I. Borisov, D. Malo, A. G. Musaev, E. I. Kameneva ,A. A. Efimov ,I. A. Volkov ,A.I. Buchnev ,I.A. Shuklov and V.V. Ivanov Spark Discharge Synthesis and Characterization of Ge/Sn Janus Nanoparticles Nanomaterials MDPI, Nanomaterials 2023, 13(10), 1701; https://doi.org/10.3390/nano13101701 (year - 2023) https://doi.org/10.3390/nano13101701

2. A. A. Lizunova, V. I. Borisov, D. Malo, A. G. Musaev, E. I. Kameneva, V.V. Ivanov Technology of manufacturing thin-film aluminum nanostructures by dry aerosol printing St Petersburg Polytechnic University Journal-Physics and Mathematics, - (year - 2023)

3. D. Malo, A. A. Lizunova, O. V. Vershinina, E. M. Filalova, V. V. Ivanov Ultraviolet photoluminescence enhancement of zinc oxide nanocrystals in colloidal mixtures with spark discharge aluminum nanoparticles Научно-технические ведомости СПбГПУ. Физико-математические науки. St. Petersburg State Polytechnical University Journal. Physics and Mathematics, - (year - 2023)

4. O.V. Vershinina, E.M. Filalova, M.F. Kerechanina, M.N. Urazov, E.S. Khramov, A.A. Lizunova THE EFFECT OF LASER RADIATION ON THE PROPERTIES OF PLATINUM NANOPARTICLES PRODUCED IN A GAS DISCHARGE Научно-технические ведомости СПбГПУ. Физико-математические науки, vol. 16, no. 3.1, pp. 138–143. (year - 2023) https://doi.org/10.18721/JPM.163.125.4.