Supporting Information for:
Multifunctional Optical Sensors for Nanomanometry & Nanothermometry: High-Pressure and Temperature Upconversion Luminescence of Lanthanide Doped Phosphates - LaPO4/YPO4:Yb3+-Tm3+ Marcin Runowski,1,* Andrii Shyichuk,2 Artur Tymiński,1 Tomasz Grzyb1, Víctor Lavín,3 and Stefan Lis1 1
Adam Mickiewicz University, Faculty of Chemistry, Umultowska 89b, 61-614 Poznań,
Poland 2
Faculty of Chemistry, University of Wrocław, F. Joliot-Curie 14, 50-383 Wrocław, Poland
3
Departamento de Física, MALTA Consolider Team, and IUdEA, Universidad de La Laguna,
Apdo. 456, E-38200 San Cristóbal de La Laguna, Santa Cruz de Tenerife, Spain *
Corresponding author:
[email protected]
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Materials Rare earth (RE) oxides: Tm2O3, Yb2O3, La2O3 and Y2O3 (99.99%, Stanford Materials, United States) were dissolved separately in nitric acid, HNO3 (65%, ultrapure, POCh. S.A., Poland), to obtain the corresponding nitrates, and then evaporated in order to remove an excess of the acid. Ammonium phosphate monobasic, NH4H2PO4 (ACS reagent 98%, Sigma Aldrich, Poland) and glycerin, (99% pure, POCh. S.A., Poland) were used as received, without further purification. Deionized water was used for the synthesis.
Synthesis of LaPO4: 20% Yb3+, 0.5% Tm3+ and YPO4: 20% Yb3+, 0.5% Tm3+ NPs The typical synthesis was performed to obtain 1 g of the final product, started by mixing the rare earth (RE) nitrate solutions in a desired molar ratio, i.e. 0.5 mol.% Tm(NO3)3, 20 mol.% Yb(NO3)3 and 79.5 mol.% La(NO3)3 or Y(NO3)3, for the Tm3+/Yb3+-doped LaPO4 and YPO4, respectively. Afterwards, the prepared RE(NO3)3 solution was mixed with 75 mL of deionized water and 25 ml of glycerin in a 200 mL beaker. Glycerin was used in order to stabilize the NPs size and prevent aggregation of crystals. The mixture was heated and magnetically stirred up to 323 K. Then, 50 mL of aqueous ammonium phosphate solution (50% molar excess), was added dropwise to the system. The white suspension was obtained immediately and it has been stirred for 30 minutes, while maintaining the temperature in the range of 323-325 K. After that, the suspension was centrifuged and washed four times with water and ethanol. The precipitate was separated from the solution and dried at 353 K in an oven, for several days. Next, the samples were annealed in the air atmosphere at 1273 K for 2 h in order to remove the organic impurities and form the nanocrystalline product. After that, products were grounded in an agate mortar and the white nanopowders were obtained. The exact elemental composition of the synthesized NPs, determined by ICP-OES analysis is 0.47 mol.% Tm, 20.38 mol.% Yb and 79.15 mol.% La (LaPO4:Yb3+/Tm3+), and 0.40 mol.% Tm, 23.81 mol.% Yb and 75.80 mol.% Y (YPO4:Yb3+/Tm3+). DAC loading procedure The high-pressure measurements at ambient temperature were performed with a membrane cell, where the pressure is adjusted by the use of helium gas. Whereas, the high-pressure measurements under high temperature conditions were performed with a small diamond anvil cell, made at The University of Paderborn (Germany), where the pressure is adjusted by the use of four metal screws. The gaskets were made of tungsten carbide sheets 200 μm thick, S-2
with the aperture of ≈150 μm (hole size). The gaskets were pre-indented to ≈50 μm thick (sample thickness). The DAC chamber was loaded with sample (white powders) and filled with methanol/ethanol/water (16:3:1 vol.) solvent system (pressure transmitting medium), to provide hydrostaticity of the systems up to ≈10 GPa. Pressure calibration Pressure was determined by the ruby R1 fluorescence line shift, excited with a solid-state diode-pumped (SSDP) 532 nm laser. The measurements were performed using a standard ruby calibration curve, available at: http://kantor.50webs.com/ruby.htm. Luminescence measurements The measurements of high-pressure up-conversion emission of the sample placed in the DAC were performed in a back illuminated configuration, with a 180 o detection geometry (transmitting mode). The laser beam was focused on the sample, being placed in a gasket hole, and the emission signal was collected from the opposite site of the DAC. The luminescence measurements under high temperature conditions were performed via placing a thin piece of the sample squeezed between two 200 μm thick microscope glasses, in a center of a specially calibrated tube furnace (± 1 K). The illumination and detection geometry were the same as for high-pressure experiments. Before the experiments, the power of the laser was adjusted to be low enough (≈0.5 W), to avoid the undesired temperature increase of the sample via a heating of the material with a laser beam. This requirement was fulfilled when no laser-induced thermalization of the levels occurred, i.e. the bands ratio remained unchanged at a constant temperature. Afterwards, when the temperature of the furnace was elevated up to the desired value, the sample stayed in the furnace tube for about 10-15 minutes each time before the luminescence measurement, to ensure a thermal equilibrium of the system. A similar protocol was applied for the luminescence measurements of the sample in DAC under high temperature and high pressure conditions. However, this time the temperature was measured with a thermocouple placed in a one of the external gap in the DAC. Additional high-pressure data The observed broadening and quenching of the Raman bands (phonon modes) with increasing pressure values, are related to the decreasing ordering of the crystal lattices, increasing S-3
amount of defects and strain in the crystals, as well as increasing non-hydrostaticity of the system above ≈10 GPa. The shift of the peaks toward higher wavenumber and their shape alterations are fully reversible, which can be clearly seen in the spectra presented. This confirms the fully reversible compression of the materials, which is important for the pressure sensor applications. The peaks corresponding to the diamond anvils from DAC (around 1030 cm-1), are denoted with an asterisk (*).
Figure S1. Normalized Raman spectra for LaPO4:Yb3+/Tm at high pressure, measured during compression-decompression cycle; *peak corresponding to the diamond anvils from DAC.
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Figure S2. Normalized Raman spectra for YPO4:Yb3+/Tm at high pressure, measured during compression-decompression cycle; *peak corresponding to the diamond anvils from DAC (overlapping with B1g mode).
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Figure S3. Normalized emission spectra (PMT) for LaPO4:Yb3+/Tm at high pressure, measured during decompression cycle; λex= 975 nm.
Figure S4. Emission spectra (PMT) for LaPO4:Yb3+/Tm at high pressure, measured during decompression cycle; λex= 975 nm.
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Figure S5. Normalized emission spectra (PMT) for YPO4:Yb3+/Tm at high pressure, measured during decompression cycle; λex= 975 nm.
Figure S6. Emission spectra (PMT) for YPO4:Yb3+/Tm at high pressure, measured during decompression cycle; λex= 975 nm.
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Figure S7. Determined pressure calibration curve based on the 3H4→3H6/1G4→3H6 band ratio of the LaPO4:Yb3+-Tm3+; λex= 975 nm.
Figure S8. Determined pressure calibration curve based on the spectral position of 1
G4→3H6 emission band of the LaPO4:Yb3+-Tm3+; λex= 975 nm.
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Figure S9. Luminescence decay curves for LaPO 4:Yb3+/Tm at high pressure, recorded during decompression cycle; λex= 975 nm, λem= 451, 480, 648 and 790 nm for 1D2→3F4, 1G4→3H6, 1
G4→3F4, 3H4→3H6 transitions, respectively.
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Figure S10. Luminescence decay curves for YPO4:Yb3+/Tm at high pressure, recorded during decompression cycle; λex= 975 nm, λem= 451, 480, 648 and 796 nm for 1D2→3F4, 1G4→3H6, 1
G4→3F4, 3H4→3H6 transitions, respectively.
S-10
Curve fitting The decay curves were normalized to [0;1] range before fitting. The fitting was performed by a custom code developed by us. The code was written in Python language and exploited SciPy module, version 0.18.1. The program used functions defined is SciPy style, and did the input file reading, results saving and plotting part. The actual fitting was performed using least_squares module of SciPy, with 3-point Jacobian, lsmr solver and x_scale option. The description of the module can be found at: https://docs.scipy.org/doc/scipy-0.19.0/reference/generated/scipy.optimize.least_squares.html In the least_squares module, the input is a vector of guess values of fit parameters, e.g. x = [ t0, I0, A0, τ1, τ2]. The module calculates gradient in each parameter, via changing it by 1e-8 and recalculating the residual function (sum of squared residuals, where residual is fitted curve minus original curve). As the absolute initial values of variables may differ by several orders of magnitude (e.g. τrise = 10 and A3 = 0.0002), they are changed with relatively different steps. However, if we define an x_scale vector equal to x, the problem is redefined in xs = x/x_scale. The guess values become coefficients and the code manipulates the initial vector of ones, [1,1,1,1,1], changing them (initially) by 1e-8. Thus, every parameter is changed proportionally to its value. Two functions were used to fit the rise and decay luminescence curves as a function of time. I = I0 + A0 (1 – exp(–(t-t0)/τrise)n ( exp(–(t-t0)/τ1-decay) + A3 exp(–(t-t0)/τ2-decay))
(1)
I =I0 + A0 (1 – exp(–(t-t0)/τrise)n exp(–(t-t0)/τ2-decay) (2) Here, I0 is ordinate-offset, and t0 is abscissa-offset. Note that the offsets were omitted in the main text function specification. The first exponential term is rise, while the others are decays. Note that coefficient before exp(–t/τ1-decay) in function (1) is redundant, it can be shown that it is included in A0. Consequently, function (1) has minimal possible number of degrees of freedom, which stabilized the numerical fitting procedure. The power of the rise component, n, was not a fit parameter; it was 2 for 3- and 4-photon processes, and 1 for 2-photon processes. The decay parts of some YVO4:Yb,Tm higher-pressure curves exhibit a certain bend, illustrating two-exponential kinetics. A two-step fitting procedure was used in order to determine if the two-exponential function (1) was required. First, the curves were fit with function (2). The values of I0, A0, t0, τrise and τdecay were used in the guess for the second-step S-11
fitting with function (1). The A 3 coefficient was set to 0.0002. With this small value, some of the fittings converged and the A3 value did not change, indicating no effect of the second decay exponent (τ2-decay) on the kinetics. Some other samples, however, converged with higher A3 or the fitting was not completed in the given 500 steps. For those samples, the fitting was repeated with A3 = 0.01 as guess. For the LaVO 4:Yb,Tm, only function (2) was used. For both cases, for 2-photon 3H4→3H6 up-conversion emission, the rise exponent power coefficient n was set to 1, resulting in a rise-times-decay kinetics. For 3-photon 1G4→3F4 and 1G4→3H6, as well as 4-photon 1D2→3F4 transitions, the coefficient was set to 2, giving a rise-squared-timesdecay kinetics. These values of n were selected via trial and effort routine, and result in the best fits. Additionally, squared rise is not surprising for higher-photonity processes: the cascade of mutually dependent populating transition is much longer. It is interesting that functions with sum of two independent rise exponents (e.g. (rise1 + rise2) times decay), or functions with two dependent rise exponents (i.e. rise1-times-rise2times-decay) did not result in good fits; the fitting residuals contained some signals. In other words, even for two-decay samples, there was certainly one rise. Such behavior is actually not surprising. Given a crystal phase change under pressure, sample volume remains rather the same, and the mutual positions of the Ln dopant ions (as well as distances between them) remain rather the same. As rise times are mostly defined by the energy transfer rates, which in turn are mostly defined by the interatomic distances, the rise times of both phases remain similar, or rather indistinguishable in the presented experimental setup. On the other hand, decay lifetimes depend, among others, on multiphonon relaxation and crystal field, the latter resulting from bond lengths and local symmetry at dopant ion sites. These two factors (especially crystal field) might be quite different in the two phases, resulting in twoexponential decays. Tables S1-S8 present the determined luminescence lifetimes (τrise - rise time; τdecay decay time) and fitting parameters (A – amplitude; R2 - correlation coefficient; to; Io) of the recorded up-conversion emission rise-decay curves, for the LaPO 4:Yb3+/Tm (S1-S4) and YPO4:Yb3+/Tm samples (S5-S8).
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Table S1 Determined luminescence lifetimes and fitting parameters for the LaPO 4:Yb3+/Tm sample at high pressure; 3H4→3H6 transition; λex= 975 nm, λem= 790 nm.
compression Pressure (GPa)
τrise (µs)
τdecay (µs)
A0
to
Io
R2
0.67 1.79 2.92 3.99 4.84 5.74 7.46 8.90 9.98 11.00 14.16 17.83 20.79 22.68 25.56
42.94 43.76 34.98 35.59 31.99 29.24 24.50 21.93 19.51 15.58 9.95 8.70 7.54 6.95 13.86
63.31 54.38 54.49 50.06 47.99 46.46 43.53 40.70 37.85 35.7 37.16 34.22 31.36 31.82 71.49
2.99 3.31 2.80 3.07 2.97 2.86 2.72 2.60 2.53 2.32 1.83 1.80 1.74 1.71 1.67
0.40276 0.84406 0.72026 0.85631 0.92217 0.8513 0.80627 0.74238 0.69111 0.62236 0.06525 0.0673 0.09584 -0.0024 -0.80268
0.00459 0.01176 0.00635 0.00975 0.00888 0.00704 0.00606 0.00559 0.00747 0.00575 0.0119 0.01064 0.01553 0.01412 -0.02208
0.99673 0.99932 0.99721 0.99928 0.99949 0.99953 0.99950 0.99937 0.99933 0.99936 0.99908 0.99940 0.99938 0.99962 0.99757
25.56 21.95 17.08 12.83 5.23 1.44
13.86 7.56 10.59 15.11 18.75 16.86
71.49 27.59 32.71 38.62 50.66 65.15
-0.80268 -0.21237 -0.35742 -0.37242 -0.64653 -0.68249
-0.02208 0.01316 0.0097 0.00901 0.00212 -0.00407
0.99757 0.99946 0.99970 0.99941 0.99882 0.99737
decompression 1.67 1.86 2.02 2.20 2.14 1.79
Table S2 Determined luminescence lifetimes and fitting parameters for the LaPO 4:Yb3+/Tm sample at high pressure; 1G4→3F4 transition; λex= 975 nm, λem= 648 nm.
compression Pressure (GPa)
τrise (µs)
τdecay (µs)
A0
to
Io
R2
0.67 1.79 2.92 3.99 4.84 5.74 7.46 8.90 9.98 11.00 14.16 17.83 20.79 22.68 25.56
26.57 25.03 23.43 22.47 21.62 20.77 18.29 16.74 14.95 13.21 9.19 7.74 6.51 6.10 20.31
79.23 69.92 66.90 61.92 57.63 54.50 50.34 45.85 41.92 38.89 43.25 38.84 35.43 36.46 87.92
2.48 2.67 2.52 2.69 2.71 2.77 2.65 2.65 2.6 2.52 1.94 1.86 1.8 1.73 2.15
-1.72 -0.56232 -0.63468 -0.15665 0.03162 -0.07269 0.09915 0.13052 0.05976 0.04863 -0.5051 -0.44995 -0.16101 -0.34849 -2.85
-0.01186 0.00167 0.00689 0.00846 0.01324 0.0151 0.01413 0.01938 0.01689 0.02055 0.02252 0.0216 0.02872 0.02616 -0.04005
0.99511 0.99918 0.99677 0.99950 0.99931 0.99925 0.99914 0.99895 0.99942 0.99952 0.99939 0.99920 0.99935 0.99964 0.99813
25.56 21.95 17.08 12.83 5.23 1.44
20.31 6.29 8.75 12.36 17.12 18.02
87.92 29.46 35.15 42.91 59.34 79.42
-2.85 -0.40209 -0.60694 -0.80045 -1.27 -2.24
-0.04005 0.02302 0.02238 0.02014 0.00641 -0.01889
0.99813 0.99952 0.99964 0.99947 0.99929 0.99806
decompression 2.15 1.94 2.11 2.29 2.33 2.06
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Table S3 Determined luminescence lifetimes and fitting parameters for the LaPO 4:Yb3+/Tm sample at high pressure; 1G4→3H6 transition; λex= 975 nm, λem= 480 nm.
compression Pressure (GPa)
τrise (µs)
τdecay (µs)
A0
to
Io
R2
0.67 1.79 2.92 3.99 4.84 5.74 7.46 8.90 9.98 11.00 14.16 17.83 20.79 22.68 25.56
26.62 25.58 23.55 23.26 22.37 21.28 19.35 17.46 15.37 13.44 9.19 7.9 6.56 5.95 22.83
79.6 69.94 66.16 61.54 57.38 54.59 50.24 46.07 42.26 40.72 44.46 40.54 30.81 37.38 88.61
2.55 2.76 2.65 2.81 2.82 2.83 2.78 2.74 2.69 2.49 1.92 1.86 1.93 1.71 2.28
-2.1 -0.98778 -0.58363 -0.48714 -0.10484 -0.10392 0.02929 0.16322 0.02699 0.25671 -0.37299 -0.33632 -0.07765 -0.23393 -2.97
-0.01468 -0.0024 0.00682 0.00773 0.01146 0.01234 0.01639 0.01884 0.01761 0.02199 0.02523 0.02154 0.02481 0.02803 -0.0391
0.99766 0.99976 0.99908 0.99973 0.99969 0.99977 0.99952 0.99958 0.99974 0.99959 0.99955 0.99960 0.99953 0.99963 0.99883
25.56 21.95 17.08 12.83 5.23 1.44
22.83 6.43 8.96 12.6 18.31 19.46
88.61 30.03 34.76 42.63 57.59 69.64
-2.97 -0.43837 -0.63517 -0.82033 -1.21 -2.09
-0.0391 0.0239 0.02224 0.02036 0.0102 -0.00438
0.99883 0.99959 0.99979 0.99970 0.99921 0.99932
decompression 2.28 1.95 2.16 2.35 2.46 2.31
Table S4 Determined luminescence lifetimes and fitting parameters for the LaPO 4:Yb3+/Tm sample at high pressure; 1D2→3F4 transition; λex= 975 nm, λem= 451 nm.
compression Pressure (GPa)
τrise (µs)
τdecay (µs)
A0
to
Io
R2
0.67 1.79 2.92 3.99 4.84 5.74 7.46 8.90 9.98 11.00 14.16 17.83 20.79 22.68 25.56
52.84 56.97 45.57 50.26 42.18 35.61 26.56 22.61 18.35 14.02 11.41 10.94 6.55 7.39 22.83
31.59 26.93 26.97 24.32 23.12 22.98 22.85 22.12 21.66 21.36 27.26 27.06 32.44 27.08 45.98
11.51 16.55 11.79 15.89 13.45 10.79 7.4 6.48 5.18 4.11 2.85 2.79 1.77 2.17 3.25
-0.88971 -0.05238 0.04476 0.3067 0.71992 0.80258 0.83641 0.82329 1.03 1.13 -0.25951 -0.10182 -0.22624 -0.30136 -1.79
0.00993 0.00533 0.01236 0.00988 0.00812 0.00725 0.01106 0.01193 0.02167 0.01553 0.01143 0.01861 0.03721 0.00919 -0.0097
0.99574 0.99930 0.99761 0.99860 0.99907 0.99945 0.99828 0.99815 0.99757 0.99813 0.99709 0.99795 0.99432 0.99880 0.99567
25.56 21.95 17.08 12.83 5.23 1.44
22.83 6.84 10.71 17.16 23.36 23.8
45.98 21.99 23.04 23.67 28.07 38.26
-1.79 -0.28541 -0.50446 -0.73472 -0.43486 -1.03
-0.0097 0.01323 0.01438 0.01201 0.02395 0.0276
0.99567 0.99887 0.99836 0.99906 0.99764 0.99267
decompression 3.25 2.35 3.09 4.59 5.1 3.56
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Table S5 Determined luminescence lifetimes and fitting parameters for the YPO 4:Yb3+/Tm sample at high pressure; 3H4→3H6 transition; λex= 975 nm, λem= 796 nm.
compression Pressure (GPa)
τrise (µs)
τ1-decay (µs)
τ2-decay (µs)
A0
A3
to
Io
R2
0.64 1.76 3.16 5.39 7.4 9.91 11.47 12.85 15.22 17.2 19.5 21.36 24.35
25.62 24.69 24.13 22.5 20.55 18.09 16.58 15.63 13.72 13.6 10.31 8.46 5.85
65.29 60.99 57.45 52.84 46.94 44.13 39.41 34.01 29.39 23.54 22.26 18.14 14.79
85.11 45.35 54.25 48.42 52.75
2.25 2.28 2.24 2.21 2.28 2.24 2.17 2.36 2.32 2.27 1.95 2.19 2.12
0.01980 0.14349 0.14303 0.07438 0.04531
1.14 1.15 1.16 1.14 1.02 1.06 1.14 0.95891 0.89383 0.73697 0.68691 0.50155 0.41584
-0.01410 -0.01041 -0.00557 0.00095 0.00304 0.00539 0.01025 0.00498 0.00355 0.00339 0.00463 0.00316 0.00148
0.99862 0.99839 0.99804 0.99568 0.99784 0.99754 0.99610 0.99867 0.99852 0.99898 0.99909 0.99951 0.99939
24.35 21.42 15.31 8.46 4.33 0.0001
5.85 6.99 11.1 15.41 19.28 23.83
14.79 16.19 21.47 36.87 46.63 55.19
52.75 46.24 69.96 -
0.04531 0.06317 0.07326 -
0.41584 0.43719 0.48804 0.7811 0.93154 1.22
0.00148 0.00293 -0.00259 0.00924 0.00517 0.0032
0.99939 0.99956 0.99876 0.99765 0.99729 0.99931
decompression 2.12 2.15 2.26 2.19 2.21 2.35
Table S6 Determined luminescence lifetimes and fitting parameters for the YPO 4:Yb3+/Tm sample at high pressure; 1G4→3F4 transition; λex= 975 nm, λem= 648 nm.
compression Pressure (GPa)
τrise (µs)
τ1-decay (µs)
τ2-decay (µs)
0.64 1.76 3.16 5.39 7.4 9.91 11.47 12.85 15.22 17.2 19.5 21.36 24.35
28.39 26.74 25.13 21.24 18.34 15.52 13.15 10.14 9.27 7.64 7.01 5.37 4.62
57.01 53.7 50.23 53.95 49.22 50.98 47.1 37.5 24.6 20.14 13.47 14.38 10.85
83.87 69.15 61.35 78.76 59.92
24.35 21.42 15.31 8.46 4.33 0.0001
4.62 5.29 8.03 11.76 17.68 23.81
10.85 12.32 15.36 39.11 46.46 56.79
59.92 62.16 54.34 -
A0
A3
to
Io
R2
3.41 3.41 3.31 2.74 2.63 2.2 2.07 2.08 2.12 2.05 1.64 2.35 2.72
0.14092 0.20159 0.51437 0.11047 0.06378
-0.33869 -0.33723 -0.09366 -0.10815 0.12816 -0.03037 -0.02842 0.50665 -0.2588 -0.17573 -0.1549 -0.04418 -0.00542
-0.01129 -0.01279 -0.00451 -0.00842 0.00687 0.00987 0.01844 0.02241 -0.00811 -0.00543 -0.0022 -0.00888 -0.00007
0.99899 0.99901 0.99736 0.99684 0.99512 0.99158 0.98915 0.99802 0.9985 0.99862 0.99737 0.99919 0.99962
0.06378 0.06604 0.24772 -
-0.00542 -0.03696 -0.10591 0.02402 -0.39263 -0.38094
-0.00007 -0.0011 0.00732 0.02112 8.2E-4 -0.00952
0.99962 0.99973 0.99796 0.99576 0.99835 0.99962
decompression 2.72 2.72 2.33 2.16 2.71 3.04
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Table S7 Determined luminescence lifetimes and fitting parameters for the YPO 4:Yb3+/Tm sample at high pressure; 1G4→3H6 transition; λex= 975 nm, λem= 480 nm.
compression Pressure (GPa)
τrise (µs)
τ1-decay (µs)
τ2-decay (µs)
0.64 1.76 3.16 5.39 7.4 9.91 11.47 12.85 15.22 17.2 19.5 21.36 24.35
28.76 27.03 26.03 22.46 19.08 14.84 12.96 10.69 9.38 7.74 7.04 6.11 4.91
56.8 53.35 48.96 51.97 47.28 47.16 44.85 36.31 24.67 20.47 14.33 13.37 10.76
154.17 87.17 58.56 66.5 59.75
24.35 21.42 15.31 8.46 4.33 0.0001
4.91 5.43 7.76 12.42 18.49 24.32
10.76 12.43 17.06 37.51 45.15 56.11
59.75 65.59 62.78 -
A0
A3
to
Io
R2
3.52 3.54 3.59 2.96 2.84 2.4 2.18 2.3 2.55 2.35 2.17 2.68 2.93
0.0775 0.11213 0.29467 0.10728 0.0529
-0.34127 -0.32874 -0.12212 -0.18504 0.10376 -0.06741 -0.10837 0.50231 -0.47826 -0.18845 -0.03314 -0.06404 -0.04062
-0.01497 -0.01314 -0.0058 -0.00459 0.00257 0.00349 0.00871 0.0214 -0.03972 -0.01288 -0.00155 -0.00412 -0.00068
0.99975 0.99966 0.99935 0.99799 0.99879 0.99823 0.99578 0.99943 0.99959 0.99947 0.99949 0.99964 0.99983
0.0529 0.05415 0.16253 -
-0.04062 -0.02561 -0.08014 -0.04868 -0.48525 -0.66052
-6.8E-4 -0.00224 -0.00224 0.01442 5.3E-4 -0.00953
0.99983 0.99984 0.99961 0.999 0.99943 0.99979
decompression 2.93 2.85 2.46 2.45 2.95 3.13
Table S8 Determined luminescence lifetimes and fitting parameters for the YPO 4:Yb3+/Tm sample at high pressure; 1D2→3F4 transition; λex= 975 nm, λem= 451 nm.
compression Pressure (GPa)
τrise (µs)
τ1-decay (µs)
τ2-decay (µs)
0.64 1.76 3.16 5.39 7.4 9.91 11.47 12.85 15.22 17.2 19.5 21.36 24.35
54.47 63.08 54.67 39.01 26.86 26.22 15.52 12.54 31.4 15.75 23.17 15.83 7.16
27.29 24.64 24.76 28.97 31.87 29.5 32.09 27.71 10.35 9.63 7.1 6.58 6.94
30.73 34.72 36.06 39.63 46.11
24.35 21.42 15.31 8.46 4.33 0.0001
7.16 9.94 27.56 14.96 28.45 42.88
6.94 7.15 7.43 31.39 25.89 27.4
46.11 38.59 33.46 -
A0
A3
to
Io
R2
15.34 21.5 16.86 7.58 4.75 5.35 2.91 2.81 20.38 8.66 22.17 13.21 5.95
0.07505 0.10955 0.06607 0.05528 0.03792
2.83 2.9 2.63 2.2 2.57 1.7 2 1.69 0.50327 0.57663 0.4226 0.43203 0.57804
0.00282 0.00558 0.01935 0.05001 0.02103 0.01448 0.02106 0.02604 0.01772 0.01119 0.02725 0.0418 0.0071
0.99934 0.99899 0.99649 0.98472 0.99006 0.9953 0.99093 0.99246 0.99104 0.99639 0.98659 0.98074 0.99780
0.03792 0.0375 0.05385 -
0.57804 0.61637 0.74882 1.5 1.95 2.34
0.0071 0.01336 0.01389 0.02572 0.0141 0.00563
0.99780 0.99824 0.99482 0.98807 0.99719 0.99874
decompression 5.95 8.33 30.49 2.85 6.86 10.99
S-16
Figure S11. Normalized emission spectra of ruby at high pressure and temperature; λex= 532 nm.
Figure S12. Normalized emission spectra (PMT) for LaPO4:Yb3+/Tm at high pressure and temperature; λex= 975 nm.
S-17
Figure S13. Emission spectra (corrected for PMT response) for LaPO4:Yb3+/Tm at high pressure and temperature; λex= 975 nm.
S-18
