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Project titlePhysico-chemical approaches to the synthesis and spectrometric studies of oxide glass ceramics doped with transition metals for elements of optoelectronic devices

Research area 02 - PHYSICS AND SPACE SCIENCES, 02-204 - Nano- and microstructures

KeywordsOptical glass ceramics, borate glass ceramics, silicate glass ceramics, transition metal ions, trivalent chromium ions, divalent manganese ions, luminescence, red phosphor, trivalent titanium ions

Annotation
Currently, laser-optical and optoelectronic technologies, which are customary combined in terms “photonics”, emphasizing the fact that they are based on emitting (absorbing) photons or manipulating photon fluxes, have become one of the drivers of the innovative development of the global economy [Roadmap photonics in the Russian Federation in 2013-2020. Explanatory note]. Today, the functional materials design for optics and photonics is a prerequisite for the development of science and technology of the Russian Federation "Industry of Nanosystems" and critical technologies for “The production and processing of functional nanomaterials”. Transparent glass-ceramic (GC) materials [J.Deubenera, M.Allix et al. Updated Definition of Glass Ceramics, Noncrystalline Solid State Journal, 501, (2018), p. 3-10]. They combine the best properties of crystals and glasses (the possibility of pressing and molding, the possibility of forming geometry elements). In the GC there is the possibility of creating around the activator ensemble ordered and disordered environment simultaneously. At the same time, there are opportunities to combine the properties of the main activators in amorphous and crystalline matrices and to obtain completely new luminescent materials. Material properties in general can vary due to controlled bulk crystallization. This project is aimed at creating new high-performance fluorescent optical glass-ceramic structures based on amorphous oxide matrices doped with ionic transition metals (TM) (chromium, manganese, titanium), which are necessary for the development of the elemental base of optical-electronic systems, in particular, to create efficient radiating systems in the visible and “red” spectral regions (600-800 nm) and / or in detection systems. The laws obtained in the project on the effect of transition metals on the spectral-kinetic characteristics make it possible to obtain luminescent characteristics, which make it possible to obtain information on the optical, physic-mechanical, and luminescent properties. The scientific novelty of the planned research consists in the combined effect of glass or crystalline systems on the optical-luminescent properties of certain transition metal ions of different valences, namely, chromium, manganese and titanium. The choice of the designated transition metals is due to the effective luminescence in both the visible and the "red" spectral region, and the shape and location of the luminescence spectrum of these ions differ from matrix to matrix. At present, due to the development and complication of scientific knowledge, it is customary to conduct focused research, concentrating on studying the properties of certain oxide matrices when they are doped with various activator ions. Because of this, studies of fluorescent GCs are rather scattered. An analysis of the current state of the problem revealed that so far no comprehensive research has been carried out on the effect of the structure and graininess of the glass-ceramic matrix on the optical-luminescent and spectral-kinetic properties. Including there is no systematic study of the relationship between the kinetics of crystallization and sintering of oxide matrices of different composition on the properties of activated additives. The mechanisms of the effect of defects artificially created in a glass-ceramic matrix on the radiative characteristics of a material are not clear enough. Models of optically active centers in nanostructured oxide glass-ceramics activated and not activated by transition metals have not been developed. There is no understanding of the nature of the relationship of structural factors (the size and shape of grains and nanocrystals, their packing density and distribution), the distribution of luminescence centers and spectral-kinetic, color, energy parameters of the glow, the mechanisms of excitation energy transfer in the glass-ceramic matrix. The luminous characteristics of optical GCs, such as quantum yield, emission spectrum, kinetic parameters of luminescence decay, depend on many factors: methods and modes of synthesis, features of the GC microstructure; type, number and distribution of defects (luminescence centers) and dopants. And the problem of systematically managing these parameters, regardless of the basis of the glass-ceramic matrix, is still relevant. The solution of these issues is the key to the implementation of this project. From a practical point of view, this project focuses on a topic of current interest for this industry - the development of materials for efficient radiating systems operating in the red region of the spectrum (600-800 nm) and / or detection systems. From a fundamental point of view, the relevance of the project is related to the study of the relationship of structural, physicochemical, optical and spectral-kinetic characteristics of glass-ceramic materials doped with PM ions. Thus, the project will reveal the general patterns of influence of the composition, structure of the environment of activating ions of chromium, manganese and titanium, the distribution of luminescence centers on spectral-kinetic, color, energy characteristics of the glow, on the mechanisms of transfer of excitation energy and luminescent properties of glass-ceramic materials. Successful implementation of this project will allow us to reach a new level in the approaches to the creation and research of optical materials of a new generation and to gain competitive advantages in such high technology areas as optical electronic devices and systems.

Expected results
During the project, the following results will be obtained: 1) Technological bases for the synthesis of highly efficient glass-ceramic luminescent materials based on optical silicate and borate glasses of composition R2O-R2O3-B2O3-SiO2 doped with transition metal ions (chromium, manganese, titanium) in different valence states (2+, 3+, 4+ ), with the ability to control the spectral and energy characteristics of their luminescence, there will be a synthesis of glasses and glass ceramics of the developed compositions. 2) The interrelation between the processes of energy transfer of luminescence excitation, degradation of ceramics, the wavelength of the excited radiation and temperature will be obtained. 3) In the course of synthesis and research, regularities will be obtained between the structure, chemical composition, parameters of crystalline inclusions (grains) and spectral-kinetic properties of glass-ceramic materials, as well as the luminescent properties of transition metal ions used as dopants. 4) Spectroscopic properties of fluorescent GCs will be investigated at various excitation energy densities, types of energy effects (nanosecond electron beam, laser effects), in a wide temperature range. The degradation resistance of the glass ceramics under study during radiation and temperature exposure will be determined depending on the optical and mechanical properties of the samples. 5) At the final stage of the project, a mock-up sample of the LED emitter with a modified luminescence spectrum will be created on the optical glass-ceramic materials doped with TM ions developed under the project, its efficiency, lighting characteristics, as well as economic feasibility of using as an industrial source of radiation for specific applications will be evaluated. 6) The results will be fully consistent with the world level. According to the results of the project, it is planned to publish 10 articles in foreign journals with Scopus / Web of Science / RSCI indexed databases, including articles with an impact factor greater than 1 (first and second quartiles). The complex of new results will be obtained on the basis of the interdisciplinary approach of the project team, including experts in the field of research of luminescent processes in ceramic and amorphous materials, as well as in materials science and the development of technologies for the synthesis of amorphous / glass-ceramic transparent materials and characterization of their properties. The research results will allow obtaining new luminescent nanostructured glass ceramics with the possibility of directional "design" of spectral and luminescent properties to create efficient radiation converters and effective radiating systems of optoelectronics. Thus, the results of the project are focused on the creation of a technologically independent domestic product, i.e. on import substitution in the field of the optical industry. Young scientists involved in the project implementation, graduate students and students will get a chance to develop their scientific career within the Russian Federation.

Annotation of the results obtained in 2021
The project is dedicated to the development and research of luminescent glass-ceramics that can be used in irradiators for plants. Plants need UV and NIR regions of the spectrum for full growth and development. Most industrial red LEDs produce mostly visible light, not infrared. A stable optical material with both red and infrared luminescence will help replace them and accelerate the development of plants under artificial lighting conditions such as greenhouses. Such a luminescence spectrum can be produced by transition elements in glass-crystalline matrices. During the third year of the project implementation, about 115 compositions of glasses and glass-ceramics were developed and synthesized. The work was divided into two areas: obtaining the red luminescence of titanium ions when they are introduced into the glass matrix as a luminescent additive and the development of glass-ceramics activated by perovskite nanocrystals with luminescence in the red region, using titanium ions as a crystallizer. Out of the developed compositions of the first group, the glasses of the lead-borate matrix with titanium had a visually red luminescence. However, the luminescence intensity of these glasses left much to be desired and was not suitable for the further development of an irradiator for plants. From the compositions of the second group, borogermanate glass-ceramics with CsPbI3 perovskite nanocrystals with luminescence in the region of 650–740 nm and a maximum quantum yield of 37% and glass-ceramics with mixed CsPb(BrxI1–x)3 perovskite nanocrystals with luminescence in the region of 517–695 nm and a maximum quantum yield of 36% were derived. The location of the luminescence maxima in both cases is determined by the composition of the crystal (pure or mixed), as well as the isothermal treatment mode. The advantage of glass-ceramics with perovskite nanocrystals lies in the stability of the luminescent characteristics of these materials in the range up to 200 degrees Celsius. Studies of the mechanical and operational properties of the developed glass-ceramics have shown that they can be used in rooms with high humidity and temperature. However, some limitations are imposed on their use, such as the use of chemically resistant protective coatings, both inorganic and polymeric. As part of the work, a model of an LED glass-ceramic irradiator with a modified spectral composition of radiation was also developed using previously developed borate glass-ceramics with chromium. The modeling process included two main stages: the first stage is the optical-lighting calculation. At this stage, the type of LED was chosen, the optimal value of the thickness of glass-ceramic samples was determined, in which the maximum value of the conversion efficiency of the incident radiation is observed, the selection of secondary optics elements that can be adapted to the task of irradiation was carried out, and the lighting characteristics were evaluated. The second stage of the design consisted in the study and modeling of the irradiator body based on the obtained glass-ceramics as a radiation converter. At this stage, a thermal calculation was carried out, the necessary estimates were made for the heat removal of the developed housing, due to LED radiation sources. We completed all types of work that were planned for the entire period of the project and received the results that we initially expected. A logical continuation of the research carried out within the framework of the project is the refinement of already developed glass-ceramics to obtain the optimal ratio between the transmission and luminescent efficiency of materials for their further use, the development of irradiators’ models for plants based on industrially available LED chips, the selection of optimal radiative and electrical characteristics of the chips, development and implementation of the irradiator design with a modified spectral composition of the radiation, as well as full-scale experiments with plants in greenhouses and evaluation of the practical effectiveness of the developed irradiators on the growth and development of plants.

Publications

1. Anastasiia Babkina, Damir Valiev, Ekaterina Kulpina, Ksenia Zyryanova, Rustam Nuryev, Aleksandra Pavliuk, Natalia Platonova Technological aspects of borate glass–ceramics preparation doped with transition metals for optoelectronic applications Journal of Non-Crystalline Solids, Vol. 570, pp. 121027 (year - 2021) https://doi.org/10.1016/j.jnoncrysol.2021.121027

2. Babkina A., Valiev D., Kulpina E., Pavliuk A., Zyryanova K., Monogarova A., Ignatiev A., Kuzmenko N., Zhizhin E., Koroleva A. Intense red emission of mixed-alkali rare-earth free germanate glass-ceramics with Mn ions Optical materials Express, Vol. 12, No. 5, p. 2072-2086 (year - 2022) https://doi.org/10.1364/OME.458233

3. Babkina A.N., Kovova M.S., Kulpina E.V., Pavliuk A.S., Zyryanova K.S., Monogarova A.A., Bukhvostov A.I., Ignatiev A.I., Nuryev R.K. Mn4+ concentration effect on spectral properties of lithium-germanate glass-ceramics Journal of Physics: Conference Series, Vol. 2086, No. 1, pp. 012129 (year - 2021) https://doi.org/10.1088/1742-6596/2086/1/012129

4. A N Babkina, M S Kovova, E V Kulpina, A S Pavlyuk, K S Zyryanova, A I Bukhvostov Mn4+ concentration effect on spectral properties of lithiumgermanate glass-ceramics "Saint Petersburg OPEN 2020" BOOK of ABSTRACTS. HSE University - St. Petersburg, p.235-236 (year - 2021)

5. Babkiba A.N., Kovova M.S., Kulpina E.V., Pavliuk A.S., Zyryanova K.S., Bukhvostov A.I., Huryev R.K., Ignatiev A.I. ВЛИЯНИЕ КОНЦЕНТРАЦИИ ИОНОВ Mn4+ НА СПЕКТРАЛЬНЫЕ СВОЙСТВА ЛИТИЕВОГЕРМАНАТНОЙ СТЕКЛОКЕРАМИКИ «Стекло: наука и практика» GlasSP2021: Сборник тезисов Третьей Российской конференции с международным участием, – СПб: ООО Издательство «ЛЕМА», c. 136-137 (year - 2021)

6. D.T. Valiev, K. Zyryanova, A. Babkina, A.Yu. Osipova LUMINESCENT PROPERTIES OF GLASS CERAMICS WITH VARIABLE ANNEALING DURATION Pulsed Lasers and Laser Applications (AMPL-2021) : Abstracts of XV International Conference. – Tomsk : STT, p.69-70 (year - 2021)

7. Kulpina E.V., Babkina A.N., Bukhvostov A.I., Zyryanova K.S. ИССЛЕДОВАНИЕ ВЛИЯНИЯ ЛИТИЯ И СУРЬМЫ НА СПЕКТРАЛЬНЫЕ СВОЙСТВА ЩЕЛОЧНОАЛЮМОБОРАТНЫХ СТЕКЛОКЕРАМИК, АКТИВИРОВАННЫХ ХРОМОМ «Стекло: наука и практика» GlasSP2021: Сборник тезисов Третьей Российской конференции с международным участием, – СПб: ООО Издательство "ЛЕМА", с. 108-109 (year - 2021)

Annotation of the results obtained in 2019
The project is dedicated to the development and study of luminescent glass-ceramics that can be used in irradiators for plants. The fact is that plants need UV and near-infrared spectral regions for full growth and development. Most industrial red LEDs produce mostly visible radiation, not reaching infrared. Stable optical material with luminescence in both the red and infrared regions will help replace them and accelerate the development of plants under artificial lighting, for example, in greenhouses. Such a spectrum of luminescence can be produced by transition elements in glass-crystalline matrices. Each of the three years of the project is dedicated to one transition element and its luminescent properties when introduced into a glass or glass-crystalline medium. The first year of the project is devoted to the development of chromium-doped glass-ceramics. Why glass-ceramics, not glass? Glass-ceramics are more durable and chemically resistant than glass. Why glass-ceramics, not crystals? The process of producing crystals is quite complicated, long and expensive. Moreover, if we are talking about powder ceramics, then in them, as in crystals, transition elements can occupy only strictly defined positions in the crystal lattice. For most crystalline compounds, the positions where dopant ions can be embedded are known, as well as the luminescent properties of materials with them. Glass-ceramics is a transitional link between crystalline and glassy, and combines a low production cost, and some uncertainty when doped with fluorescent additives. This uncertainty is not a disadvantage, but an advantage: being able to control the environment of transition metal ions, it is possible to flexibly change the luminescent properties of the material. In the first year of the project, about 100 glass and glass-ceramics compositions were developed and synthesized. There were two quality criteria for a glass matrix: firstly, it should be optically transparent in the visible range, and secondly, it should be prone to crystallization. From all the selected compositions, we realized that the most suitable is an alkali-aluminum borate matrix, in which two alkalis are simultaneously introduced in equal amounts: potassium and lithium. Potassium plays the role of a glass-forming ion, and lithium increases the tendency of the matrix to crystallize. An important aspect was the large amount of aluminum in the glass. Chromium ions were very close in radius to aluminum ions and were easily integrated into the structure in the same vacant places. During the project, it turned out that chromium during synthesis in the air atmosphere became hexavalent. This type of chromium did not have luminescence. The selection of reducing agents showed that antimony transferred chrome to a trivalent state, bypassing the tetravalent state. Thus, a separate study was born of the effect of redox conditions in a glass melt on the luminescent properties of chromium ions. The more antimony was introduced to the glass, the more chromium was transferred to the trivalent state, the better the glass-ceramic shone. Several pitfalls were found in the technology of glass-ceramics synthesis. The fact was that the region of exothermic reactions in these compositions laid at high temperatures, which were close to softening, read - destruction, of the matrix. We had to balance on a fine line between to form as many crystals in the glass as possible, and so that it would not melt. Therefore, we determined the optimal technological regime for the synthesis of glass-ceramics. The quantum yield of luminescence in the first successful compositions was about 14%. We continued to modify the composition, regulate the synthesis technology, study the lifetime, quantum yield, and absorption spectra of glass-ceramics, even created defects in them by an electron beam, and obtained cathodoluminescence spectra. The last study turned out to be rich in fundamental results, because before that, almost no one had studied glass-ceramics under an electron beam. Finally, the maximum quantum yield of luminescence that we were able to obtain was 50%. Compared to laser crystals, which had a quantum yield of about 98%, this was not much, but compared to luminescent glass, it was quite good. We completed all types of work that were planned for the first year of the project and got the results that we expected. We will continue these studies outside the framework of the project in the next years in order to achieve more interesting results and get closer to their implementation.

Publications

1. A.N. Babkina, K.S. Zyryanova, D.A. Agafonova, R.K. Nuryev, A.I. Ignatiev, D. Valiev The effect of chromium concentration on luminescent properties of alkali-alumina- borate glass-ceramics Journal of Non-Crystalline Solids, Babkina A.N., Zyryanova K.S., Agafonova D.A., Nuryev R.K., Ignatiev A.I., Valiev D. The effect of chromium concentration on luminescent properties of alkali-alumina-borate glass-ceramics // Journal of Non-Crystalline Solids - 2019, Vol. 521, pp. 119487 (year - 2019) https://doi.org/10.1016/j.jnoncrysol.2019.119487

2. Babkina A.N., Valiev D.T., Zyryanova K.S., Osipova A., Aseev V.A., Kulpina E.V., Nuryev R.K. Luminescent properties of chromiumdoped borate glass-ceramics for red radiation sources Proceedings of SPIE, Vol. 11357, pp. 113570A-1 - 113570A-8 (year - 2020) https://doi.org/10.1117/12.2555370

3. Valiev D.T., Babkina A.N., Zyryanova K.S., Nuryev R.K., Ignatiev A.I., Osipova A.Y. Radiation-induced processes in alkali-alumina-borate glass-ceramics doped with Cr3+ ions Journal of Non-Crystalline Solids, Vol. 534, pp. 119947 (year - 2020) https://doi.org/10.1016/j.jnoncrysol.2020.119947

4. D. Valiev, A. Babkina, K. Zyryanova, D. Agafonova, K. Oreshkina, A. Osipova Luminescent properties of Li2O-K2O-Al2O3-B2O3 glass-ceramics doped with Cr3+ ions Proceedings of the 14th International Forum on Strategic Technology (IFOST 2019), Tomsk: TPU Publishing House, IEEE, Proceedings of the 14th International Forum on Strategic Technology (IFOST 2019) - 2019, pp. 91-94 (year - 2019)

Annotation of the results obtained in 2020
The project is dedicated to the development and research of luminescent glass-ceramics that can be used in irradiators for plants. Plants need UV and NIR regions of the spectrum for full growth and development. Most industrial red LEDs produce mostly visible light, not infrared. A stable optical material with both red and infrared luminescence will help replace them and accelerate the development of plants under artificial lighting conditions such as greenhouses. Such a luminescence spectrum can be produced by transition elements in glass-crystalline matrices. During the second year of the project implementation, about 70 glass compositions and glass-ceramics based on them were developed and synthesized. There were two quality criteria for a glassy matrix: firstly, it must be optically transparent in the visible range, and secondly, it must be prone to crystallization. Of all the possible valence states of manganese, we were most interested in the 4+ state, which gives intense red luminescence. However, divalent manganese also meets the requirements for creating radiation sources, and at the same time it is the most stable modification of this ion. Tetravalent manganese is an intermediate state, and therefore, within the framework of the project, it was necessary to determine the conditions under which manganese ions pass exactly into the 4+ state. Of all the formulations developed, only two met both criteria for choosing a matrix: alkaline-borate and alkaline-germanate. However, in alkali-borate glass, manganese ions remained in a bivalent state even after crystallization of the matrix, while the intensity of their luminescence in all the developed compositions was minimal. Therefore, it was decided to change the criteria for choosing a matrix to: (1) transparency in a wide spectral range and (2) intense manganese luminescence. Based on these criteria, a borate matrix with alkaline earth elements was selected. In it, it was possible to transfer most of the manganese ions into a bivalent state, so that the maximum quantum yield of their luminescence reached 22%. The only matrix in which it was possible to create manganese ions in the tetravalent state was the alkali-germanate one. In the process of glass crystallization, crystals of the R2O-7GeO2 type (where R = Li, K, Na) were precipitated, in which germanium had an oxidation state of 4+. In this case, the radius of germanium coincided with the ionic radius of Mn 4+, which created favorable conditions for the entry of manganese into the crystalline phase by replacing germanium. Alkaline germanate glass-ceramics showed luminescence in the red region (660-680 nm), which was the goal of development at the second stage of the project. We have completed all types of work that were planned for the second year of the project and received the results we expected. We will continue this research outside the scope of the project in the future in order to improve the luminescence characteristics of the obtained tetravalent manganese glass-ceramics and get closer to their implementation. The results of the projects were covered by the media in several articles that can be found on the Naked Science portal (https://naked-science.ru/article/column/v-itmo-predlozhili-novyj-sposob-uskorit-rost-rastenij), Siberian Science News (http://www.sib-science.info/ru/heis/steklokeramika-pomozhet-19062020) and ITMO University News portal (https://news.itmo.ru/ru/science/new_materials/news/9523/).

Publications

1. Babkina A.N., Valiev D.Т., Zyryanova K.S., Nuryev R.K., Ignatiev A.I., Kulpina E.V., Kuzmenko N., Osipova A.Y., Koroleva A., Platonova N. Spectroscopic properties of chromium/antimony co-doped alkali-alumina-borate glass-ceramics Optical Materials, Volume 106, pp. 109983 (year - 2020) https://doi.org/10.1016/j.optmat.2020.109983

2. E. Kulpina, A. Babkina, K. Zyryanova, A. Bukhvostov, N. V. Platonova Chromium-doped borate glass ceramics for optical temperature sensors Proceedings of SPIE, Vol. 11772, pp. 117721G (year - 2021) https://doi.org/10.1117/12.2589152

3. Kulpina E., Babkina A., Zyryanova K. Antimony concentration effect on luminescent properties of chromium-doped borate glasses AIP Conference Proceedings, Vol. 2308, pp. 060004 (year - 2020) https://doi.org/10.1063/5.0033252

4. Kulpina E.V., Babkina A.N., Zyryanova K.S. Исследование влияния лития на люминесцентные свойства хромсодержащей боратной стеклокерамики X МЕЖДУНАРОДНАЯ КОНФЕРЕНЦИЯ ПО ФОТОНИКЕ И ИНФОРМАЦИОННОЙ ОПТИКЕ: Сборник научных трудов, С. 207-208 (year - 2021)

5. Kulpina E.V., Babkina A.N., Zyryanova K.S. Влияние температуры на люминесцентные свойства стеклокерамики с добавками хрома: in situ измерения Сборник трудов XI Международной конференции «Фундаментальные проблемы оптики–2020», С. 282-283 (year - 2020)

6. - В ИТМО предложили новый способ ускорить рост растений Naked Science, - (year - )

7. - Ученые нашли способ, как ускорить рост растений благодаря лампам со стеклокерамикой ITMO.NEWS, - (year - )

8. - Исследователи нашли способ ускорить рост растений Новости сибирской науки, - (year - )