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Article

The Effects of the Incorporation of Luminescent Vanadate Nanoparticles in Lithium Borate Glass Matrices by Various Methods

by
Oksana Chukova
1,2,3,*,
Ihor Fesych
1,
Tetiana Voitenko
1,
Volodymyr Baran
2,
Aleksei Kotlov
2,
Robin L. Conner
3,
Luiz G. Jacobsohn
3,
Alexandra Manousaki
4 and
Emmanuel Stratakis
4
1
Faculty of Chemistry, Taras Shevchenko National University of Kyiv, Volodymyrska Str. 64/13, 01601 Kyiv, Ukraine
2
FS-PETRA-S, Deutsches Elektronen-Synchrotron DESY, Notkestr. 85, 22607 Hamburg, Germany
3
Department of Materials Science and Engineering, Clemson University, Clemson, SC 29634, USA
4
Institute of Electronic Structure & Laser, IESL-FORTH, Vassilika Vuton 100, 71110 Heraklion, Greece
*
Author to whom correspondence should be addressed.
Solids 2024, 5(4), 485-498; https://doi.org/10.3390/solids5040032
Submission received: 3 September 2024 / Revised: 27 September 2024 / Accepted: 2 October 2024 / Published: 5 October 2024
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Abstract

:
The glass-ceramic materials studied in this work are designed using combinations of lithium vanadate borate glass matrices and lanthanum/rare earth (RE) vanadate nanoparticles. Three different techniques of sintering of the glass matrix and vanadate nanoparticles are investigated. The morphological characteristics and spectral properties of the glass-ceramic samples obtained by different techniques are investigated and analyzed in comparison with the properties of the original glass matrices and nanoparticles. The luminescence spectra of all glass-ceramic samples consist of a wideband glass matrix emission and the characteristic line emission of the RE ions that are incorporated into the glass matrices as nanoparticles. The RE luminescence of these glass-ceramics is promising for various optoelectronic applications.

1. Introduction

The development of new efficient luminescent glass and glass-ceramic materials is an important practical task, as such materials are used in various applications across different industries. Luminescent materials are used in the production of phosphors for LEDs, and they also can be integrated into optoelectronic devices, such as lasers and amplifiers, for applications in telecommunications and data transmission [1,2,3,4,5,6]. Oxide-based glass-ceramics are a promising class of solid-state materials that combine the characteristics of both glasses and ceramics. The basic structure of oxide-based glass-ceramics consists of a glassy matrix containing crystalline particles that are dispersed throughout. This combination provides several advantages, such as thermal stability, chemical inertness, mechanical strength, and optical transparency.
Thus, efforts to develop efficient luminescent glass and glass-ceramic materials contribute to advancements in these various fields, promoting energy efficiency, improved performance, and innovative applications in technology and design [7,8,9,10,11,12]. The most common technique for obtaining glass-ceramics is based on controlled crystallization of certain glasses, resulting in a material with a crystalline structure embedded in a glassy matrix [13,14,15]. According to this technique, glass-ceramics are produced through a two-step process. In the first step, a glass is formed by cooling a molten mixture. In the second step, this glass is subjected to a controlled heat treatment to induce crystallization. Another well-known method is sol–gel synthesis, which involves the conversion of a colloidal suspension (sol) into a gel and subsequent heat treatment to obtain a glass-ceramic material. The sol–gel approach can include hydrothermal treatments, where the glass precursor is subjected to crystallization in a water-based environment under high-pressure and -temperature conditions [16,17,18]. However, none of these methods work if the aim is to incorporate already prepared crystalline nanoparticles into a glass matrix. But just the incorporation of pre-synthesized luminescent nanoparticles into a glass matrix is currently an actual task for the development of new luminescent materials that can be integrated into optoelectronic devices.
In contrast to the spontaneous crystalline phase formation in a glass, the incorporation of pre-synthesized crystalline nanoparticles allows for direct control of the size and concentration of crystalline areas in a glass matrix. The techniques that can be used for the creation of glass-ceramic materials from two different pre-synthesized components are the powder sintering process and the cooling template-assisted method. In the first technique, glass-ceramics can be produced from glass powder by sintering it with a crystalline component [19,20,21,22,23]. In the latter technique, the cooling of the melted glass is carried out into a template with a crystalline component. A third feasible way is to add crystalline components to the glass-forming blend before the glass synthesis. However, this method does not guarantee that the shapes, sizes, and crystal structures of the initial nanoparticles will be the same as those of the final product. All three processes could result in the formation of a glass-ceramic material, but the main difficulty is the combination of different characteristics of two materials such as their melting temperatures, heat capacity, chemical reactivity, etc.
The glass-ceramic materials developed in this work are based on lithium vanadate borate glass (LVBG) and vanadate/rare earth (RE) nanoparticles. Vanadate nanoparticles were chosen for this study because orthovanadates have been widely known as efficient matrices for luminescent rare earth (RE) ions for more than 70 years. In particular, YVO4:Eu3+ crystalline compositions are widely used as red phosphor [24]. Today, the traditional application of vanadate phosphors extends to a range of technical fields, such as luminescent temperature and pressure sensors and light spectra transformers [25,26,27]. The La1−xRExVO4 luminescent compositions have also attracted increased research interest in the last decade with regard to their potential application as incident radiation converters for the enhancement of solar light harvesting in renewable energy production [27,28,29]. The luminescent converters are usually applied to a solar cell as a component of one of the covering layers. Thus, the task of incorporation of vanadate nanoparticles into transparent matrices without losing their excellent luminescent characteristics, which is precisely what is investigated in this paper, is an important part of this application. Boron oxide was chosen, since it is a well-known glass-forming oxide that is commonly used in the development of glass and glass-ceramic materials. It has several characteristics that make it a favorable component in optoelectronics. The LVBG compositions have already been reported as suitable glass matrices for the incorporation of the vanadate nanoparticles [30,31,32].

2. Materials and Methods

2.1. Synthesis

The glass-ceramic samples studied in this work for the first time were obtained using three different methods, as described below:
  • Method I—sintering of glass powders and vanadate nanoparticles. In this method, we used the pre-synthesized xLi2O-yV2O5-(100−x−y)B2O3 LVBG reported in [31,32] and La1−xRExVO4 vanadate nanoparticles reported in [33,34]. According to previous studies, the compositions of the glass matrix and crystalline nanoparticles were chosen to yield the most intense luminescent emission. The glass compositions used for the synthesis of the Method I samples contain 48% Li2O (x = 48) and 2% V2O5 (y = 2). For the crystalline nanoparticles, x = 0.1. The initial glass was broken, ground, and then mixed with crystalline nanoparticles. The MSE PRO 2L (4 × 500 mL) Vertical High Energy Planetary Ball Mill was used to promote the effective interaction of the crystalline nanoparticles and glass components to obtain high-quality glass-ceramic samples. The applied milling parameters were as follows: 100 rpm milling speed, steel mortar and balls, the ball-to-powder-weight ratio (BPR) = 15:1, and the milling time was 120 min. After milling, the obtained mixture was heated to 950 °C, held for 1 h at this temperature, and then quickly quenched on a non-magnetic metal plate.
  • Method II uses a previously described melt quenching procedure [31,32]. The chemically pure reagents of boric acid H3BO3, lithium carbonate Li2CO3, and vanadium pentoxide V2O5 were used for the synthesis. The reagents were ground and mixed, and then, pre-synthesized La0.9Eu0.1VO4 vanadate nanoparticles were added to the blended mixture, and the mixed blend was ground again and placed in porcelain crucibles. Then, the obtained blend was melted in air with gradual heating to 400 °C for 2 h and for 4 h to 950 °C in an electric muffle furnace. The final blend was melted and then quickly quenched on a non-magnetic metal plate. The main difference of the Method II procedure compared to the previous one is that the crystalline nanoparticles were added to the blend, which is usually used for the glass synthesis.
  • Method III uses a melt quenching procedure with a modification to the quenching part of the process. The blend for the glass synthesis was prepared as described above for Method II from the chemically pure reagents of boric acid H3BO3, lithium carbonate Li2CO3, and vanadium pentoxide V2O5. The melted blend was quickly quenched on the non-magnetic metal plate covered with a thick powder layer of vanadate nanoparticles. The quantity of the powder was calculated to achieve a 10% content of the crystalline component in the final samples. But considering that in this method, the entire amount of prepared powder was not incorporated in the obtained samples, we will not refer to the concentration for the Method III samples.
The composition of the samples was selected to cover a greater range of options with minimal consumption. Thus, Method I and Method II samples have the same glass composition, and Method I and Method III samples have the same nanoparticle composition. Keeping in mind that the main goal of this work was to investigate three different synthesis methods for glass-ceramics, the small difference of only 4% in Li content and the change from an Eu dopant to Sm in the LaVO4 nanoparticles are not expected to lead to noticeable differences in the final structural properties of the glass-ceramics. Indeed, the nanoparticles used were synthesized by the same method under the same conditions and have identical morphological and crystallographic characteristics, regardless of the rare earth dopant [33,34].

2.2. Experimental Methods

The microstructure and chemical composition of the samples were characterized with a JEOL JSM-7000F scanning electron microscope (SEM) equipped with the Oxford X- Max 20 energy-dispersive X-ray spectroscope (EDX). Before SEM measurements, the surfaces of the samples were covered with thin Au metal-conducting films. Reflectance spectroscopy of the samples was performed using a Perkin Elmer Lambda 950 spectrometer. Raman backscattering measurements were executed using a Horiba LabRAM HR Evolution confocal microscope using the 532 nm line of a Nd:YAG laser. The photoluminescence (PL) properties were investigated using two types of excitations. There are excitations with synchrotron radiation and Xenon lamps. Spectra with synchrotron radiation excitation were measured at the PETRA III P66 beamline of the Deutsches Elektronen-Synchrotron DESY (Hamburg, Germany). The registering monochromator was a 0.3 m Kymera 328i (Andor) device with F/4.1 aperture (200–1200 nm) and 0.4 nm spectral resolution. Luminescence properties were investigated for wide temperature range from room temperature (RT) to 10 K. Low-temperature measurements were carried out with a TIC-500 flow-type cryostat from CryoVac. PL properties with Xenon lamp excitation were investigated with an FLS1000 Fluorescence spectrometer with the application of two types of Xenon lamp sources: Xe2 continuous Xenon lamp for spectra recording and µF2 Xenon Flash lamp for decay time measurements. All the measured spectra were corrected for the spectral response of the instrument. The SEM, Raman, and PL measurements were conducted using as-synthesized thick round glass ball pieces, whereas the reflectance spectra were measured in diffuse mode using grounded samples to avoid any effects of the samples’ thicknesses and surface ripples on the measured spectra.

3. Characterization of the Samples

3.1. Method I Samples

The pre-synthesized glass samples used in this method were transparent pieces with light yellow coloring. But, contrary to the initial glass matrices, the obtained glass-ceramic samples looked black if their thickness was over 3–4 mm, and only the thin pieces were transparent (Figure 1a). As the added vanadate nanoparticles are transparent in the entire visible range, they cannot be responsible for the observed coloration/darkening (Figure 1b). The UV–Visible spectroscopy of the samples did not reveal additional absorption bands in the obtained glass-ceramic samples. The main band at 320 nm corresponded to the absorption transitions in the VO43− vanadate groups [33,34,35,36]. The band at 470 nm observed for the glass sample corresponded to the V2O5 component of a glass composition [31]. Consequently, the observed overall decrease in transparency of the glass-ceramic samples is caused by the inner scattering of the light inside the samples. The EDX analysis of these samples conducted in the specially selected region with agglomeration of inclusions showed the presence of a large amount of C, Al, and Si impurities in the synthesized glass-ceramics (Figure 2). It is noted that the signals from Li and B could not be detected due to the Be window used in the SEM/EDX setup, and the Au signal is due to sputtering of the samples. We suppose that the C, Al, and Si impurities came into the blend during grinding in the planetary milling. We speculate that the black coloring is due to scattering of the light by the noted micropieces, which originated in the milling process.

3.2. Method II Samples

The glass-ceramic samples prepared by Method II are remarkably close to the pure glass matrix of the same compositions, as the visual inspection indicates that it is transparent with a light yellow coloring. Their reflectance spectra present two reflection bands around 320 and 470 nm. These bands are caused by the absorption transitions in the VO43− vanadate groups and the V2O5 component of glass composition, respectively (Figure 3, left) [31,33,34,35,36]. The SEM investigation of the surface of the glass and glass-ceramic samples showed that the pure glass surface has quite a good flat quality and that the nanoparticles are incorporated in the glass-ceramic samples as inclusions with a tendency to agglomerate (Figure 3, right).

3.3. Method III Samples

This technique was applied to distribute crystalline nanoparticles in the glass melt immediately after synthesis before the melt solidified. However, we did not achieve any mixing of the two phases, and the nanoparticles did not dissolve or spread into the molten glass. Instead, we observed the formation of core–shell structuring in the obtained samples. This process can be described as follows: First, a thick layer of crystalline nanoparticle powder was placed on a non-magnetic metal plate, onto which the molten glass was to be poured for cooling. Second, the melted blend was poured onto the layer of nanoparticles. At that moment, when a hot drop of molten glass fell, a wave of warm air pushed up the powder. Then, the volatile particles of the powder were attracted by the falling drop of molten glass and covered it. After hardening, the nanoparticles formed a stable thin layer on the surface of the synthesized glass. As a result, we obtained a sample consisting of a transparent yellow glass core covered with a sintered white nontransparent layer of luminescent nanoparticles. The described steps are schematically presented in Figure 4, left. The photograph of the obtained samples is shown in Figure 4, right top.
Thus, the Method III samples possess a two-component structure, and this means that UV–Visible reflectance spectra and SEM measurements are not applicable for their characterization, as they will obtain a simple combination of contributions of the different parts of the samples. That is why we used other methods, in particular, Raman spectroscopy, to study possible mutual effects of the crystalline component on the network structure of the glass matrix, taking the signals from the different points of the obtained samples, as shown in Figure 4, right top. The Raman peaks around 240, 350, 490, 780, and 905 (strong) cm−1 are observed for both the pure glass matrix and for the glass core of the obtained two-component samples (Figure 4, right, curves 1 and 2, respectively). The Raman spectra of the crystalline shell are completely different (curve 3). No effects of the crystalline shell on the Raman spectra of the glass core were observed. The Raman peaks around 240 and 350 cm−1 were attributed to O-V-O and V-O-V bending vibrations, respectively [37,38]. The peaks at 490 and 780 cm−1 were assigned to the stretching vibrations in isolated diborate groups and to B–O–B bending modes, respectively [39,40,41]. The band at 905 cm−1 was assigned to VO2 groups. Two peaks corresponding to O-V-O vibrations can be observed in the following range: a peak at 910 cm−1, corresponding to the VO2 symmetric stretching mode, and a peak at 900 cm−1, corresponding to the antisymmetric stretching mode [41,42]. The stretching vibrations of the BO4 groups could also contribute to the band with maxima at 905 cm−1, as their vibrational modes are usually observed around 880 cm−1 [38,39,40,41]. However, it was not possible to resolve these three modes in the Raman spectra. The Raman peaks observed for the core–shell samples prepared by Method III were assigned to several vibrations of the VO4 groups in the crystalline surrounding with different symmetries, tetragonal and monoclinic. These crystalline phases were already present in the original vanadate nanoparticles [33,34]. In particular, the antisymmetric stretching mode ν3 of the VO4 groups in the monoclinic phase was identified by the 736, 758, and 797 cm−1 peaks and in the tetragonal phase by the 863 cm−1 peak [43]. Other vibrational modes and their corresponding peaks were not further considered, as this is not within the theme of this work. The main result obtained from the Raman spectroscopy measurements was that the crystalline shell keeps its crystalline characteristics, and the glass core keeps its glass characteristics, in the synthesized two-component samples prepared by Method III.

4. Effects of the Synthesis Method on the Luminescence Properties

The glass matrices used for the creation of glass-ceramic samples are characterized by an intense and broad luminescence emission covering the entire visible range, with maxima at 570 and 610 nm (Figure 5a). The luminescence spectra of the glass-ceramic samples contain two types of emission: the above-noted broadband emission and the RE characteristic line emission from the crystalline component, as per the composition of the nanoparticles (Figure 6). Both types of emission can be effectively excited from the UV energy range, including vacuum UV photons and their spectra profiles, which have not revealed noticeable dependencies on the excitation wavelengths (Figure 5). The excitation spectra of the glass samples are formed by three strongly overlapping wide bands with maxima around 205, 270, and 320 nm (Figure 5b). The excitation spectra of the ceramic samples also contain additional bands at 250 and 300 nm, which correspond to RE—O charge transfer transitions and 1A1 → 1T1,2 electron transitions in the VO43− molecular anions, respectively [44,45,46]. Focusing on the emission spectra that are excited through the glass matrix, the next series of measurements were conducted using excitation at 205 nm. Under these conditions, the excitation of the glass matrix is more intense than the excitation of the vanadate nanoparticles. In addition, this excitation wavelength is near the actual maximum of the applied Al grating for the synchrotron excitation source [47], and the intensities of the emission spectra in Figure 5a were not divided by the intensity of the excitation wavelengths.
The nature of luminescence processes in the xLi2O-yV2O5-(100−x−y)B2O3 LVBG was discussed previously in [31,32]. The observed PL of the glass matrix is assumed to be caused by recombination processes with the participation of self-localized holes in the borate network and electrons trapped in the vanadium-related defects. Consequently, according to the goals of the present work, the focus of the discussion below will be on the interaction of the glass matrices and their emissions when the crystalline component of glass-ceramic samples is synthesized by different methods.
Despite the black coloration and the large scattering due to the impurity inclusions, the luminescence emission of the samples prepared by Method I is quite intense. The broadband contribution of the emission spectra is comparable in intensity with the spectra of the initial glass matrix used for the synthesis (Figure 6a) [31]. The narrow lines in the emission spectra correspond to internal f-f transitions in the Sm3+ ions of the La0.9Sm0.1VO4 crystalline nanoparticles that are incorporated in these glass-ceramic samples [28]. Groups of lines observed around the 550–580, 580–620, 630–670, and 680–720 nm spectral regions were assigned to the 4G5/2 → 6H5/2, 6H7/2, 6H9/2, and 6H11/2 electron transitions in the Sm3+ ions, respectively.
The most intensive line of the Sm3+ emission is observed around 607 nm and belongs to the so-called “orange” 4G5/2 → 6H7/2 multiplet. The predominance of this transition over the line at 645 nm of the “red” 4G5/2 → 6H9/2 multiplet reveals a lower symmetry of oxygen surrounding the Sm3+ ions in the obtained samples compared to the initial vanadate nanoparticles [34,35]. An increase in the La0.9Sm0.1VO4 concentration in the glass-ceramic samples leads to the broadening of the spectral lines. This is an indication of the appearance of the Sm3+ ions in different symmetry positions due to several arrangements in the glass network [48,49]. The contribution of the glass matrix emission in the spectra of the Method I ceramic samples corresponds with the increase in temperature, whereas the intensity of the Sm3+ ions’ emission is nearly the same (Figure 6a).
The luminescence spectra of the glass-ceramic samples prepared by Method II also consist of a broadband emission from the glass and the RE narrow bands from the original La0.9Eu0.1VO4 crystalline nanoparticles that were used for the synthesis. The luminescence lines in the 580–720 nm spectral range were assigned to the 5D0 → 7FJ (J = 0, 1, 2, 3, 4) transitions in the Eu3+ ions [33,50]. The contribution of the glass matrix emission is not suppressed by the crystalline component, showing the absence of competition between the luminescence processes in both components of the investigated samples under UV excitation (Figure 6b). It is noted that the relative intensity of the spectral line at 580 nm corresponding to the 5D0 → 7F0 transition is increased about three times in the spectra of the ceramic samples compared to the spectra of the crystalline nanoparticles (marked by vertical dots in Figure 6b). This spectral feature reveals changes in the symmetry of the nearest oxygen surrounding the Eu3+ ions in the ceramic samples, as the 5D0 → 7F0 transition can be observed mainly for the Eu3+ ions arranged with local Cs symmetry or lower [43,44,45].
The main difference in the spectra is that the contribution of the crystalline component in the emission spectra of the Method II glass-ceramic samples increases considerably with the increase in temperature of the samples. This is in opposition to the Method I samples, where the contribution of the crystalline component is similar at various temperatures (Figure 6a,b). This effect can be caused by a more efficient excitation energy transfer from the glass matrix to the crystalline nanoparticles incorporated in its composition. Clearly, a better interaction between both components was achieved with Method II.
The luminescence spectra of the Method III glass-ceramics were taken from the core part of the sample, as marked by arrow 2 in Figure 4, right. The spectra show the highest emission intensity of the crystalline component, i.e., of the La0.9Eu0.1VO4 nanoparticles [33,50]. On the other hand, only the Method III samples showed a decrease in the glass matrix emission (Figure 6c). Considering the unique structural architecture of the samples obtained with this method, the observed spectral features could be a result of the efficient transfer of excitation energy from the transparent glass core to the nontransparent crystalline shell. While in the Method III samples, the components are not mixed and it is not possible to obtain a classical glass-ceramic using this method, these samples have demonstrated the highest luminescence efficiency and, therefore, from this point of view, the Method III samples could have promising practical applications. We have estimated the quantum efficiency of the best Method III ceramic sample by comparison of its emission spectra with the emission of the sodium salicylate sample as a reference material (quantum yield is around 60% in 60–360 nm excitation range [51]) under all the same experimental conditions, determining a 310 nm excitation to be the most efficient according to Figure 4, right. The obtained results showed our material to be 70% of the integral emission of the reference material within the 350–850 nm spectral window (Figure 6d). Thus, we can roughly estimate the quantum efficiency of this sample as around 40%.
An investigation of the low-temperature PL spectral properties was conducted to obtain additional insights into the excitation energy transfer between the glass matrix and the crystalline components. As in the case of Method II, the temperature dependence of the PL intensity of the crystalline component of the Method III samples strongly increases with temperature. Such a temperature behavior is not expected for the luminescence of the original nanoparticles [34,52]. Therefore, we suppose that the observed behavior is caused by a glass matrix effect on the emission of the crystalline component, e.g., by the increase in efficiency of excitation energy transfer from the glass to the crystalline phase. This means that the energy transfer takes place with the participation of phonons or partially forbidden electron transitions that are activated with temperature. On the other hand, the presence of a crystalline component does not influence the shape of the glass matrix emission in any of the investigated spectral ranges.
The investigation of the decay kinetics showed that the line emission of the crystalline component and wideband glass matrix emission have quite different quenching characteristics (Figure 7). The luminescence decay time of the glass matrix emission can be described by one exponent with a 1.25 µs decay time, regardless if it is from a pure glass sample or from a glass-ceramic sample (Figure 7, curves 1, 2). The luminescence decay time of the Eu3+ ion emission can be described by two exponential functions with 0.53 and 1.1 ms lifetimes at 270 nm and 396 nm excitations. The decay times are essentially the same for both the excitations. A similar biexponential decay has been observed before for Eu3+ ions in phosphate crystalline hosts [44]. These results showed that the decay behavior of the luminescence emission values of the Eu3+ ions that were excited through the glass matrix (270 nm) and directly in the 7F0 → 5L6 transition (396 nm) are the same. This confirms that the Eu3+ ions are not dispersed in the glass matrix but are still a part of the initial crystalline nanoparticles.
The fact that we did not observe a similar temperature-driven increase in the emission of the crystalline component of the Method I glass-ceramics was tentatively attributed to the presence of steel inclusions in their structure. It is supposed that the excitation light is scattered or/and absorbed on those unwanted inclusions, thus not promoting luminescence. Therefore, it is obvious that the emission intensity of the incorporated La1−xRExVO4 vanadate nanoparticles in the xLi2O-yV2O5-(100−x−y)B2O3 glass matrix could increase considerably if favorable synthesis conditions are achieved.

5. Conclusions

Glass-ceramic samples derived from the combination of the xLi2O-yV2O5-(100−x−y)B2O3 glass matrix and La1−xRExVO4 vanadate nanoparticles were prepared by three different methods and investigated. An overall evaluation of the luminescence characteristics showed that all three synthesis methods yielded glass-ceramic samples with promising luminescence characteristics. The samples demonstrated intense emissions from both glassy and crystalline components, with the spectra covering the whole visible range. The analysis of the low-temperature PL spectral properties revealed that the energy transfer takes place with the participation of phonons or partially forbidden electron transitions that are activated with temperature. While the latter property is a promising characteristic for the use of these glass-ceramics as luminescent materials for various optoelectronic purposes, this investigation revealed limitations of the synthesis techniques. It is our understanding that they require further improvement for the development of luminescent materials for certain applications.

Author Contributions

All authors were involved in developing the manuscript. O.C. contributed to the study conception. V.B., O.C., I.F. and T.V. prepared the samples. The SEM/EDX measurements were conducted and analyzed by A.M. The diffuse reflection spectra were measured by O.C. and E.S. The Raman spectra and luminescence decay curves were measured and analyzed by O.C., R.L.C. and L.G.J. O.C., A.K. and L.G.J. performed luminescence spectroscopy measurements and their analysis. The first draft of the manuscript was written by O.C. and all authors commented on previous versions of the manuscript. All authors have read and agreed to the published version of the manuscript.

Funding

This work has received funding through the Science in Universities program of the Ministry of Education and Science of Ukraine, the MSCA4Ukraine project Grant ID number 1233117, which is funded by the European Union. Supported by the European Union within Project 101120397—APPROACH. Oksana Chukova and Luiz G. Jacobsohn acknowledge the Fulbright Visiting Scholar Program under Grant ID PS00350114. Luiz G. Jacobsohn and Robin L. Conner acknowledge support from the National Science Foundation under Grant No. DMR-1653016.

Informed Consent Statement

This paper contains no research involving human participants and/or animals. The authors have no relevant financial or non-financial interests to disclose.

Data Availability Statement

The data generated or analyzed during this study are included in this article, further inquiries can be directed to the corresponding author.

Acknowledgments

The authors thank the Horizon-Europe research and innovation program within the framework of the NFFA-Europe Pilot Transnational Access Activity Project Proposal ID 281 for the facility access provided by the Institute of Electronic Structure and Laser IESL-FORTH, Heraklion, Greece. The authors thank Konstantina Alexaki and Zacharias Viskadourakis for their help with these experiments. The authors acknowledge DESY (Hamburg, Germany), a member of the Helmholtz Association HGF, for the provision of experimental facilities. Parts of this research were conducted at PETRA III Beamline P66.

Conflicts of Interest

The authors declare no conflicts of interest.

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Figure 1. (a) Samples of the glass with 48Li2O-2V2O5-50B2O3 composition (1) and of the Method I glass-ceramics made from this glass (2–4), wherein the concentration of the nanoparticles in the blend is 5% (2, 4) and 10% (3), while there are thick (2, 3) and thin (4) pieces; (b) diffuse reflectance spectra of the glass with 48Li2O-2V2O5-50B2O3 composition (1), the Method I glass-ceramics made from this glass (2, 3), where the concentration of the nanoparticles in the blend is 5% (2) and 10% (3), and the initial La0.9Sm0.1VO4 vanadate nanoparticles (4).
Figure 1. (a) Samples of the glass with 48Li2O-2V2O5-50B2O3 composition (1) and of the Method I glass-ceramics made from this glass (2–4), wherein the concentration of the nanoparticles in the blend is 5% (2, 4) and 10% (3), while there are thick (2, 3) and thin (4) pieces; (b) diffuse reflectance spectra of the glass with 48Li2O-2V2O5-50B2O3 composition (1), the Method I glass-ceramics made from this glass (2, 3), where the concentration of the nanoparticles in the blend is 5% (2) and 10% (3), and the initial La0.9Sm0.1VO4 vanadate nanoparticles (4).
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Figure 2. SEM image and EDX spectra (top—Spectrum 1, bottom—Spectrum 2) of the Method I glass-ceramic samples; the concentration of the La0.9Sm0.1VO4 vanadate nanoparticles in the blend is 10%.
Figure 2. SEM image and EDX spectra (top—Spectrum 1, bottom—Spectrum 2) of the Method I glass-ceramic samples; the concentration of the La0.9Sm0.1VO4 vanadate nanoparticles in the blend is 10%.
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Figure 3. Diffuse reflectance spectra, SEM images, and a photograph of the 48Li2O-2V2O5-50B2O3 LVBG (1) and of the Method II ceramic sample with the same glass composition (2), where the concentration of the La0.9Eu0.1VO4 vanadate nanoparticles in the blend is 5%.
Figure 3. Diffuse reflectance spectra, SEM images, and a photograph of the 48Li2O-2V2O5-50B2O3 LVBG (1) and of the Method II ceramic sample with the same glass composition (2), where the concentration of the La0.9Eu0.1VO4 vanadate nanoparticles in the blend is 5%.
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Figure 4. (Left) Schematic presentation of the glass-ceramic synthesis by Method III (1—crucible with melting glass blend, 2—melting glass and droplets, 3—crystalline nanoparticles in powder state, 4—non-magnetic metal plate (copper)); (Right) photograph and Raman spectra of the sample and of the related glass sample with the same 44Li2O-4V2O5-52B2O3 composition, obtained by Method III.
Figure 4. (Left) Schematic presentation of the glass-ceramic synthesis by Method III (1—crucible with melting glass blend, 2—melting glass and droplets, 3—crystalline nanoparticles in powder state, 4—non-magnetic metal plate (copper)); (Right) photograph and Raman spectra of the sample and of the related glass sample with the same 44Li2O-4V2O5-52B2O3 composition, obtained by Method III.
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Figure 5. (a) The as-measured emission spectra of the 48Li2O-2V2O5-50B2O3 LVBG at various excitation wavelengths; (b) excitation spectra of the 48Li2O-2V2O5-50B2O3 (1) and 44Li2O-4V2O5-52B2O3 (2) LVBGses and of the Method III ceramic sample made from the 44Li2O-4V2O5-52B2O3 glass (3, 4); at synchrotron excitation, λem = 570 (1–3) and 618 nm (4), and all T = 10 K.
Figure 5. (a) The as-measured emission spectra of the 48Li2O-2V2O5-50B2O3 LVBG at various excitation wavelengths; (b) excitation spectra of the 48Li2O-2V2O5-50B2O3 (1) and 44Li2O-4V2O5-52B2O3 (2) LVBGses and of the Method III ceramic sample made from the 44Li2O-4V2O5-52B2O3 glass (3, 4); at synchrotron excitation, λem = 570 (1–3) and 618 nm (4), and all T = 10 K.
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Figure 6. (a) Emission spectra of the 48Li2O-2V2O5-50B2O3 LVBG (1); of the Method I glass-ceramic samples (2, 3) made from this glass and the initial La0.9Sm0.1VO4 vanadate nanoparticles (4); with a glass-ceramic sample concentration of the La0.9Sm0.1VO4 nanoparticles in the blend of 5% (2) and 10% (3) at synchrotron excitation; λex = 205 nm; (b) emission spectra of the 48Li2O-2V2O5-50B2O3 LVBG (1), Method II glass-ceramic samples (2) and initial La0.9Eu0.1VO4 vanadate nanoparticles (3); with a glass-ceramic sample (2) concentration of crystalline nanoparticles in the blend of 5% at synchrotron excitation; λex = 205 nm; (c) luminescence emission spectra of the 44Li2O-4V2O5-52B2O3 LVBG (1), Method III glass-ceramic samples (2) made from this glass with the addition of a La0.9Eu0.1VO4 crystalline component, and of the initial La0.9Eu0.1VO4 nanoparticles (3) at synchrotron excitation; λex = 205 nm; (d) luminescence emission spectra of the sodium salicylate reference and of the Method III glass-ceramic sample made from 44Li2O-4V2O5-52B2O3 LVBG and a La0.9Eu0.1VO4 crystalline component at synchrotron excitation; λex = 310 nm.
Figure 6. (a) Emission spectra of the 48Li2O-2V2O5-50B2O3 LVBG (1); of the Method I glass-ceramic samples (2, 3) made from this glass and the initial La0.9Sm0.1VO4 vanadate nanoparticles (4); with a glass-ceramic sample concentration of the La0.9Sm0.1VO4 nanoparticles in the blend of 5% (2) and 10% (3) at synchrotron excitation; λex = 205 nm; (b) emission spectra of the 48Li2O-2V2O5-50B2O3 LVBG (1), Method II glass-ceramic samples (2) and initial La0.9Eu0.1VO4 vanadate nanoparticles (3); with a glass-ceramic sample (2) concentration of crystalline nanoparticles in the blend of 5% at synchrotron excitation; λex = 205 nm; (c) luminescence emission spectra of the 44Li2O-4V2O5-52B2O3 LVBG (1), Method III glass-ceramic samples (2) made from this glass with the addition of a La0.9Eu0.1VO4 crystalline component, and of the initial La0.9Eu0.1VO4 nanoparticles (3) at synchrotron excitation; λex = 205 nm; (d) luminescence emission spectra of the sodium salicylate reference and of the Method III glass-ceramic sample made from 44Li2O-4V2O5-52B2O3 LVBG and a La0.9Eu0.1VO4 crystalline component at synchrotron excitation; λex = 310 nm.
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Figure 7. Luminescence decay curves of the 44Li2O-4V2O5-52B2O3 LVBG (1) and Method III glass-ceramic samples made from the 44Li2O-4V2O5-52B2O3 LVBG with the addition of La0.9Eu0.1VO4 nanoparticles. All decay curves were obtained at RT with a pulsed xenon lamp excitation with λex = 270 nm (1–3) and 396 nm (4), and emission was monitored at λem = 570 nm (1, 2) and 618 nm (3, 4).
Figure 7. Luminescence decay curves of the 44Li2O-4V2O5-52B2O3 LVBG (1) and Method III glass-ceramic samples made from the 44Li2O-4V2O5-52B2O3 LVBG with the addition of La0.9Eu0.1VO4 nanoparticles. All decay curves were obtained at RT with a pulsed xenon lamp excitation with λex = 270 nm (1–3) and 396 nm (4), and emission was monitored at λem = 570 nm (1, 2) and 618 nm (3, 4).
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MDPI and ACS Style

Chukova, O.; Fesych, I.; Voitenko, T.; Baran, V.; Kotlov, A.; Conner, R.L.; Jacobsohn, L.G.; Manousaki, A.; Stratakis, E. The Effects of the Incorporation of Luminescent Vanadate Nanoparticles in Lithium Borate Glass Matrices by Various Methods. Solids 2024, 5, 485-498. https://doi.org/10.3390/solids5040032

AMA Style

Chukova O, Fesych I, Voitenko T, Baran V, Kotlov A, Conner RL, Jacobsohn LG, Manousaki A, Stratakis E. The Effects of the Incorporation of Luminescent Vanadate Nanoparticles in Lithium Borate Glass Matrices by Various Methods. Solids. 2024; 5(4):485-498. https://doi.org/10.3390/solids5040032

Chicago/Turabian Style

Chukova, Oksana, Ihor Fesych, Tetiana Voitenko, Volodymyr Baran, Aleksei Kotlov, Robin L. Conner, Luiz G. Jacobsohn, Alexandra Manousaki, and Emmanuel Stratakis. 2024. "The Effects of the Incorporation of Luminescent Vanadate Nanoparticles in Lithium Borate Glass Matrices by Various Methods" Solids 5, no. 4: 485-498. https://doi.org/10.3390/solids5040032

APA Style

Chukova, O., Fesych, I., Voitenko, T., Baran, V., Kotlov, A., Conner, R. L., Jacobsohn, L. G., Manousaki, A., & Stratakis, E. (2024). The Effects of the Incorporation of Luminescent Vanadate Nanoparticles in Lithium Borate Glass Matrices by Various Methods. Solids, 5(4), 485-498. https://doi.org/10.3390/solids5040032

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