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S1
Supporting information
CsRe2F7@Glass Nanocomposites with Efficient Up-/Down-Conversion
Luminescence: from In-Situ Nanocrystallization Synthesis to Multi-
Functional Applications
Jiangkun Chena,b,c, Shaoxiong Wanga,b,c, Jidong Lina,b,c, Daqin Chena,b,c,*
[a] College of Physics and Energy, Fujian Normal University, Fujian Provincial Key Laboratory of Quantum Manipulation and New Energy Materials, Fuzhou, 350117, China
*Corresponding author. E-Mail: [email protected]
[b] Fujian Provincial Collaborative Innovation Center for Optoelectronic Semiconductors and Efficient Devices, Xiamen, 361005, China
[c] Fujian Provincial Engineering Technology Research Center of Solar Energy Conversion and Energy Storage, Fuzhou, 350117, China
Electronic Supplementary Material (ESI) for Nanoscale.This journal is © The Royal Society of Chemistry 2019
S2
Theoretical calculation laser-irradiation-induced temperature for Er: CsYb2F7@glass. Based
on the Boltzmann distribution theory, UC fluorescence intensity ratio (FIR) of Er3+ 2H11/2 and 4S3/2
thermally coupled states satisfies the following equation:
(1)525
545
= exp( ) exp( )H H H H
S S S S B B
I g A w E EFIR CI g A w k T k T
where I525 and I545 are the integrated UC intensities corresponding to the 2H11/2→4I15/2 and
4S3/2→4I15/2 transitions of Er3+, respectively, g, A, σ and w are the degeneracy, the spontaneous
radiative transition rate, the fluorescence cross-section and the angular frequency of emission
transitions from the 2H11/2 or 4S3/2 excited state to the 4I15/2 ground state of Er3+, ΔE is the energy gap
of the two thermally coupled states, kB is the Boltzmann constant, T is the absolute temperature, and
C is the constant. Eq. (1) can be expressed as the follow:
(2)( ) ( ) ( )B
ELn FIR Ln Ck T
The plot of Ln(FIR) versus inverse absolute temperature is linear and the slope ( ) and B
Ek
intercept ( ) can be determined via the linear fitting of experiment data. According to Eq. ( )Ln C
(1), FIR alters in terms of temperature while this FIR also depends on laser pumping power,
therefore temperature can be correlated with pumping power by the following equation:
(3)
[ ( ) ( )]B
ETk Ln C Ln FIR
where all the parameters have their usual meanings. As a consequence, the temperature in the Er:
CsYb2F7@glass sample induced by laser photothermal effect can be evaluated.
S3
Table S1 Crystallographic data of CsGd2F7, showing possible 8 cation sites of Gd. The data for the
other CsRe2F7 compounds are similar. [S1]
[S1] K. Friese, N. Khaidukov, A. Grzechnik, Twinned CsLn2F7 compounds (Ln=Nd, Gd, Tb, Er, Yb): The role of a highly symmetrical cation lattice with an arrangement analogous to the Laves phase MgZn2. Zeitschrift für Kristallographie - Crystalline Materials. 2016, 231, DOI: 10.1515/zkri-2016-1972.
Atom X Y Z Uiso
Cs1 0.16251(2) 0.08903(2) 0.07580(2) 0.01965(9)Cs2 0.16784(2) 0.07660(2) 0.42425(2) 0.02243(10)Cs3 0.35333(2) 0.42573(2) 0.58117(2) 0.01848(9)Cs4 0.315461(18) 0.416092(18) 0.920588(19) 0.01485(7)Gd1 0.409549(11) 0.344796(10) 0.220919(13) 0.00585(4)Gd2 0.407914(11) 0.070520(10) 0.253225(13) 0.00601(4)Gd3 0.185212(10) 0.341803(10) 0.279355(13) 0.00579(4)Gd4 0.088215(11) 0.431558(10) 0.746485(13) 0.00575(4)Gd5 0.090222(11) 0.160077(10) 0.748438(13) 0.00592(4)Gd6 0.317906(10) 0.158727(10) 0.754130(13) 0.00620(4)Gd7 0.001401(10) 0.249843(10) 0.492695(12) 0.00648(4)Gd8 0.499928(11) 0.250234(10) 0.507500(12) 0.00679(4)F1 0.4205(2) 0.33383(18) 0.03976(19) 0.0176(10)F2 0.47143(18) 0.10718(16) 0.08637(19) 0.0150(8)F3 0.11304(19) 0.3092(2) 0.1213(2) 0.0232(10)F4 0.32105(15) 0.41672(15) 0.15250(17) 0.0098(6)F5 0.39210(18) 0.19534(15) 0.1770(2) 0.0142(7)F6 0.24459(16) 0.00391(15) 0.2304(2) 0.0134(7)F7 0.01106(15) 0.00348(15) 0.2504(2) 0.0124(6)F8 0.24811(16) 0.24264(16) 0.2515(2) 0.0140(7)F9 0.05449(16) 0.19118(15) 0.3225(2) 0.0153(7)F10 0.05165(16) 0.35736(16) 0.3256(2) 0.0133(7)F11 0.34567(15) 0.41885(15) 0.34517(17) 0.0103(6)F12 0.4509(2) 0.3160(2) 0.3797(2) 0.0237(12)F13 0.38632(18) 0.11122(17) 0.4223(2) 0.0171(8)F14 0.16492(16) 0.33016(20) 0.46060(19) 0.0182(8)F15 0.03126(19) 0.39133(17) 0.57452(19) 0.0164(8)F16 0.03442(19) 0.14130(16) 0.57554(19) 0.0165(8)F17 0.35684(17) 0.35684(17) 0.5848(2) 0.0165(8)F18 0.16671(16) 0.08251(15) 0.65466(17) 0.0101(6)F19 0.43925(16) 0.43925(16) 0.6774(2) 0.0161(8)F20 0.09720(19) 0.29931(16) 0.6926(2) 0.0186(9)F21 0.09720(19) 0.49515(15) 0.73895(19) 0.0119(6)F22 0.25433(16) 0.25433(16) 0.7499(2) 0.0123(6)F23 0.49281(16) 0.49280(15) 0.7778(2) 0.0131(6)F24 0.0131(6) 0.29690(16) 0.8088(2) 0.0185(7)F25 0.16355(15) 0.08395(14) 0.84842(16) 0.0095(6)F26 0.11183(16) 0.39401(16) 0.91592(19) 0.0137(7)F27 0.11487(16) 0.22308(17) 0.91730(18) 0.0140(7)F28 0.35557(17) 0.14311(17) 0.92848(19) 0.0166(7)
S4
Table S2 Nominal glass compositions (mol%) for all the investigated fluoride-embedded glasses.
The samples were prepared by melt-quenching and subsequent heat-treatment at a certain
temperature for 2 h. Hexa, cub and orth represents hexagonal, cubic and orthorhombic phases,
respectively.
Glass composition(mol%)
Re3+ radius(Å)
Crystallizaiton T&time
Crystallized phase
49SiO2-10Al2O3-12Cs2O-15CsF-14LaF3 RLa=1.19 700℃/2h hexa-CsLa2F7
49SiO2-10Al2O3-12Cs2O-15CsF-14CeF3 RCe=1.15 800℃/2h hexa-CsCe2F7
49SiO2-10Al2O3-12Cs2O-15CsF-14PrF3 RPr=1.14 800℃/2h hexa-CsPr2F7
49SiO2-10Al2O3-12Cs2O-15CsF-14NdF3 RNd=1.12 800℃/2h hexa-CsNd2F7
49SiO2-10Al2O3-12Cs2O-15CsF-14SmF3 RSm=1.10 800℃/2h hexa-CsSm2F7
49SiO2-10Al2O3-12Cs2O-15CsF-14EuF3 REu=1.09 800℃/2h hexa-CsEu2F7
49SiO2-10Al2O3-12Cs2O-15CsF-14GdF3 RGd=1.08 900℃/2h hexa-CsGd2F7
49SiO2-10Al2O3-12Cs2O-15CsF-14TbF3 RTb=1.06 900℃/2h hexa-CsTb2F7
49SiO2-10Al2O3-12Cs2O-15CsF-14DyF3 RDy=1.05 900℃/2h hexa-CsDy2F7
49SiO2-10Al2O3-12Cs2O-15CsF-14HoF3 RHo=1.04 950℃/2h hexa-CsHo2F7
49SiO2-10Al2O3-12Cs2O-15CsF-14YF3 RY=1.04 950℃/2h hexa-CsY2F7
49SiO2-10Al2O3-12Cs2O-15CsF-14ErF3 REr=1.03 950℃/2h hexa-CsEr2F7
49SiO2-10Al2O3-12Cs2O-15CsF-14TmF3 RTm=1.02 950℃/2h hexa-CsTm2F7
49SiO2-10Al2O3-12Cs2O-15CsF-14YbF3 RYb=1.01 950℃/2h hexa-CsYb2F7
49SiO2-10Al2O3-12Cs2O-15CsF-14LuF3 RLu=1.00 950℃/2h hexa-CsLu2F7
59SiO2-10Al2O3-12Cs2O-5CsF-14ScF3 RSc=0.89 750℃/2h hexa-CsSc2F7
55SiO2-6Al2O3-12Na2O-19NaF-8YF3 650℃/2h hexa-NaYF4
55SiO2-11Al2O3-7Na2O-19NaF-8YbF3 650℃/2h cub-NaYbF4
53SiO2-6Al2O3-12K2O-15KF-14YbF3 750℃/2h hexa-KYbF4
41SiO2-6Al2O3-9K2O-19KF-25YbF3 750℃/2h orth-KYb2F7
S5
Table S3 The calculated lattice constants (a&c) of CsRe2F7 NCs inside glass based on XRD
patterns. The lattice constants show a rise tendency as Re3+ radius gradually increases.
Table S4 The calculated temperature (Tc) of Er: CsYb2F7@glass sample induced by laser irradiation
with various power density. As a comparison, the actually measured temperature (Tm) recorded by
a laser sight infrared thermometer is provided.
Laser power density (W/cm2) FIR Tc (℃) Tm (℃)
55 0.701 202 200
95 0.957 282 299
130 1.274 393 366
170 1.634 496 487
195 1.963 635 599
230 2.547 837 825
275 3.001 1154 -
Re3+ Sc3+ Lu3+ Yb3+ Tm3+ Er3+ Y3+ Ho3+ Dy3+
R (Å) 0.89 1.00 1.01 1.02 1.03 1.04 1.04 1.05
a (Å) 7.625 7.790 7.806 7.818 7.809 7.910 7.951 8.036
c (Å) 18.571 19.062 19.145 19.170 19.188 19.224 19.287 19.332
Re3+ Tb3+ Gd3+ Eu3+ Sm3+ Nd3+ Pr3+ Ce3+ La3+
R (Å) 1.06 1.08 1.09 1.10 1.12 1.14 1.15 1.19
a (Å) 7.976 8.101 8.108 8.139 8.191 8.297 8.370 8.418
c (Å) 19.404 19.476 19.503 19.611 19.908 19.926 20.052 20.205
S6
Figure S1 Schematic illustration of a typical CsLu2F7 crystal structure. The ionic sites in the unit
cell are tabulated in Table S1. Inset is the detailed crystallographic data. [S2]
[S2] V. N. Makhov, N. M. Khaidukov, D. Lo, M. Kirm, G. Zimmerer, Spectroscopic properties of
Pr3+ luminescence in complex fluoride crystals. Journal of Luminescence, 2003, 102-103, 638.
10 nm10 nm
Figure S2 HRTEM image of an individual CsLu2F7 NC inside glass.
CsLu2F7 NC
S7
400 800 1200 1600
CsLu2F7@glass
PG1046776595447
Tran
mitt
ance
(%)
Wavenumber (cm-1)Figure S3 FTIR spectra of precursor glass (PG) and the corresponding CsLu2F7@glass.
200 400 600 800 1000 1200 1400
CsLu2F7@glass
Inten
sity
(nm
)
Raman shift (cm-1)
PG
Figure S4 Raman spectra of precursor glass and the corresponding CsLu2F7@glass.
S8
1000 800 600 400 200 0
Lu 4dSi 2p
Al 2pC 1s
Cs 3dO 1s
PG
CsLu2F7@glass
Inten
sity
(a.u
.)
Binding energy (eV)
F 1s
(a)
108 104 100 96
(b) Si 2p
PG
CsLu2F7@glass
Inte
nsity
(a.u
.)
Binding energy (eV)84 80 76 72 68
(c) Al 2p
PG
CsLu2F7@glass
Inten
sity (
a.u.)
Binding energy (eV)544 540 536 532 528
(d) O 1s
PG
CsLu2F7@glass
Inten
sity
(a.u
.)
Binding energy (eV)
740 735 730 725 720
(e) Cs 3d
PG
CsLu2F7@glass
Inten
sity
(a.u
.)
Binding energy (eV)208 204 200 196
(f) Lu 4d
PG
CsLu2F7@glass
Inten
sity
(a.u
.)
Binding energy (eV)696 692 688 684 680
(g) F 1s
PG
CsLu2F7@glass
Inten
sity
(a.u
.)
Binding energy (eV)
Figure S5 (a) XPS full spectra for precursor glass and the corresponding CsLu2F7@glass. High-
resolution XPS spectra of (b) Si 2p, (c) Al 2p, (d) O 1s, (e) Cs 3d, (f) Lu 4d and (g) F 1s for precursor
glass and CsLu2F7@glass samples.
S9
400 450 500 550 600 650 700 750
Eu: CsLu2F7 @glass
Wavelength (nm)
Eu-doped PG
Norm
alize
d in
tensit
y (a
.u.)
xenon lamp (ex=393 nm) 5D0
7F3
7F3
5D0
7F2
5D0
7F1
5D0
7F0 7F
4 5D
0
7F2
5D1
7F1
5D1
7F2
5D2
5D2
7F0
5D1
7F0
5D2
0 10 20 30 40
Eu-doped PG Eu: CsLu2F7 @glass
Inten
sity
(a.u
.)
Time (ms)Figure S6 PL spectra and decay curves for Eu-doped precursor glass and Eu: CsLu2F7@glass.
400 450 500 550 600 650 700 750
Eu: CsLa2F7@glass
Wavelength (nm)
Eu-doped PG
Nom
alize
d In
tensit
y (a
.u.)
0 10 20 30 40
Inten
sity
(a.u
.)
Time (ms)
Eu-doped PG Eu: CsLa2F7 @glass
Figure S7 PL spectra and decay curves for Eu-doped precursor glass and Eu: CsLa2F7@glass.
400 450 500 550 600 650 700 750
Eu: CsGd2F7 @glass
Wavelength (nm)
Eu-doped PG
Nom
alize
d In
tensit
y (a
.u.)
0 10 20 30 40
Eu-doped PG Eu: CsGd2F7@glass
Inten
sity
(a.u
.)
Time (ms)Figure S8 PL spectra and decay curves for Eu-doped precursor glass and Eu: CsGd2F7@glass.
S10
450 500 550 600 650 700 750
Eu-doped PG
Norm
alize
d in
tensit
y (a
.u.)
Wavelength (nm)
Eu: CsY2F7 @glass
0 10 20 30 40
Eu-doped PG Eu: CsY2F7 @glass
Inten
sity
(a.u
.)
Time (ms)Figure S9 PL spectra and decay curves for Eu-doped precursor glass and Eu: CsY2F7@glass.
400 450 500 550 600 650 700 750
Eu: CsYb2F7 @glass
Wavelength (nm)
Eu-doped PG
Nom
alize
d In
tensit
y (a
.u.)
0 5 10
Eu-doped PG Eu: CsYb2F7 @glass
Inten
sity
(a.u
.)
Time (ms)Figure S10 PL spectra and decay curves for Eu-doped precursor glass and Eu: CsYb2F7@glass.
400 450 500 550 600 650 700 750
Eu: CsSc2F7 @glass
Eu-doped PGNom
alize
d In
tensit
y (a
.u.)
Wavelength (nm)
0 10 20 30 40
Eu-doped PG Eu:CsSc2F7 @glass
Inten
sity
(a.u
.)
Time (ms)Figure S11 PL spectra and decay curves for Eu-doped precursor glass and Eu: CsSc2F7@glass.
S11
0
1
2
3 Eu-doped PG Eu:CsRe2F7@glass
CsSc2F 7
CsLu 2F 7
CsYb 2F 7
CsY 2F 7
CsGd 2F 7
ED/M
D (a
.u.)
CsLa 2F 7
Figure S12 Emission intensity ratio between electric dipolar (ED) 5D0→7F2 transition and magnetic
dipolar (MD) 5D0→7F1 one for the Eu: CsRe2F7@glass (Re=La, Gd, Y, Yb, Lu, Sc) samples and the
corresponding Eu-doped precursor glasses.
400 450 500 550 600 650 700 750
x40
Yb/Er: CsLu2F7 @glass
PG
Wavelength (nm)
UC in
tensit
y (a
.u.)
Figure S13 UC emission spectra for Yb/Er-doped precursor glass and Yb/Er: CsLu2F7@glass.
S12
400 500 600 700
UC in
tensit
y (a
.u.)
Wavelength (nm)
x17
Yb/Ho: CsLu2F7 @glass
PG
Figure S14 UC emission spectra for Yb/Ho-doped precursor glass and Yb/Ho: CsLu2F7@glass.
400 500 600 700
Wavelength (nm)
PG
UC in
tensit
y (a
.u.)
Yb/Tm: CsLu2F7 @glass
x10
Figure S15 UC emission spectra for Yb/Tm-doped precursor glass and Yb/Tm: CsLu2F7@glass.
S13
400 500 600 700
PG
x3
UC in
tensit
y (a
.u.)
Wavelength (nm)
Yb/Er: CsLa2F7 @glass
Figure S16 UC emission spectra for Yb/Er-doped precursor glass and Yb/Er: CsLa2F7@glass.
400 450 500 550 600 650 700 750
Wavelength (nm)
x10
PG
UC in
tensit
y (a
.u.) Yb/Er: CsGd2F7 @glass
Figure S17 UC emission spectra for Yb/Er-doped precursor glass and Yb/Er: CsGd2F7@glass.
S14
400 500 600 700
x20
Yb/Er: CsY2F7 @glass
PG
UC in
tensit
y (a
.u.)
Wavelength (nm)
Figure S18 UC emission spectra for Yb/Er-doped precursor glass and Yb/Er: CsY2F7@glass.
400 500 600 700
PG
Yb/Er: CsYb2F7 @glass
UC in
tensit
y (a
.u.)
Wavelength (nm)
x5
Figure S19 UC emission spectra for Yb/Er-doped precursor glass and Yb/Er: CsYb2F7@glass.
S15
0 2 4 6 8
(a)ex=980nm em=545nm
PG Yb/Er:CsY2F7 @glass
Log [
UC in
tensit
y (a.u
.)]
Time (ms) 0 2 4 6 8
(b)
PG Yb/Er:CsY2F7 @glass
Log [
UC in
tensit
y (a.u
.)]
Time (ms)
ex=980nm em=655nm
0 2 4 6 8
(c)ex=980nm em=545nm
Log
[UC
inten
sity
(a.u
.)]
Time (ms)
PG Yb/Er:CsGd2F7 @glass
0 2 4 6 8
(d)
PG Yb/Er:CsGd2F7 @glass
ex=980nm em=655nm
Log [
UC in
tensit
y (a.u
.)]
Time (ms)
0 2 4 6
(e)
PG Yb/Er:CsLu2F7 @glass
ex=980nm em=545nm
Log [
UC in
tensit
y (a.u
.)]
Time (ms)0 2 4 6
(f) PG Yb/Er:CsLu2F7 @glass
ex=980nm em=655nm
Log
[UC
inten
sity(
a.u.)]
Time (ms)
0 2 4
(g) ex=980nm em=541nm
PG Yb/Ho:CsLu2F7 @glass
Log
[UC
inten
sity
(a.u
.)]
Time (ms)0 2 4 6
(h) ex=980nm em=480nm PG Yb/Tm:CsLu2F7 @glass
Log
[UC
inten
sity
(a.u
.)]
Time (ms)
Figure S20 (a-f) UC decay curves for Yb/Er-doped precursor glass and Yb/Er: CsRe2F7@glass
(Re=Y, Gd, Lu) by monitoring Er3+ green and red emissions. (g) UC decay curves for Yb/Ho-doped
precursor glass and Yb/Ho: CsLu2F7@glass by monitoring Ho3+ red emission. (h) UC decay curves
for Yb/Tm-doped precursor glass and Yb/Tm: CsLu2F7@glass by monitoring Tm3+ blue emission.
S16
0
2
4
6
8
10
12
3.132.70
10.84
1.381.100.36
CsSc2F7CsLu2F7
CsYb2F7
CsY2F7CsGd2F7
R/G
ratio
CsLa2F7
Figure S21 UC red-to-green ratio for Yb/Er: CsRe2F7@glass (Re=La, Gd, Y, Yb, Lu, Cs) samples.
Insets are the corresponding UC emissive photographs under irradiation of 980 nm laser
10 20 30 40 50 60 70 80
Inten
sity
(a.u
.)
2 (degree)
JCPDS NO.16-0334
(a)
Figure S22 (a) XRD pattern and (b) HAADF-STEM image of Yb/Er: NaYF4@glass sample. Bars
represent diffraction data of hexagonal NaYF4 crystal (JCPDS No. 16-0334). The precipitated phase
inside glass is hexagonal NaYF4, and the particle sizes are in the range of 40~100 nm.
(b)
NaYF4 NCs
glass matrix
S17
400 500 600 700
(a)
x3Yb/Er:NaYF4
Yb/Er:CsLu2F7
UC
inte
nsity
(a.u
.)
Wavelength (nm)
400 500 600 700
(b)
Yb/Tm:CsLu2F7
Wavelength (nm)
x13
Yb/Tm:NaYF4
UC
inte
nsity
(a.u
.)
400 500 600 700
Yb/Ho:NaYF4
UC
inte
nsity
(a.u
.)
Wavelength (nm)
Yb/Ho:CsLu2F7
x5
(c)
Figure S23 Comparison of UC emission profile and intensity between Yb/Ln: CsLu2F7@glass and
Yb/Ln: NaYF4@glass: (a) Ln=Er, (b) Ln=Tm, (c) Ln=Ho. The corresponding spectra are recorded
under the identical conditions.
400 500 600 700
0.0
0.4
0.8
1.2
1.6
2.0(a)
Er: CsYb2F7@glass
Nor
mal
ized
inte
nsity
(a.u
.)
Wavelength (nm)
Figure S24 (a) 980 nm laser power density (55~275 W/cm2) dependent UC emission spectra of Er:
CsYb2F7@glass samples. Arrow represents elevation of laser power density. (b) Color coordinates
of UC luminescence for Er: CsYb2F7@glass in CIE diagram with increase of laser powder density.
Insets show remarkable change of UC emissive color for Er: CsYb2F7@glass samples irradiated by
elevated laser power density (from bottom to top).
(b)
S18
0 1 2 3 4 5 60
2
4
6
8
10 (a)
R/G
inte
grat
ed ra
tio (a
.u.) 55 W/cm2
230 W/cm2
Cycling number 10 20 30 40 50 60 70
(b) Er: CsYb2F7@glass
After laser irradiation
Inte
nsity
(a.u
.)
2 (degree)
Pristine
JCPDS NO.43-0505
Figure S25 (a) Er3+ red-to-green UC emissive ratio for Er: CsYb2F7@glass in cycles of low laser
power density (55 W/cm2) and high laser power density (230 W/cm2). (b) XRD patterns of pristine
Er: CsYb2F7@glass and the sample after laser irradiation for 6 cycling times.
0
5
10
15
20
25
4F7/22H11/24S3/24F9/24I9/24I11/2
4I13/2
4I15/2
2F5/2
2F7/2
Ener
gy (1
03 cm-1
)
Yb3+ Er3+
980
nm la
ser
Thermally coupled states
400 500 600 700
(b) 95 W/cm2In
tens
ity (a
.u.)
Wavelength (nm)
2H11/2 4S3/2
4F9/2
Rat
io(F
/S)=
0.22
:1
400 500 600 700
(c) 170 W/cm2
2H11/2
4S3/2
Wavelength (nm)
4F9/2
Inte
nsity
(a.u
.)
Wavelength (nm)
Rat
io(F
/S)=
0.34
:1
400 500 600 700
4F9/2
4S3/2Inte
nsity
(a.u
.)
Wavelength (nm)
275 W/cm22H11/2
Rat
io(F
/S)=
0.52
:1
(d)
Figure S26 (a) Energy levels of Yb3+ and Er3+, Yb-to-Er energy transfer UC processes and Er3+
2H11/2 and 4S3/2 thermally couple states of in Er: CsYb2F7@glass. (b-d) Laser power dependent UC
emission spectra. The peak ratio between4S3/2→4I15/2 transition and 4F9/2→4I15/2 one is provided.
(a)
S19
400 450 500 550 600 650 700
power increasing
Norm
alize
d in
tensit
y (a
.u.)
Wavelength (nm)
Figure S27 980 nm laser power dependent UC emission spectra of Er: CsYb2F7@glass recorded at
a low temperature (77 K).
10 20 30 40 50 60 70
Inten
sity
(a.u
.)
2(degree)
JCPDS No.77-2043
Er: NaYbF4@glass
10 20 30 40 50
Er: KYbF4@glass
Inten
sity
(a.u
.)
2 (degree)
JCPDS No.27-0457
10 20 30 40 50
JCPDS No. 27-0459
Er: KYb2F7@glass
2 (degree)
Inten
sity
(a.u
.)
Figure S28 XRD patterns of (a) Er: NaYbF4@glass, (b) Er: KYbF4@glass and (c) Er:
KYb2F7@glass samples. Bars represent cubic NaYbF4 (JCPDS No. 77-2043), hexagonal KYbF4
(JCPDS No. 27-0457) and orthorhombic KYb2F7 (JCPDS No. 27-0459) crystals diffraction data.
(a) (b)
(c)
S20
400 500 600 700
0.0
0.2
0.4
0.6
0.8
1.0
Er: NaYbF4@glassN
orm
alize
d in
tensit
y (a
.u.)
Wavelength (nm)400 500 600 700
0.0
0.2
0.4
0.6
0.8
1.0
Norm
alize
d in
tensit
y (a
.u.)
Wavelength (nm)
Er: KYbF4@glass
400 450 500 550 600 650 7000.0
0.2
0.4
0.6
0.8
1.0
Norm
alize
d in
tensit
y (a
.u.)
Wavelength (nm)
Er: KYb2F7@glass
Figure S29 980 nm laser power density (55~275 W/cm2) dependent UC emission spectra of (a) Er:
NaYbF4@glass, (b) Er: KYbF4@glass and (c) Er: KYb2F7@glass samples. Arrows represent
elevation of laser power density.
50 100 150 200 250 3000
200
400
600
800
1000
1200
CsYb2F7-Calculated values CsYb2F7-Measured data KYb2F7-Measured data KYbF4-Measured data NaYbF4-Measured data
T (℃
)
Laser power density ( W/cm2) Figure S30 Experimental measured temperatures for the Er: NaYbF4@glass, Er: KYbF4@glass, Er:
KYb2F7@glass and Er: CsYb2F7@glass samples exposed to different 980 nm laser power densities.
Theoretical calculated temperature values based on repopulation of Er3+: 2H11/2 and 4S3/2 thermally
coupled states for Er: CsYb2F7@glass are also provided.
(c)
(a) (b)
S21
500 520 540 560 580 600
UC in
tensit
y (a.u
.)
Wavelength (nm)
293K 313K 333K 353K 373K 393K 413K 433K 453K
(a)
500 520 540 560 580 600
0.0
0.2
0.4
0.6
0.8
1.0(b)
Temperature increasing
Norm
alize
d Inte
nsity
(a.u.
)
Wavelength (nm)
280 320 360 400 4400.1
0.2
0.3
0.4
0.5
0.6 Experimental Data
FIR
T (K)0.0022 0.0024 0.0026 0.0028 0.0030 0.0032 0.0034
-1.8
-1.6
-1.4
-1.2
-1.0
-0.8
-0.6
-0.4(d)
Experimental data Fitting curve
Ln (F
IR)
1/T (K-1)
Slope=-1088 ± 19Intercept=1.91 ± 0.05
Figure S31 (a) Temperature (313~453 K) dependent UC emission spectra of Er: CsYb2F7@glass.
(b) Normalized UC emission spectra of (a). (c) FIR values versus temperature. (d) Monolog plot of
FIR versus inverse absolute temperature. The fitting line is also provided in (d).
Figure S32 Real-time observation of the change of UC emissive color for Er: CsYb2F7@glass on a
hot plate with elevation of temperature from 30 oC to 550 oC under the irradiation of fixed laser
power (500 mW). The temperature of sample from left to right is 30 oC, 100 oC, 200 oC, 300 oC,
400 oC, 500 oC and 550 oC.
(c)
S22
350 400 450 500
Ce (x mol%): CsLu2F7
100%
20%
10%
5%
2.8%
1.4%
0.7%
Wavelength (nm)
PL in
tens
ity (a
.u.)
0.1 0.2 0.3 0.4 0.5
(b)
1.4%
0.7%
Time (s)
Ce (x mol%): CsLu2F7
PL in
tens
ity (
a.u.
)
100%
20%
10%
5%
2.8%
Figure S33 Ce doping content (0.7~100 mol%) dependent PL spectra and decay behaviors for Ce:
CsLu2F7@glass.
400 450 500 550 600 650 700 750
UC in
tensit
y (a
.u.)
Wavelength (nm)
0 day 1 day 3 days 7 days 15 days 30 days
Yb/Er: CsLu2F7@glass
400 450 500 550 600 650 700 750
UC in
tensit
y (a
.u.)
Wavelength (nm)
0 day 1 day 3 days 7 days 15 days 30 days
Yb/Er: CsLu2F7@glass powders
0 5 10 15 20 25 300
20
40
60
80
100
Relat
ive i
nten
sity
(%)
Time (day)
Yb/Er: CsLu2F7 @glass
0 5 10 15 20 25 300
20
40
60
80
100
Relat
ive i
nten
sity
(%)
Time (day)
Yb/Er: CsLu2F7 @glass powders
Figure S34 (a, b) UC emission spectra of Yb/Er: CsLu2F7@glass and the corresponding powders
immersing in water for different times (0~30 days). (c, d) UC integrated intensities versus
immersing durations in water solution.
(a)
(a) (b)
(c) (d)
S23
0 2 4 6
Yb/Er: CsLu2F7@glass in waterLo
g [U
C in
tensit
y (a
.u.)]
Time (ms)
0 day 1 day 3 days 7 days 15 days 30 days
ex=980 nm em=545 nm
0 2 4 6 8
Yb/Er: CsLu2F7@glass in water
Log
[UC
inten
sity
(a.u
.)]
Time (ms)
0 day 1 day 3 days 7 days 15 days 30 days
ex=980 nm em=655 nm
0 2 4 6
0 day 1 day 3 days 7 days 15 days 30 days
Log
[UC
inten
sity
(a.u
.)]
Time (ms)
ex=980 nm em=545 nmYb/Er: CsLu2F7@glass in oil solution
0 2 4 6 8
Yb/Er: CsLu2F7@glass in oil solution
Log
[UC
inten
sity
(a.u
.)]
Time (ms)
0 day 1 day 3 days 7 days 15 days 30 days
ex=980 nm em=655 nm
Figure S35 UC decay curves of Yb/Er: CsLu2F7@glass immersing in solution for different
durations (0~ 30 days): (a, b) in water by monitoring Er3+ green and red emissions, (c, d) in oil
solution by monitoring Er3+ green and red emissions.
(a) (b)
(c) (d)
