Optical Pressure Sensor Based on the Emission and Excitation Band

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Functional Inorganic Materials and Devices

Optical Pressure Sensor Based on the Emission and Excitation Band Width (FWHM) and Luminescence Shift of Ce3+ Doped Fluorapatite – High-Pressure Sensing Marcin Runowski, Przemys#aw Wo#ny, Natalia Stopikowska, Qingfeng Guo, and Stefan Lis ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b19500 • Publication Date (Web): 07 Jan 2019 Downloaded from http://pubs.acs.org on January 9, 2019

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ACS Applied Materials & Interfaces

Optical Pressure Sensor Based on the Emission and Excitation Band Width (FWHM) and Luminescence Shift of Ce3+ Doped Fluorapatite – High-Pressure Sensing

Marcin Runowski,1,* Przemysław Woźny,1 Natalia Stopikowska,1 Qingfeng Guo,2 Stefan Lis1

1Adam

Mickiewicz University, Faculty of Chemistry, Department of Rare Earths, Umultowska

89b, 61-614 Poznań, Poland 2

School of Gemology, China University of Geosciences, Beijing 100083, China.

KEYWORDS: Ce3+ doping; Contactless pressure gauge; Compression in DAC; Lanthanide ions (Ln3+); Luminescent functional materials; Y6Ba4(SiO4)6F2 apatite phosphors

Abstract A novel, contactless optical sensor of pressure based on the luminescence red-shift and band width (full width at half maximum - FWHM) of the Ce3+-doped fluorapatite - Y6Ba4(SiO4)6F2 powder, has been successfully synthesized via a facile solid-state method. The obtained material exhibits a bright blue emission under UV light excitation. It was characterized using powder X-ray diffraction, scanning electron microscopy and luminescence spectroscopy, including high-pressure measurements of excitation and emission spectra, up to above ≈30 GPa. Compression of the material resulted in a significant red-shift of the allowed 4f→5d and 5d→4f transitions of Ce3+ in the excitation and emission spectra, respectively. The pressureinduced monotonic shift of the emission band, as well as changes in the excitation/emission band widths, have been correlated with pressure for sensing purposes. The material exhibits a high pressure sensitivity (dλ/dP ≈0.63 nm/GPa), and outstanding signal intensity at high1 ACS Paragon Plus Environment

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pressure conditions (≈90% of the initial intensity at around 20 GPa) with minimal pressureinduced quenching of luminescence.

Introduction Lanthanide (Ln3+) doped luminescent materials have been extensively studied because of their favorable spectroscopic, magnetic and catalytic properties.1–7 Compounds based on Ln3+ (e.g. Nd3+, Sm3+, Eu3+, Tb3+, Er3+, Tm3+) and some Ln2+ ions (e.g. Sm2+, Eu2+) exhibit a tunable multicolor emission, ranging from UV-Vis to NIR range, long luminescence lifetimes (μs-ms range) and narrow absorption/emission bands.8–15 Such unique spectroscopic properties originate from their specific, ladder-like electronic structure, the forbidden (by Laporte selection rules) character of the intrinsic 4f-4f transitions, crystal-field effects, and shielding of the 4f electrons by 5s and 5p ones.8,16–18 Inorganic materials such as simple and complex oxides, fluorides, phosphates, borates, vanadates, silicates, and the others may exhibit intense, bright emission when excited by electromagnetic radiation from the range of UV or NIR (upconversion).1,11,19–25 Among them, the Ln2+/3+-doped apatite-type compounds with general chemical formula A10(BO4)6C2 (A = Ca2+, Sr2+, Ba2+, Eu2+, La3+; B = P5+, As5+, Si4+, S6+; C = F-, Cl-, OH-) were extensively studied because of their biocompatibility, thermal stability, intense and efficient luminescence due to the energy and charge transfer processes, possibility of industrial applications as e.g. white-light emitting diodes (WLEDs), etc.7,26–30 Moreover, they have a flexible network structure, which can be easily substituted by different ions, alike in cationic and anionic sites.26–30 In contrast to organic compounds, such inorganic crystals are much more resistant to high temperature treatment and photo-degradation processes, which are important features for their application in various fields of science and industry, e.g. sensing methods, bio-detection and imaging, labelling, lighting techniques, documents and textiles protection, forensics, etc.11,21,31,32

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The spectroscopic properties of Ln2+/3+-doped materials can be changed continuously by applying temperature and pressure, hence they can be utilized in optical, contactless thermometry and manometry, respectively.1,20,21,31,33–35 Hence pressure is a fundamental physical quantity affecting the physicochemical properties of materials, its accurate and precise determination is of crucial importance for scientific and industrial applications.21,36,37 High-pressure experiments can be utilized for investigation of continuous changes of some spectroscopic and structural properties of the compounds studied, formations of novel materials under extreme conditions, phase transitions, simulation of some geological processes occurring inside the planets/stars, etc.1,20,21,36,37

The materials are usually

compressed and subjected to pressure in a diamond anvil cell (DAC) due to the hardness and high transparency of diamonds.36,37 Their compression leads to the decrease of interatomic distances and bonds shortening, resulting in the spectral red-shift of their absorption/emission bands (smaller energy difference between the ground and excited states of Ln2+/3+), as well as changes of band intensity ratios and their width, altered luminescence lifetimes, etc.1,20,21,36,37 The reversible and monotonic changes of the mentioned parameters can be applied for the pressure sensing purposes.1,20,21 A good optical pressure sensor should show as high as possible change in the measured parameter (MP; e.g. band shift, ratio, width, lifetime) with pressure (dMP/dP), to guarantee high sensor sensitivity.37 Other very important factors determining the overall performance of the pressure sensor are: i) luminescence intensity, related to the emission quantum yield (QY), and ii) the rate/extent of the usually observed, pressure-induced decrease in its emission intensity. Determination of the local pressure value of compressed system subjected to high-pressure conditions is usually done by a ruby R1 line fluorescence shift (dλ/dP ≈0.35 nm/GPa),38,39 or by the 5D0→7F0 line shift (dλ/dP ≈0.25 nm/GPa) of Sm2+ ions embedded in the complex strontium borate host matrices (SrB2O4, SrB4O7).21,40,41 However,



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some other optical pressure sensors and nanosensors based on the luminescence of Ln3+ ions (e.g. Nd3+, Eu3+, Sm3+, Er3+ and Tm3+ ions) embedded in different inorganic host matrices were reported.1,20,42–44 They usually utilize the emission line shift (dλ/dP ≈0.1-0.3 nm/GPa), but also the band ratios (dMP/dP ≈8%/GPa) and luminescence lifetimes (dMP/dP ≈68%/GPa).1,20,42–44 The example of a sensor with better sensitivity than ruby, is YAlO3:Cr3+ (dλ/dP ≈0.7 nm/GPa), but its fluorescence intensity is much lower than that of ruby.42 Another example is a sensor based on the SrFCl:Sm2+, which exhibited an exceptional sensitivity (dλ/dP ≈1.1 nm/GPa), but unfortunately also shown a very significant pressure-induced intensity decrease limiting its use to the low pressure range, below 20 GPa.37,45 Generally, the luminescence intensity of optical pressure sensors such as ruby (QY ≈0.9) and other Ln2+/3+-based materials, significantly decreases with pressure, from a few to several dozen times around 20-30 GPa (depending on Ln ion and host). For example, in the case of ruby and SrBxOy:Sm2+, the high pressure influence leads to the signal intensity deterioration to about ≈5% around 20 GPa, compared to initial values (at ambient pressure).1,20,21,33,36–45 Concluding, an ideal optical (luminescent) pressure sensor should exhibit high sensitivity, e.g. large shift of the emission line relative to its width, favorably ≥1 nm/GPa, to provide facile detection of pressure changes and high pressure resolution. Moreover, its QY should be as high as possible (1; 100%); luminescence signal intensity should increase or only slightly decrease with pressure, to guarantee good sensing accuracy and precision; the measured effects should be monotonic (favorably linear or conform a well-defined, simple function) and reversible, i.e. the material should not undergo plastic deformations under pressure; its excitation and emission characteristics should match the commercially available and commonly used light sources and detectors; it should be abundant in its natural form, or be easily synthesized via a facile and reproducible protocol.


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Here, we report, for the first time, the use of a novel optical pressure sensor based on the luminescence red-shift and band width (full width at half maximum - FWHM) of the Ce3+doped fluorapatite - Y6Ba4(SiO4)6F2 exhibiting very high pressure sensitivity (dλ/dP ≈0.63 nm/GPa) and excellent signal intensity under high-pressure conditions. Namely, the reported sensor shows approx. ≈90% of the initial intensity at around 20 GPa.

EXPERIMENTAL PART Ce3+-doped fluorapatite Y5.95Ce0.05Ba4(SiO4)6F2 was synthesized via a high temperature solidstate reaction carried out in a reducing atmosphere similarly to the procedure described in our previous work, i.e. Guo et al.30 The raw materials, i.e. BaCO3 (99.9%), SiO2 (99.9%), NH4HF2 (99.9%), Y2O3 (99.995%) and CeO2 (99.995%) were purchased from Aldrich. To compensate fluorine loss at high temperature, NH4HF2 was used with 50% stoichiometric excess. The balance reaction can be given as follows: 4 BaCO3 + 6 SiO2 + NH4HF2 + 5.95/2 Y2O3 + 0.05 CeO2 → Y5.95Ce0.05Ba4(SiO4)6F2 + H2O↑ + CO2↑ + NH3↑

(1)

The starting materials were thoroughly mixed by grinding in an agate mortar. The wellgrounded mixture was transferred into a corundum crucible and preheated at 1023 K for 3 h in the air atmosphere. Afterwards, the material was again grounded thoroughly in an agate mortar, and the sample was again annealed at 1673 K for 4 h in a flowing reducing atmosphere of 10% H2 + 90% N2. The final product was slowly cooled to room temperature, and then grounded for further studies. Characterization The phase identification of the synthesized compound was performed by powder X-ray diffraction - XRD (XD-3, PGENERAL, China), using Cu Kα radiation (λ = 0.15406 nm),



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operating at 40 kV and 40 mA. Scanning electron microscopy (SEM) studies were performed using a Scanning Electron Microscope FEI Quanta 250 FEG. Excitation and emission spectra were recorded using a Hitachi F-7000 spectrofluorometer equipped with a 150 W xenon lamp, and they were corrected for the apparatus response. Technical details concerning quantum yield measurements and pressure determination are provided in the Supporting Information (SI). DAC loading procedure High-pressure experiments were performed in a Merrill-Bassett diamond-anvil cell (DAC), modified by mounting the anvils directly on steel supporting plates. The gaskets were made of stainless steel foil 0.25 mm thick with the aperture of 150 µm. Pressure was determined from the ruby R1 fluorescence line shift, with accuracy of ≈0.1 GPa. To provide quasi hydrostatic conditions, the methanol/etahanol/water (16/3/1 vol.) solvent system was used as a pressure transmitting medium. Luminescence measurements The high-pressure luminescence measurements (excitation and emission spectra) of the sample placed in the DAC were performed in an optimized configuration, in a back illuminated configuration, with a 180o detection geometry (transmitting mode). The UV light of the xenon lamp was focused on the sample, being placed in a gasket hole, and the emission signal was collected from the opposite site of the DAC. Each luminescence measurement was repeated 3-times and averaged.

RESULTS AND DISCUSSION Properties at ambient conditions Powder X-ray diffraction pattern of the Y5.95Ce0.05Ba4(SiO4)6F2 (abbreviated as YBSF:Ce3+) sample (Figure 1a) fits well with the reference pattern from the Inorganic Crystal Structure 6 ACS Paragon Plus Environment

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Database (ICSD) of the hexagonal fluorapatite La6Ba4(SiO4)6F2 crystallized in the space group P63/m, card no. 170852.46 The week reflexes at 23.9 and 27.3° (2θ) were ascribed to the trace amounts of SiO2 (03-0419) and Y2Si2O7 (21-1454), respectively. The detailed structural analysis including Rietveld refinement can be found in the SI (Figure S1). Visualization of the crystal structure along the c axis (Figure 1b) reveals the presence of two cationic sites with different local symmetries, i.e. nine-fold coordinated C3 (Wyckoff site 4f ) and seven-fold coordinated Cs (Wyckoff site 6h).7,30 Both sites are suitable for substitution with lanthanide ions. The YBSF:Ce3+ compound forms irregular micro-crystals, whose size is of about ≈5-10 µm (see SEM image in Figure 1c). The excitation and emission spectra (Figure 1d) consist of very broad, split bands corresponding to the allowed 4f1→4f05d1 and 4f05d1→4f1 transitions of Ce3+, respectively. The broad character of those bands is related to several factors: i) the presence of two emitting sites; ii) crystal field splitting of the 4f multiplet; iii) splitting of the ground 4f1 (2F7/2 and 2F5/2 components) and excited 4f05d1 (2D5/2 and 2D3/2) electronic configurations into two components due to the spin-orbit coupling; iv) spatially extended character of the 5d orbital, resulting in a strong overlapping of the excited 5d1 electron with the ligand orbitals, and enhanced electron-phonon coupling.47–50 The excitation band is located in the UV range from 250 to 400 nm, whereas the emission band covers the range from 375 to 700 nm. It is clearly seen that both bands could be deconvoluted into four separate peaks (Figure S2), confirming the presence of two different sites occupied by Ce3+ ions (discussion in SI). Additionally, the absolute quantum yield (QY) of the YBSF:Ce3+ luminescence was determined, i.e. QY ≈ 24.5 ± 0.5%, at λex = 340 nm. The relatively high value of the QY supports the idea of using this material as an optical pressure sensor.



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Figure 1. (a) Experimental powder XRD and ICSD reference patterns, (b) visualization of the crystal structure along the c axis, (c) SEM image, (d) normalized excitation (violet dotted line) and emission (continuous blue line) spectra of the Y5.95Ce0.05Ba4(SiO4)6F2 fluorapatite (YBSF:Ce3+); the inset (d) shows the photograph of the sample luminescence under UV light (λex= 340 nm).

Properties at high-pressure conditions Excitation spectra recorded in the DAC show a slightly different shape compared to the spectrum at ambient conditions. This is because of the absorption threshold (below ≈300 nm) of diamond anvils used for high-pressure measurements. The compression of YBSF:Ce3+ at high-pressure conditions (up to above ≈30 GPa) induced a significant excitation spectrum change (Figure 2a), namely a reversible red-shift of the Ce3+ 4f1→4f05d1 excitation peak centroid and broadening of this band. The peak shifts (≈750 cm-1) from about 342 to 351 nm


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(Figure 2b) with pressure due to the shortening of the interionic Ce-O and Ce-F distances, resulting in stronger interactions between the Ce3+ ions and the surrounding ligands (nephelauxetic effect), i.e. increased covalency of the shorter bonds, leading to a lower energy difference between the ground and excited states of Ce3+ (lower energy of the 5d level).1,21,36,37 The pressure-induced increase of the crystal-field strength (larger band splitting), may also contribute to the smaller energy separation between the states. The small peak position hysteresis observed during the decompression cycle (pressure release) is probably related to some inelastic structural deformations, e.g. the formation of crystal defects, typical of high-pressure experiments.1,20,21 The excitation and emission spectra recorded during decompression cycle are presented in SI (Figures S3 and S4). The width (FWHM) of the excitation band, initially ≈43 nm, increases (≈2650 cm-1) to about ≈76 nm at the highest pressure value, i.e. dMP/dP ≈85 cm-1/GPa (Figure 2c). This is due to the pressure-induced increase of the crystal-field strength, leading to the larger band splitting; enhanced electron-phonon coupling; increase of strains and distortions in the crystals; deviations from hydrostaticity at higher pressure values and formation of crystal defects.1,47 As the change was fully reversible, we correlated it with pressure using a 2nd order polynomial, with R2 > 0.99, i.e. FWHM = -0.00883P2 + 1.4021P + 42.133. The accuracy of pressure sensing using this method is about ±0.5 GPa, and the pressure sensitivity (change in the measured parameter per GPa) is ≈2.5% GPa-1.



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Figure 2. (a) Normalized excitation spectra, (b) spectral positions of the excitation band, and (c) band width (FWHM) of the YBSF:Ce3+ as a function of pressure; λem= 445 nm; the line (c) corresponds to the applied 2nd order polynomial fit.

As in the excitation spectra, the emission spectra are also significantly affected by compression of the YBSF:Ce3+ phosphor (Figure 3a), i.e. a reversible red-shift of the Ce3+ 4f05d1→4f1 emission peak centroid and band broadening are observed. This is due to similar effects mentioned in the previous paragraph concerning the pressure-induced changes of the excitation spectra. The band shifts (≈700 cm-1) from about 466 to 482 nm at around ≈31 GPa (Figure 3b), i.e. dλ/dP ≈0.63 nm/GPa (≈30 cm-1/GPa in the lower pressure range, up to ≈10 GPa). Thanks to the fully reversible shift, it was correlated with the pressure using a 2nd order polynomial, with R2 > 0.99, i.e. λ = -0.00614P2 + 0.71991P + 465.38. The accuracy of pressure sensing using this method is about ±0.2 GPa, and the pressure sensitivity is ≈0.63 nm GPa-1 in the mentioned pressure range. 10 ACS Paragon Plus Environment

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The width of the emission band at ambient pressure is about ≈124 nm and increases (≈2300 cm-1) with pressure to about ≈180 nm, i.e. dMP/dP ≈74 cm-1/GPa (Figure 3c). We correlated this change with pressure by a linear fitting, with R2 > 0.98, i.e. FWHM = 1.8127P + 121.197. The accuracy of the pressure determination by the use of this method is about ±1 GPa, and the pressure sensitivity is ≈1.5% GPa-1.



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Figure 3. (a) Emission spectra, (b) spectral positions of the emission band, and (c) band width (FWHM) of the YBSF:Ce3+ as a function of pressure; λex= 340 nm; the lines (b, c) correspond to the applied 2nd order polynomial (b) and linear fits (c).

The total luminescence intensity (Figure 4) of the compound studied initially decreases slightly (≈up to 2 GPa), then increases significantly with pressure (≈up to 12 GPa), and finally decreases again. Usually, in the case of various luminescent materials doped with different emitting ions, only the deterioration of the emission signal is observed as the pressure in the system increases. This is due to the increased probability of the non-radiative energy transfer cross-relaxation (shorter interionic distances), larger electron-phonon coupling in the compressed materials, enhanced multiphonon relaxation processes (due to higher phonon energy), altered energy of excited states, as well as the pressure-induced formation of crystal defects and strains in the crystals.1,20,21,33,37 However, the emission intensity of Ce3+ may be strongly dependent on the energy of the emitting 5d state relative to the conduction band edge of the host lattice, charge transfer states, energy transfer efficiency and local defects energy levels.47 By applying high pressure, it is possible to tune the relative energies of the mentioned states and to influence the energy transfer rates in the compressed structures. That is why it is possible to enhance the 5d→4f emission of Ce3+ by subjecting the material to high-pressure. Rodriguez-Mendoza et al.47 observed a similar effect of the Ce3+ luminescence enhancement over the low pressure range (up to ≈0.6 GPa) in Lu2SiO5:Ce3+. The Authors explained this phenomenon by photoionization processes competing with Ce3+ luminescence, related to the resonance of the 5d emitting level and the conduction band. They concluded that the emission intensity of Ce3+ is proportional to the concentration of electron-hole pairs in the lattice and the corresponding increase in energy transfer efficiency. On the other hand, a further decrease in the luminescence intensity is due to the saturation of enhancement processes when the competing, previously mentioned quenching effects start to play a dominant role. 12 ACS Paragon Plus Environment

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It is worth noting that the usually observed hysteresis (typical for high-pressure measurements) causes a deterioration in the emission intensity, i.e. lower signal intensity in the decompression cycle, due to the inelastic structural deformations, e.g. formation of crystal defects, permanently quenching some of the active centers.1,20,21,33 However, in this case, we did not observe such unfavorable effect, and the signal intensity was even higher in the decompression run, plausibly due to the mentioned pressure-induced changes of the excited states energy.

Figure 4. Integrated luminescence intensity of the YBSF:Ce3+ as a function of pressure; λex= 340 nm.

Table 1 shows the comparison of the measured luminescence parameters (dMP/dP) of the YBSF:Ce3+ material with performance of other available pressure sensors doped with Cr3+, Nd3+, Eu3+, Sm3+, Sm2+, Tm3+ and Er3+ ions.

Table 1. Performance and the measured parameters (line shift, FWHM, band ratio, lifetime) of the optical pressure sensors based on the materials doped with Ln2+/3+ or Cr3+ ions; band width, spectral range of the transitions used and the corresponding references. 13 ACS Paragon Plus Environment


Host

Dopant ion

Y6Ba4(SiO4)6F2 (fluorapatite)

Ce3+

Al2O3 (ruby) YAlO3 YAlO3 Y3Al5O12 (YAG) Y3Al5O12 (YAG) SrFCl SrB4O7 nano - SrB2O4 nano - LaPO4

Cr3+ Cr3+ Nd3+ Eu3+ Sm3+ Sm2+ Sm2+ Sm2+ Tm3+

nano - SrF2

Er3+

Measured parameter line width

dMP/dP (x/GPa) 2.5%

FWHM (nm) 43

line width line shift

1.5% 0.63 nm

124

line shift line shift line shift line shift line shift line shift line shift line shift line shift band ratio lifetime lifetime lifetime

0.365 nm 0.70 nm -0.13 nm 0.197 nm 0.30 nm 1.10 nm 0.255 nm 0.244 nm 0.1 nm 8% 7.7% 6.4% 6.2%

0.75 1 2 ≈0.3 ≈1 0.15 0.13 0.15 14 -

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Transitions 2F

J→

λ (nm)

2D (4f→5d) J excitation 2D →2F (5d→4f) J J emission

342

2E→4A

2

2E→4A

2

694 723 875 591 618 690 685 685 475 800/475 653 538 516

4F

4 3/2→ I9/2 (Stark) 5D →7F 0 1 4G →6H 5/2 7/2 (Stark) 5D →7F 0 0 5D →7F 0 0 5D →7F 0 0 1G →3H 4 6 3H →3H /1G →3H 4 6 4 6 4F 4S 2H

9/2 →

4I

3/2 →

15/2

4I

11/2 →

15/2

4I

15/2

466

Ref. this work [38] [42] [42] [43] [44] [51] [40] [21] [1] [20]

Conclusions A novel, contactless optical sensor of pressure based on fluorapatite - Y6Ba4(SiO4)6F2:Ce3+ crystals has been successfully synthesized via a facile solid state method. The obtained sensor exhibits a high pressure sensitivity and exceptional signal intensity under high pressure conditions. The pressure-induced large and monotonous red-shift (dλ/dP ≈0.63 nm/GPa) of the Ce3+ emission band (4f05d1→4f1 transition), initially located around 466 nm, is caused by the shortening of the interionic distances and stronger interactions between the ions in the compressed material. The band widths (FWHM) of excitation and emission spectra monotonically increase with pressure (dMP/dP ≈2.5 and 1.5%/GPa, respectively) due to the increased strength of the crystal-field, electron-phonon coupling, strains and distortions in the crystals, etc. Thanks to the reversibility of changes of those parameters and their high sensitivity, they have been successfully correlated with pressure for sensing purposes up to above ≈30 GPa. In contrast to the currently used sensors, which exhibit very significant luminescence quenching (signal deterioration) under high pressure conditions, the obtained


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material reveals a very low, almost negligible decrease of its emission intensity, which is beneficial for the pressure sensing purposes.

ASSOCIATED CONTENT Supporting Information Rietveld refinement; deconvoluted emission spectrum; excitation and emission spectra recorded during the decompression cycle. This material is available free of charge via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION Corresponding Author M.R.: Phone: +48618291778 E-mail: [email protected] Notes The authors declare no conflict of interest. ACKNOWLEDGEMENTS This work was supported by the Polish National Science Centre (grant No. 2016/23/D/ST4/00296) and by the National Natural Science Foundations of China (Grant No. 51672257), and by the Fundamental Research Funds from China University of Geosciences, Beijing (Grant No. 2652017091).

REFERENCES (1)

Runowski, M.; Shyichuk, A.; Tymiński, A.; Grzyb, T.; Lavín, V.; Lis, S. Multifunctional Optical Sensors for Nanomanometry and Nanothermometry: High15 ACS Paragon Plus Environment


Page 16 of 23

Pressure and High-Temperature Upconversion Luminescence of Lanthanide-Doped Phosphates—LaPO4/YPO4:Yb3+–Tm3+. ACS Appl. Mater. Interfaces 2018, 10, 17269– 17279. (2)

Suo, H.; Zhao, X.; Zhang, Z.; Guo, C. 808 nm Light-Triggered Thermometer–Heater Upconverting Platform Based on Nd3+-Sensitized Yolk–Shell GdOF@SiO2. ACS Appl. Mater. Interfaces 2017, 9, 43438–43448.

(3)

Skwierczyńska, M.; Runowski, M.; Goderski, S.; Szczytko, J.; Rybusiński, J.; Kulpiński, P.; Lis, S. Luminescent–Magnetic Cellulose Fibers, Modified with Lanthanide-Doped Core/Shell Nanostructures. ACS Omega 2018, 3, 10383–10390.

(4)

Gnach, A.; Bednarkiewicz, A. Lanthanide-Doped up-Converting Nanoparticles: Merits and Challenges. Nano Today 2012, 7, 532–563.

(5)

Tsang, M.-K.; Bai, G.; Hao, J. Stimuli Responsive Upconversion Luminescence Nanomaterials and Films for Various Applications. Chem. Soc. Rev. 2015, 44, 1585– 1607.

(6)

Mazierski, P.; Lisowski, W.; Grzyb, T.; Winiarski, M. J.; Klimczuk, T.; Mikołajczyk, A.; Flisikowski, J.; Hirsch, A.; Kołakowska, A.; Puzyn, T.; Zaleska-Medynska, A.; Nadolna, J. Enhanced Photocatalytic Properties of Lanthanide-TiO2 Nanotubes: An Experimental and Theoretical Study. Appl. Catal., B 2017, 205, 376–385.

(7)

Ye, H.; He, M.; Zhou, T.; Guo, Q.; Zhang, J.; Liao, L.; Mei, L.; Liu, H.; Runowski, M. A Novel Reddish-Orange Fluorapatite Phosphor, La6-xBa4(SiO4)6F2: xSm3+ - Structure, Luminescence and Energy Transfer Properties. J. Alloy. Compd. 2018, 757, 79–86.

(8)

Wybourne, B. G.; Smentek, L. Optical Spectroscopy of Lanthanides, CRC Press.; New York, 2007. 16 ACS Paragon Plus Environment

Page 17 of 23 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(9)

Zheng, W.; Huang, P.; Tu, D.; Ma, E.; Zhu, H.; Chen, X. Lanthanide-Doped Upconversion Nano-Bioprobes: Electronic Structures, Optical Properties, and Biodetection. Chem. Soc. Rev. 2015, 44, 1379–1415.

(10)

Runowski, M.; Stopikowska, N.; Goderski, S.; Lis, S. Luminescent-Plasmonic, Lanthanide-Doped Core/Shell Nanomaterials Modified with Au Nanorods – UpConversion Luminescence Tuning and Morphology Transformation after NIR Laser Irradiation. J. Alloy. Compd. 2018, 762, 621–630.

(11)

Binnemans, K. Lanthanide-Based Luminescent Hybrid Materials. Chem. Rev. 2009, 109 (9), 4283–4374.

(12)

Runowski, M.; Lis, S. Synthesis of Lanthanide Doped CeF3:Gd3+, Sm3+ Nanoparticles, Exhibiting Altered Luminescence after Hydrothermal Post-Treatment. J. Alloy. Compd. 2016, 661, 182–189.

(13)

Li, G.; Lin, C. C.; Chen, W.-T.; Molokeev, M. S.; Atuchin, V. V.; Chiang, C.-Y.; Zhou, W.; Wang, C.-W.; Li, W.-H.; Sheu, H.-S.; et al. Photoluminescence Tuning via Cation Substitution in Oxonitridosilicate Phosphors: DFT Calculations, Different Site Occupations, and Luminescence Mechanisms. Chem. Mater. 2014, 26, 2991–3001.

(14)

Atuchin, V. V.; Aleksandrovsky, A. S.; Chimitova, O. D.; Diao, C.-P.; Gavrilova, T. A.; Kesler, V. G.; Molokeev, M. S.; Krylov, A. S.; Bazarov, B. G.; Bazarova, J. G.; et al. Electronic Structure of β-RbSm(MoO4)2 and Chemical Bonding in Molybdates. Dalt. Trans. 2015, 44, 1805–1815.

(15)

Ji, H.; Huang, Z.; Xia, Z.; Molokeev, M. S.; Atuchin, V. V.; Fang, M.; Liu, Y. Discovery of New Solid Solution Phosphors via Cation Substitution-Dependent Phase Transition in M3(PO4)2:Eu2+ (M = Ca/Sr/Ba) Quasi-Binary Sets. J. Phys. Chem. C 17 ACS Paragon Plus Environment


Page 18 of 23

2015, 119, 2038–2045. (16)

Malta, O. L. Mechanisms of Non-Radiative Energy Transfer Involving Lanthanide Ions Revisited. J. Non-Cryst. Solids 2008, 354, 4770–4776.

(17)

Shyichuk, A.; Moura, R. T.; Carneiro Neto, A. N.; Runowski, M.; Zarad, M. S.; Szczeszak, A.; Lis, S.; Malta, O. L. Effects of Dopant Addition on Lattice and Luminescence Intensity Parameters of Eu(III)-Doped Lanthanum Orthovanadate. J. Phys. Chem. C 2016, 120, 28497–28508.

(18)

Tanner, P. A. Some Misconceptions Concerning the Electronic Spectra of Tri-Positive Europium and Cerium. Chem. Soc. Rev. 2013, 42, 5090–5101.

(19)

Kumar, P.; Nagpal, K.; Gupta, B. K. Unclonable Security Codes Designed from Multicolor Luminescent Lanthanide-Doped Y2O3 Nanorods for Anticounterfeiting. ACS Appl. Mater. Interfaces 2017, 9, 14301–14308.

(20)

Runowski, M.; Marciniak, J.; Grzyb, T.; Przybylska, D.; Shyichuk, A.; Barszcz, B.; Katrusiak, A.; Lis, S. Lifetime Nanomanometry – High-Pressure Luminescence of upConverting Lanthanide Nanocrystals – SrF2:Yb3+,Er3+. Nanoscale 2017, 9, 16030– 16037.

(21)

Runowski, M.; Woźny, P.; Lavín, V.; Lis, S. Optical Pressure Nano-Sensor Based on Lanthanide Doped SrB2O4:Sm2+ Luminescence – Novel High-Pressure Nanomanometer. Sens. Actuators B Chem. 2018, 273, 585–591.

(22)

Szczeszak, A.; Ekner-Grzyb, A.; Runowski, M.; Szutkowski, K.; Mrówczyńska, L.; Kaźmierczak, Z.; Grzyb, T.; Dąbrowska, K.; Giersig, M.; Lis, S. Spectroscopic, Structural and in Vitro Cytotoxicity Evaluation of Luminescent, Lanthanide Doped Core@shell Nanomaterials GdVO4:Eu3+5%@SiO2@NH2. J. Colloid Interface Sci. 18 ACS Paragon Plus Environment

Page 19 of 23 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


2016, 481, 245–255. (23)

Xia, Z.; Zhang, Y.; Molokeev, M. S.; Atuchin, V. V. Structural and Luminescence Properties of Yellow-Emitting NaScSi2O6:Eu2+ Phosphors: Eu2+ Site Preference Analysis and Generation of Red Emission by Codoping Mn2+ for White-Light-Emitting Diode Applications. J. Phys. Chem. C 2013, 117, 20847–20854.

(24)

Lim, C. S.; Aleksandrovsky, A.; Molokeev, M.; Oreshonkov, A.; Atuchin, V. The Modulated Structure and Frequency Upconversion Properties of CaLa2(MoO4)4:Ho3+/Yb3+ Phosphors Prepared by Microwave Synthesis. Phys. Chem. Chem. Phys. 2015, 17, 19278–19287.

(25)

Lim, C. S.; Aleksandrovsky, A. S.; Molokeev, M. S.; Oreshonkov, A. S.; Atuchin, V. V. Microwave Synthesis and Spectroscopic Properties of Ternary Scheelite-Type Molybdate Phosphors NaSrLa(MoO4)3:Er3+,Yb3+. J. Alloy. Compd. 2017, 713, 156– 163.

(26)

Li, G.; Zhang, Y.; Geng, D.; Shang, M.; Peng, C.; Cheng, Z.; Lin, J. SingleComposition Trichromatic White-Emitting Ca4Y6(SiO4)6O: Ce3+/Mn2+/Tb3+ Phosphor: Luminescence and Energy Transfer. ACS Appl. Mater. Interfaces 2012, 4, 296–305.

(27)

Guo, Q.; Wang, Q.; Jiang, L.; Liao, L.; Liu, H.; Mei, L. A Novel Apatite, Lu5(SiO4)3 N:(Ce,Tb), Phosphor Material: Synthesis, Structure and Applications for NUV-LEDs. Phys. Chem. Chem. Phys. 2016, 18, 15545–15554.

(28)

Li, K.; Geng, D.; Shang, M.; Zhang, Y.; Lian, H.; Lin, J. Color-Tunable Luminescence and Energy Transfer Properties of Ca9Mg(PO4)6F2:Eu2+, Mn2+ Phosphors for UVLEDs. J. Phys. Chem. C 2014, 118, 11026–11034.

(29)

Kim, D.; Park, D.; Oh, N.; Kim, J.; Jeong, E. D.; Kim, S.-J.; Kim, S.; Park, J.-C. 19 ACS Paragon Plus Environment


Page 20 of 23

Luminescent Properties of Rare Earth Fully Activated Apatites, LiRE9(SiO4)6O2 (RE = Ce, Eu, and Tb): Site Selective Crystal Field Effect. Inorg. Chem. 2015, 54, 1325– 1336. (30)

Guo, Q.; Liao, L.; Lis, S.; Liu, H.; Mei, L. Effect of Ionic Substitution (Ca/Sr/Ba) on Structure and Luminescent Properties of Ce3+doped Fluorapatite. J. Lumin. 2018, 196, 285–289.

(31)

Bednarkiewicz, A.; Trejgis, K.; Drabik, J.; Kowalczyk, A.; Marciniak, L. PhosphorAssisted Temperature Sensing and Imaging Using Resonant and Nonresonant Photoexcitation Scheme. ACS Appl. Mater. Interfaces 2017, 9, 43081–43089.

(32)

Liu, Y.; Tu, D.; Zhu, H.; Chen, X. Lanthanide-Doped Luminescent Nanoprobes: Controlled Synthesis, Optical Spectroscopy, and Bioapplications. Chem. Soc. Rev. 2013, 42, 6924–6958.

(33)

Wisser, M. D.; Chea, M.; Lin, Y.; Wu, D. M.; Mao, W. L.; Salleo, A.; Dionne, J. A. Strain-Induced Modification of Optical Selection Rules in Lanthanide-Based Upconverting Nanoparticles. Nano Lett. 2015, 15, 1891–1897.

(34)

Runowski, M.; Bartkowiak, A.; Majewska, M.; Martín, I. R.; Lis, S. Upconverting Lanthanide Doped Fluoride NaLuF4:Yb3+-Er3+-Ho3+ - Optical Sensor for Multi-Range Fluorescence Intensity Ratio (FIR) Thermometry in Visible and NIR Regions. J. Lumin. 2018, 201, 104–109.

(35)

Jaque, D.; Vetrone, F. Luminescence Nanothermometry. Nanoscale 2012, 4, 4301– 4326.

(36)

Bray, K. L.; Glasbeek, M.; Kunkely, H.; Vogler, A.; Yersin, H. ed. Transition Metal and Rare Earth Compounds Excited States, Transitions, Interactions I, Springer.; New 20 ACS Paragon Plus Environment

Page 21 of 23 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


York, 2001. (37)

Tröster, T. Optical Studies of Non-Metallic Compounds under Pressure. In Handbook on the Physics and Chemistry of Rare Earths, volume 33; Gschneidner, K. A., Bünzli, J.-C. G., Pecharsky, V. K., Eds.; North-Holland, 2003; pp 515–589.

(38)

Mao, H. K.; Xu, J.; Bell, P. M. Calibration of the Ruby Pressure Gauge to 800 Kbar under Quasi-Hydrostatic Conditions. J. Geophys. Res. 1986, 91, 4673–4676.

(39)

Dewaele, A.; Torrent, M.; Loubeyre, P.; Mezouar, M. Compression Curves of Transition Metals in the Mbar Range: Experiments and Projector Augmented-Wave Calculations. Phys. Rev. B 2008, 78, 104102.

(40)

Datchi, F.; LeToullec, R.; Loubeyre, P. Improved Calibration of the SrB4O7:Sm2+ Optical Pressure Gauge: Advantages at Very High Pressures and High Temperatures. J. Appl. Phys. 1997, 81, 3333–3339.

(41)

Rashchenko, S. V.; Kurnosov, A.; Dubrovinsky, L.; Litasov, K. D. Revised Calibration of the Sm:SrB4O7 Pressure Sensor Using the Sm-Doped Yttrium-Aluminum Garnet Primary Pressure Scale. J. Appl. Phys. 2015, 117, 2–7.

(42)

Barnett, J. D.; Block, S.; Piermarini, G. J. An Optical Fluorescence System for Quantitative Pressure Measurement in the Diamond-Anvil Cell. Rev. Sci. Instrum. 1973, 44, 1–9.

(43)

Arashi, H.; Ishigame, M. Diamond Anvil Pressure Cell and Pressure Sensor for HighTemperature Use. Jpn. J. Appl. Phys. 1982, 21, 1647–1649.

(44)

Hess, N. J.; Exarhos, G. J. Temperature and Pressure Dependence of Laser Induced Fluorescence in Sm:YAG—a New Pressure Calibrant. High Press. Res. 1989, 2, 57–



Page 22 of 23

64. (45)

Shen, Y. R.; Holzapfel, W. B. Effect of Pressure on Energy Levels of Sm2+ in BaFCl and SrFCl. Phys. Rev. B 1995, 51, 15752–15762.

(46)

Gong, X.; Lin, Y.; Chen, Y.; Huang, Z.; Huang, Y.; Luo, Z. Syntheses, Structure, and Characterization of Crystal La6Ba4(SiO4)6F2, a Promising Laser Host. Chem. Mater. 2005, 17, 1135–1138.

(47)

Rodriguez-Mendoza, U. R.; Cunningham, G. B.; Shen, Y.; Bray, K. L. High-Pressure Luminescence Studies in Ce3+ :Lu2SiO5. Phys. Rev. B 2001, 64, 195112.

(48)

Sato, M.; Kim, S. W.; Shimomura, Y.; Hasegawa, T.; Toda, K.; Adachi, G. Rare EarthDoped Phosphors for White Light-Emitting Diodes, Vol. 49, Chap. 278. In Handbook on the Physics and Chemistry of Rare Earths; Bunzli, J.-C. G., Pecharsky, V. K., Eds.; Elsevier, 2016; p 16.

(49)

Sastri, D. V. S.; Bünzli, D. J.-C.; Rao, D. V. R.; Rayudu, D. G. V. S.; Perumareddi, D. J. R. Modern Aspects of Rare Earths and Their Complexes; Elsevier, 2003.

(50)

Ramanantoanina, H.; Urland, W.; García-Fuente, A.; Cimpoesu, F.; Daul, C. Calculation of the 4f1→4f05d1 Transitions in Ce3+-Doped Systems by Ligand Field Density Functional Theory. Chem. Phys. Lett. 2013, 588, 260–266.

(51)

Lorenz, B.; Shen, Y. R.; Holzapfel, W. B. High Press. Res. 1994, 12, 91–99.


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Optical Pressure Sensor Based on the Emission and Excitation Band

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