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org/JPCC Article

Effect of Temperature and High Pressure on Luminescence

Properties of Mn3+ Ions in Ca3Ga2Ge3O12 Single Crystals
Yongjie Wang,* Damian Włodarczyk, Mikhail G. Brik, Justyna Barzowska, A. N. Shekhovtsov,
K. N. Belikov, Wojciech Paszkowicz, Li Li, Xianju Zhou, and A. Suchocki*
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ABSTRACT: In this work, the temperature and high-pressure

behaviors of Mn3+-doped garnet-type Ca3Ga2Ge3O12 single crystals
have been investigated by means of photoluminescence and
Downloaded via UNIV OF SFAX on January 9, 2022 at 10:55:23 (UTC).

Raman spectroscopy, respectively. The Jahn−Teller stabilization

energy in the 5E ground state was found to be 1630 cm−1, being as
much as 6 times greater than that in the 5T2 excited state, that is,
237 cm−1. The room-temperature emission spectrum is dominated
by the spin-allowed 5T2 → 5E transition at 670 nm upon 532 nm
excitation. The temperature dependences of photoluminescence
spectra and time decays reveal strong thermalization between 5T2
and 1T2 levels. Cooling to 50 K empties the 5T2 level by virtue of
multiphonon transition to the lower-lying 1T2 level. As a result, the
1
T2 → 3T1/5E electric-dipole transitions are induced by coupling to
odd-parity phonons. The existence of a small amount of Mn4+ can be ascertained by lowering the temperature or applying high
pressure. Upon compression up to 100 kbar, the 5T2 → 5E transition of Mn3+ undergoes a blue shift at a rate of ∼10.5 cm−1/kbar.
Since both 5T2 and 1T2 have inverse crystal field dependences, the quenching process from the 5T2 level becomes stronger under
high pressure. Cryogenic luminescence ratiometric thermometry based on the diverse thermal quenching behaviors of Mn3+ and
Mn4+ was explored. Furthermore, theoretical calculations employing the exchange-charge model of crystal field for Mn3+ and Mn4+
ions in Ga3+ octahedral sites (C3i) in garnet-type Ca3Ga2Ge3O12 remain in perfect agreement with the experimental data.

1. INTRODUCTION
Manganese is a well-known luminescence activator in garnet
single crystals, utilized mainly as solid-state laser media which
offer a broad tuning range. Oxide single crystals and, in
particular, those with the A3B2C3O12 garnet structure are
considered as prospective host materials for trivalent tran-
sition-metal ions in solid-state laser and scintillator applica-
tions.1−5 Such ions prefer occupying octahedral B3+ sites, which
undergo weak trigonal distortions and thus are of great interest
for solid-state laser applications. The calcium gadolinium
germanium garnet Ca3Ga2Ge3O12 (CGGG), which belongs to
the rich family of garnet-type laser-host crystals,6−9 is also well
known as a substrate material for magnetic memories and optical
recording.10 Structural and optical studies were recently carried
out on Cr3+-doped CGGG phosphors in search of near-infrared
(NIR) persistent luminescence materials.11,12 Photo-induced
optical absorption in Mn3+-doped CGGG single crystals was
studied as promising optical recording material.13
In general, the energy levels of 3d transition-metal ions in a
crystal field are described by the well-known Tanabe−Sugano
diagram.14 Mn3+ has the 3d4 electronic configuration, where the
free ion ground term, 5D, is the only spin quintet, while the other
terms are triplets and singlets. The 5D term splits into the lower
5
E and upper 5T2 terms in an octahedral crystal field. For low
crystal field strengths (Dq/B < 2.5), the ground state is 5E, and
thus, only spin-allowed 5E → 5T2 transitions are expected in the
absorption spectra. Since all higher excited terms are singlets or
triplets, excited-state absorption (ESA) transitions from the
upper spin quintet state are spin-forbidden.15 In the 3d4
configuration, however, the Jahn−Teller effect16 has to be
taken into account as a result of its significant influence on the
optical properties of 3d ions in crystals. The Jahn−Teller
distortion for the 5E ground state is expected to be higher17 than
that for 5T2 and 1T2 excited states.18,19 The ability to synthesize
materials containing solely Mn3+ ions still remains challenging
due to the fact that the Mn3+ ion is relatively unstable and readily
undergoes oxidation, reduction, and disproportionate reactions,
forming more stable divalent and tetravalent states, that is, Mn2+
and Mn4+.20 Moreover, suffering from strong ESA due to
Received: November 1, 2020
Revised: February 13, 2021
Published: February 24, 2021

© 2021 American Chemical Society https://dx.doi.org/10.1021/acs.jpcc.0c09845

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transitions from the slightly lower-lying metastable 1T2 spin
singlet level, laser action is unlikely in crystals with octahedrally
coordinated Mn3+ions.19 Therefore, further investigation of
Mn3+-activated new materials is required from the viewpoint of
scientific research as well as for extending their potential
applications.
In this work, we report the result of a systematic study of the
temperature- and high-pressure-dependent optical properties of
Mn3+-doped garnet-type CGGG single crystals. The work aims
to elucidate the mechanisms of Mn3+ luminescence quenching
induced by temperature and high pressure as well as the Jahn−
Teller effect responsible for the 5T2 and 5E splitting in the
studied material. In addition, theoretical calculations employing
the exchange-charge model (ECM) of the crystal field effect
were performed for the interpretation of experimental data. The
potential application for cryogenic luminescence ratiometric
thermometry based on the diverse thermal quenching behaviors
of Mn3+ and Mn4+ in CGGG/Mn single crystals was explored as
well.
2. EXPERIMENTAL AND THEORETICAL METHODS
2.1. Sample Preparation. The Mn3+-doped
Ca3Mn0.01Ga1.99Ge3O12 (CGGG:Mn) single crystal with the
⟨100⟩ orientation was grown by the Czochralski technique in
platinum crucibles in argon (in order to prevent Mn3+ oxidation)
and addition of an oxygen (to prevent the formation of oxygen
vacancies) atmosphere at ambient pressure using inductive
heating. The growth atmosphere consisted of 98 vol % of Ar + 2
vol % of O2. A similar technological approach was developed
earlier for the growth of high-quality YAG:Nd crystals.21 The
charge for the growth was prepared in advance through solid-
state synthesis using a stoichiometric mixture of Ga2O3, GeO2,
and CaCO3 with addition of Mn2O3. The Mn content in the
charge was 0.82 wt %. The charge was heated at 900 °C for 25 h.
The crystal was grown by pulling from the melt at a rate of 2
mm/h and a rotation rate of 30−40 cycles per minute (for more
details, see refs 13 and 22).
Chemical analysis indicated the presence of the Cr impurity at
a level as low as 0.0003 wt %. Detailed X-ray diffraction (XRD)
analysis indicates that the main component of the sample is the
garnet phase. The minority phases are identified as
Ca3Ga3Ge4O14 (the P321/150 space group) and GeO2 (the
P3221/154 space group). Their peak intensities are very weak
(<0.5%). A tiny reduction of the a lattice parameter is observed
in respect to the undoped sample [12.25035(2) vs 12.2562 Å].23
The reduction is as small as 0.05%. The oxygen position (x,y,z) =
(0.10004(13), 0.19602(13), 0.28262(12)) marginally differs
from that given in ref 22, that is, (0.0999, 0.1997, 0.2838). The
dominating valence of the Mn dopant is Mn3+; however, a small
amount of Mn4+ ions is present in the crystals, as shown in
forthcoming paragraphs. They are visible in the photo-
luminescence (PL) and photoluminescence excitation (PLE)
experiments only at low temperature. A very small amount of
Mn2+ ions was only detected by electron paramagnetic
resonance (EPR), as shown in Figure S9. They are not observed
by any optical measurements described in this paper.
The sample was cut in the form of a plane−parallel, 1.0 mm
thick plate perpendicular to the [100] direction.
2.2. Characterization Methods. A Cary 5000 UV−
visible−NIR (UV−vis−NIR) spectrophotometer was used for
the UV−vis−NIR absorption spectra. Continuous-flow cryo-
stats with appropriate windows were used for temperature-
dependent absorption measurements. The ambient-pressure
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PLE spectra and PL spectra were recorded using a HORIBA
Jobin-Yvon Fluorolog-3 spectrofluorometer equipped with a
450 W xenon lamp for excitation and a Hamamatsu R928P
photomultiplier. In the measurements of luminescence kinetics
and time-resolved emission spectra (TRES), the PL 2251A-20
pulse laser, followed by a parametric optical generator PG401/
SH, was used as an excitation light source. The luminescence
signal was obtained using the Bruker Optics 2501S spectrograph
coupled with a Hamamatsu Streak Camera C4334. In the TRES
experiment, the sample was placed in a closed-cycle helium
cryostat, the system consisting of a water-cooled helium
compressor ARS-4HW, an expander DE-204SI (Advanced
Research System, Inc.), and Lake-Shore temperature controller
model 336.
Raman measurements were recorded using a confocal Raman
microscope (MonoVista CRS+) with a Cobolt 532 nm solid-
state laser. High-pressure luminescence spectra were recorded
with the same equipment using a Monovista CRS+ spectrometer
equipped with a single-mode Cobolt Samba 532 nm laser, a 0.75
m Acton-Princeton single-turret monochromator with a 600
grooves/mm holographic grating, and a Princeton Instruments
back-thinned, deep-depleted, nitrogen-cooled charge-coupled
device (1340 × 100 pixel array) camera. The laser was focused
using a 5× Mitutoyo Objective from TM Series with a numerical
aperture of 0.10. The high-pressure experiments were carried
out using a low-temperature diamond anvil cell (CryoDAC LT,
easyLab Technologies Ltd.), which was mounted in an Oxford
Optistat CF cryostat equipped with a temperature controller for
low-temperature measurements. Argon was used as a pressure-
transmitting medium. The samples, cut and polished down to a
thickness of 20−30 μm, were loaded into the cell along with a
small ruby crystal for pressure calibration.
The XRD measurements were performed using a Philips
(Panalytical) X’Pert PRO Alpha1 diffractometer (Cu Kα1
radiation) equipped with a primary-beam Johansson mono-
chromator and strip detector.
2.3. Theoretical Calculation Methods. The ECM24 of
crystal field was employed for calculating the energy levels of the
Mn3+ and Mn4+ ions in Ca3Ga2Ge3O12 (Ga octahedral site
C3i). The crystal structural data25 were used to analyze the
symmetry properties of the impurity ion site and generate a
cluster consisting of more than 92,200 ions (this is required to
ensure proper convergence of the crystal lattice sums needed for
the calculations of the crystal field parameters). The details of
the calculation methods as well as all relevant equations can be
found in our previous publications26−29 and are not repeated
here for the sake of brevity. The nonzero crystal field parameters
are listed in Table 1. The calculated values of the Racah
parameters B and C were chosen on the ground of the best
agreement with experimental data. The crystal field splittings of
all 16 LS terms for the Mn3+ ions and 8 LS terms for the Mn4+
ions were calculated by diagonalizing the crystal field
Hamiltonian with all crystal field parameters.
The calculated values of energy levels of Mn3+ and Mn4+ in
Ca3Ga2Ge3O12 are presented later (Tables 3 and 4).
3. RESULTS AND DISCUSSION
3.1. Crystal Structure and Band Structure Calcula-
tions. The representation of the unit cell and the coordination
environment of Ca2+, Ga3+, and Ge4+ cation sites in the
Ca3Ga2Ge3O12 crystal structure are displayed in Figure 1a. The
garnet-type CGGG has the Oh10-Ia3d (230) cubic space group
with Ca2+ ions situated at D2 sites, Ge4+ at S4 sites, and Ga3+ at
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Table 1. Nonzero Crystal Field Parameters Bpk (Stevens Studio (see more details in the Supporting Information). As
Normalization) and Racah Parameters B and C (All in cm−1) shown in Figure S2, the calculated band gap is 3.01 eV, which is
for Mn4+ and Mn3+ Ions in Ca3Ga2Ge3O12 (Ga Octahedral smaller than that from experimental data (3.12 eV).
Site)a 3.2. Temperature Dependence of Absorption Spectra
and the Room-Temperature PL Spectrum of the CGGG/
Mn4+, Ga site Mn3+, Ga site
Mn Single Crystal. The absorption spectra of a polished single
0
B2 2191 1954 crystal in the 4.5−400 K range (Figure 2a) show similar overall
B4−3 73,695 90,516 behaviors. The absorption spectrum at room temperature is
B40 −2794 −3420 dominated by a strong band at 531 nm, which is attributed to the
B43 −10,414 −13,246 5
E → 5T2 spin-allowed transition of Mn3+. The crystal field
G 5.655 5.51 strength Δo = 10Dq in the octahedral field equals to the energy of
B 685 900 the 5E → 5T2 transition. The maximum of its absorption band is
C 3265 3435 therefore taken as the Δo energy; hence, the crystal field
parameter Dq was determined to be 1883 cm−1. The crystal field
a
The value of the ECM parameter G is also given.
stabilization energy (CFSE)31 for Mn3+ ions in CGGG can be
Table 2. Energies (in cm−1) and Assignment of Observed subsequently determined as (3/5)·Δo = 11,300 cm−1. In the IR
Bands in the Raman Spectrum of CGGG:Mn in Comparison range, a weak, broad band at 1532 nm (6527 cm−1) is most
with Ca3Sc2Ge3O12 (wWeak; shShoulder) probably attributable to a transition between two sublevels of
Ca3Sc2Ge3O12, ref Ca3Ga2Ge3O12, this assignment of phonon the 5E ground state (5E′ → 5E″) split due to the Jahn−Teller
30 work symmetry effect, which is caused by a weak trigonal distortion of the
133 142 lattice oxygen octahedron. Hence, the Jahn−Teller stabilization energy
169 183 T2g (the difference between the bottoms of the 5E′ and 5E″
267 278 ν2(E), ν4(T2) parabolas and their crossover) for the 5E ground state in CGGG,
295 316 T2g ΔEJT(5E), can be estimated as
330 336 A1g E IR
402 354 Eg ΔE JT(5 E) =
4 (1)
468 423 A1g
500 443 Eg where EIR is the energy that corresponds to the maximum of the
688 496 ν1(A1), ν3(T2) IR absorption band (5E′ → 5E″). With use of eq 1, the obtained
705 671 T2g ΔEJT (5E) is 1630 cm−1.
730 713 T2g Moreover, a small feature at ∼510 nm, attributed to Fano
804 813 A1g antiresonance, is observed in the absorption spectrum at room
830 (w, sh) 836 (w, sh) T2g temperature. The phenomenon is caused by overlap of the
(sharp) spin-forbidden transitions to the crystal-field-independ-
C3i sites, adopting a unit cell showing body-centered cubic ent 3E term with the quasi continuum of spin-allowed transitions
symmetry.10 The Ca2+, Ga3+, and Ge4+ cations are coordinated to the crystal-field-dependent 5T2 term.31,32 The wavelength of
by eight, six, and four oxygen anions forming a dodecahedron, an such a feature is practically independent of the crystal field. In
octahedron, and a tetrahedron, respectively. beryl,31 garnets,19 and YAlO332 compounds, Fano antiresonan-
Figure 1b presents the Raman spectrum of CGGG:Mn ces were observed at 511, 500, and 504 nm, respectively. From
measured at room temperature. We assigned the Raman-active the antiresonance position, the energy ratio of the 3E to 5T2
modes in a way similar to that adopted by Cavalli et al.30 for the levels was evaluated to be ∼1.04. According to the Tanabe−
Ca3Sc2Ge3O12 single crystal. The four normal modes ν1(A1), Sugano diagram for the 3d4 ion, shown in Figure 2c, the ratio
ν2(E), ν3(T2), and ν4(T2) of the regular tetrahedral (Td corresponds to the Dq/B value of ∼2.25. Hence, the Racah
symmetry) are Raman-active. The two bands centered near parameter of B = 837 cm−1 was determined. Both values are
423 and 815 cm−1 belonging to totally symmetric A1g vibrational similar to the ones calculated: Dq/B = 2.10 and B = 900 cm−1.
modes of the GeO4 tetrahedral groups were easily identified. A At temperatures below 100 K, the main absorption band splits
total of 13 active modes are observed, and their assignments in into two with the maxima at 524 and 587 nm, related to the spin-
comparison with the results reported for the Ca3Sc2Ge3O12 allowed transitions from the 5E ground state to the two Jahn−
single crystal are given in Table 2. First-principles calculations of Teller 5T2 sublevels. The splitting of the 5T2 excited state equals
the band structure and electronic properties were performed for to 2123 cm−1, which is much smaller than that of the 5E ground
a pure CGGG crystal using the CASTEP module of Materials state (6527 cm−1). Hence, the analysis of absorption spectra

Table 3. Calculated Energy Levels (All in cm−1) for the Mn3+ Ion in Ca3Ga2Ge3O12 (Ga Octahedral Site)a
“parent” Oh states C3i group notation energy, calculated averaged energy, observed
5
Eg (5D) {5Eg(1) + 5Eg(2)} 0
3
T1g (3H) {3Eg(1) + 3Eg(2)}+3Ag 1954*, 2736 2345
1
T2g (1I) 1
Ag + {1Eg(1) + 1Eg(2)} 11,711, 12,119* 11,915
1
Eg (1I) {1Eg(1) + 1Eg(2)} 13,326* 13,326
5
T2g (5D) 5
Ag + {5Eg(1) + 5Eg(2)} 18,003, 19,253* 18,628 ∼18,833
3
Eg (3H)+ 3T1g (3H) 2{3Eg(1) + 3Eg(2)} + 3Ag 18,223*, 18,679, 19,275* 18726 ∼19607

a
The orbital doublet states are denoted with asterisks. The energy of the ground state is taken as 0.

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Table 4. Calculated Energy Levels (All in cm−1) for the Mn4+ Ion in Ca3Ga2Ge3O12 (Ga Octahedral Site)a
“parent” Oh states C3i group notation energy, calculated averaged energy, observed
4
A2g (4F) 4
Ag 0
2
Eg (2G) {2Eg(1) + 2Eg(2)} 14,704* 14,705 (680 nm ZPL)
2
T1g (2G) 2
Ag + {2Eg(1) + 2Eg(2)} 15,263*, 15,673 15,400
4
T2g (4F) 4
Ag + {4Eg(1) + 4Eg(2)} 15,049*, 15,858 15,319 15,314 (653 nm)
2
T2g (2G) {2Eg(1) + 2Eg(2)} + 2Ag 21,388, 22,348* 22,028
4
T1g (4F) 4
Ag + {4Eg(1) + 4Eg(2)} 21,608, 22,233* 22,025 22,026 (454 nm)
4
T1g (4P) 4
Ag + {4Eg(1) + 4Eg(2)} 33,403*, 36,240 34,349
a
The orbital doublet states are denoted with an asterisk.

Figure 1. (a) Unit cell representation and the coordination environment of Ca2+, Ga3+, and Ge4+ cation sites in the Ca3Ga2Ge3O12 crystal structure; (b)
Raman spectrum of CGGG:Mn measured at room temperature.

revealed a much stronger Jahn−Teller effect in the 5E ground
state than in the 5T2 excited state of Mn3+ at octahedral sites with
local symmetry C3i in CGGG, as shown in Figure 2d. The
calculated crystal field parameters and energy levels of Mn3+ ions
in CGGG are consistent with experimental results, as
summarized in Table 3.
Under 532 nm laser excitation, the room-temperature PL
spectrum with a full width at half-maximum (fwhm) of 1504
cm−1, shown in Figure 2b, consists of two broad bands
corresponding to the 5T2 → 5E′ transition at 670 nm and the
5
T2 → 5E″ transition at 804 nm. Accordingly, the Jahn−Teller
stabilization energy of the 5T2 state, ΔEJT(5T2), can be estimated
as19
(ΔE(5 T2))2
ΔE JT(5 T2) =
4E IR
where ΔE(5T2) is the energy difference between the maxima of
the 5T2 → 5E′ and 5T2 → 5E″ emission bands and EIR
corresponds to the IR absorption maximum between the
sublevels of the 5E ground state, that is, 5E′ → 5E″ (6527 cm−1).
Thus, ΔEJT(5T2) is determined as 237 cm−1, much smaller than
the value for the 5E ground state [ΔEJT(5E) = 1.63 × 103 cm−1].
Both ΔEJT(5T2) and ΔEJT(5E) values are smaller than those
reported by Kück et al. in the case of garnet single crystals.19
3.3. Temperature-Dependent and Time-Resolved PL
Spectra. Temperature-dependent PL spectra of the CGGG:Mn
single crystal in the 5−300 K range were recorded under 532 nm
laser excitation. The spectra, normalized to the maximum
intensity, are presented in Figure 3a, while the measured PL
intensity is shown in Figure 3b. As can be seen, with decreasing
temperature, the broad PL band related to the 5T2 → 5E
transition of Mn3+ undergoes a blue shift (from 670 nm at 300 K
to 665 nm at 50 K). Below 75 K, an additional PL band (∼680−
900 nm) featuring sharp lines emerges, related to intrashell
transitions of Mn4+. While the intensity of the latter increases
continuously with decreasing temperature, the PL intensity of
Mn3+ drops abruptly below 50 K. This is accompanied by a
sudden red shift of the peak position from 665 nm to about 690
nm. We ascribe the broad band in the 630−700 nm range visible
in the emission spectra below 50 K to the 1T2 → 5E transition of
Mn3+. Lowering the temperature empties the 5T2 level by virtue
of multiphonon transition to the lower-lying 1T2 level. Since
Mn3+ ions in CGGG are located at the octahedral Ga3+ sites,
electric dipole transitions within the d-electron shell are, in
principle, parity-forbidden because of inversion symmetry.
However, vibronic electric-dipole transition probability of
Mn3+ in a weak, trigonally distorted octahedral crystal field
can be induced due to interactions with odd-parity phonons. As
(2)
a result, the 1T2 → 3T1/5E electric-dipole transitions can take
place. Similar temperature-dependent behaviors of Mn3+
luminescence in garnet crystals were reported by Kück et
al.18,19 The weak NIR (∼1100 nm) emission, which is observed
under 532 nm laser excitation at 4.5 K and displayed in Figure
3d, is related to the 1T2 → 3T1 transition of Mn3+.
The temperature dependence of the integrated PL intensities
of Mn3+ and Mn4+ ions is shown in Figure 3c. In the 75−300 K
range, the thermal quenching of Mn3+ luminescence intensity
can be described by the Arrhenius equation
I(T ) = Imax /[1 + A exp( −ΔE /kBT )] (3)
where Imax is the maximum intensity at T = 0, A is a fitting
parameter, kB is the Boltzmann constant, and ΔE is the PL
deactivation energy. Fitting eq 3 to the experimental data in the
temperature range of 75−300 K gives ΔE2 = 0.07 eV, which is
the energy barrier height between the 5T2 state and the
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Figure 2. (a) Temperature-dependent absorption spectra of the CGGG:Mn single crystal; (b) room-temperature PL spectrum under 532 nm
excitation and the photograph of the single crystal with a length of 1 cm and a thickness of 1 mm; (c) Tanabe−Sugano diagram for Mn3+ in octahedral
symmetry; (d) schematic energy level diagram for the Mn3+ ion in a crystal field of octahedral symmetry with trigonal distortion (the Ga site with C3i
point symmetry).
quenching state (3T1 level). On the other hand, strong
luminescence quenching at 5 K can be interpreted as efficient
depopulation of the 5T2 state due to crossover with the 1T2 state.
This process becomes less efficient with increasing temperature
due to thermal depopulation of the 1T2 state over the energy
barrier ΔE1. Two possible nonradiative relaxation pathways
involving 1T2 and 3T1 levels are shown in Figure 3e.
The PL band with sharp lines in the 680−900 nm range
dominating at low temperatures (5−25 K) is assigned to the
spin-forbidden 2E → 4A2 transition superimposed on the spin-
allowed 4T2 → 4A2 transition of Mn4+. Luminescence of Mn4+
ions was also observed in Mn-doped garnet crystals at low
temperature.19 Normalized TRES integrated over each 0.25 ms
time interval after the 530 nm laser pulse, measured at 10, 25,
and 50 K, are shown in Figure 4a. The shape of the emission
spectra changes over time. The sharp lines related to the 2E →
4
A2 transition of Mn4+ vanish relatively fast so that only the
emission of Mn3+ is visible at 1 ms after the laser pulse. The
broad bands with maxima around 690 and 665 nm are assigned
to 1T2 → 5E and 5T2 → 5E transitions of Mn3+, respectively.
Green, red, and blue traces correspond to measurement
temperatures of 10, 25, and 50 K, respectively. Temperature-
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dependent decays of Mn3+ and Mn4+-related emission can be
fitted with double to triple-exponential functions
n
I(t ) = ∑i = 1 Ai exp( −t /τi), n = 2, 3, as shown in Figure S3.
The obtained lifetimes are displayed in Figure 4b as a function of
temperature. The luminescence decay of Mn3+ is dominated by
the shorter components, that is, τ1 and τ2, which increase slightly
with temperature up to 75 K, while the longer decay component
τ1 continuously decreases with increasing temperature. The
increase of the decay time can be explained by thermal
population of the 1T2 state, which contributes to the PL
intensity of Mn3+. For comparison, average decay times were
t
∫0 max tI(t )dt
calculated using a nonexponential function: τ = ,
t
∫0 max I(t )dt
where tmax is the duration of the decay measurement, I(t) is the
luminescence intensity, and τ is the lifetime. The obtained data
sets are shown in Figure 4c. The temperature dependence of the
Mn3+ luminescence decay time can be described by the Mott−
Seitz model
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Figure 3. Temperature dependence of (a) PL spectra and (b) PL intensities of CGGG:Mn in the 4.5−300 K range under 532 nm laser excitation. (c)
Integrated PL intensity vs temperature and Arrhenius fit of the intensity in the 75−300 K range. The calculated deactivation energy is given in the
figure. (d) Emission spectrum (4.5 K) of CGGG/Mn in the NIR region. (e) Single-configurational coordinate model of Mn3+ states for the a1g mode,
according to ref 19. The numbers denote possible nonradiative relaxation pathways, and the red arrows indicate the shift of the 5T2 and 3T1 levels with
decreasing crystal field strength.

Figure 4. (a) Normalized TRES integrated over each 0.25 ms time interval after the 530 nm laser pulse at different temperatures (T = 10, 25, and 50 K);
(b) Mn3+ luminescence decay times as a function of temperature (λex = 530 nm, λem = 670 nm); (c) average decay time of Mn3+ luminescence as a
function of temperature and a fit of eq 4 to the data.

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Figure 5. (a) PL excitation at 4.5 K by monitoring the emissions at 670, 714, and 805 nm; (b) PL spectra of CGGG:Mn upon excitation at 342, 432,
and 532 nm; (c) temperature-dependent PL mapping under 432 nm excitation; (d) integrated intensity as a function of temperature; the solid line is a
fit with eq 3.

Figure 6. (a) Low-temperature and room-temperature PL and PLE spectra of the Mn4+-doped CGGG powder sample; (b) Tanabe−Sugano energy
diagram for a 3d3 ion in an octahedral crystal field.

τ0 contains a component associated with the initial low-temper-

τ (T ) =
ΔE
1 + α exp ( − kT ) (4)
where α is a fitting parameter associated with the radiative and
nonradiative transition probabilities and k is the Boltzmann
constant. The determined activation energy, ΔE, is equal to ΔE
= 0.033 eV, which is the energy barrier height between the 5T2
state and the quenching state. Here, the obtained value of ΔE is
smaller than that estimated according to eq 3 because the barrier
height estimated from integrated luminescence intensity also
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ature growth of the luminescence intensity.
3.4. Luminescence Properties of Mn4+ in CGGG. To
further elucidate the energy structure of Mn4+ in CGGG, we
analyze the PL excitation spectra recorded by monitoring the
emissions peaks at 666, 714, and 805 nm. As shown in Figure 5a,
two excitation bands are observed when monitoring the 5T2 →
5
E transition at 670 nm: one assigned to the O2− → Mn3+
charge-transfer transition (peaked at a wavelength shorter than
300 nm) and the other (around 525 nm) corresponding to the
spin-allowed 5E → 5T2 transition of Mn3+, consistent with the
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Figure 7. Pressure dependence of (a) PL spectra and (b) PL peak energies at room temperature under 532 nm excitation. Orange and blue traces in (a)
indicate deconvolution into components related to transitions from the 5T2 excited state to the 5E″ and 5E′ sublevels of the 5E ground state. (c)
Evolution of the 5T2 energy level with increasing pressure.
absorption spectrum. However, three bands peaked at 340, 430,
and 590 nm are observed by monitoring the maximum of the
sharp peak at 714 nm. Apparently, these bands are typical
absorption bands of Mn4+ ions in the CGGG crystal. Under 340
and 430 nm illumination, only the emission of Mn4+ is observed,
as presented in Figure 5b. The PL spectrum consisting of Mn3+
(5T2/1T2 → 5E) and Mn4+ PL was obtained under illumination
with 532 nm light due to the overlapping excitation bands. The
PL spectrum of Mn4+ in CGGG is an overlap of 2E → 4A2 (sharp
lines at shorter wavelengths) and 4T2 → 4A2 (broad bands at
longer wavelengths) transitions. Two peaks visible at shorter
wavelengths (∼680 and 683 nm) are zero phonon lines (ZPLs)
corresponding to the 2E → 4A2 transition. In fact, the same, weak
ZPLs were observed in the low-temperature absorption spectra
(see Figure S4). The two ZPLs can be assigned to the
components of the 2E state split due to the trigonal distortion of
the Mn4+ octahedral centers in CGGG. The separation energy is
60 cm−1, which is larger than those found in Y2Mg3Ge3O12:Mn4+
(16 cm−1) and YAG:Mn4+ (19 cm−1).33,34 Figure 5c shows the
temperature dependence of Mn4+ PL spectra in the 4.5−125 K
range under 432 nm excitation. The integrated PL intensity as a
function of temperature (Figure 5d) and the fit with use of eq 3
reveal a small activation energy of 0.021 eV, indicating strong
thermal quenching of the Mn4+ luminescence.
The spectral overlap (Figure 5a) makes it difficult to separate
the PLE spectra of the Mn4+ ion using a deconvolution
operation. To determine the crystal field parameters of Mn4+
CGGG:2% Mn4+powder samples with and without charge
compensation of Ca, Mg was synthesized by solid-state reaction
(see the Supporting Information). The Mn4+ ions were
intentionally substituted for Ga ions in the octahedral sites.
Both room- and low-temperature PL and PLE were measured, as
presented in Figure 6. The same PL and PLE spectra were
recorded at low temperature in the powder and single-crystalline
samples, proving the correctness of our assignment of these
features to Mn4+. At room temperature, only a broad band with a
maximum at 744 nm is observed in the Mn4+ PL spectrum,
indicating that Mn4+ experiences an intermediate (Dq close to
the crossover point of the 4T2 and 2E states) crystal field in
CGGG. The temperature evolution of the PL spectra measured
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in CGGG:Mn4+ powders, provided in Figure S5, implies a large
lattice relaxation of the 4T2 state of Mn4+ in the CGGG host. The
excitation bands observed at 300, 454, and 653 nm in the room-
temperature PLE spectra are attributed to the fully allowed
O2−−Mn4+ charge-transfer transition and spin-allowed intra-
configurational 4A2 → 4T1 (4F) and 4A2 → 4T2 (4F) transitions
of the Mn4+ ion in the octahedral coordination, respectively.
The determination of Mn4+ transition energies enables us to
estimate the crystal field parameters of Mn4+ in CGGG.
According to Tanabe−Sugano crystal field theory, the crystal
field strength (Dq) can be estimated from the 4A2 → 4T2
transition energy, E
Dq = E(4 A 24A 2 → 4 T2)/10 (5)
The Racah parameters B and C can be extracted from the
experimental PL spectra with following relations
Dq 15(x − 8)
=
B x 2 − 10x (6)
E(4 A 2 → 4 T1) − E(2 A 2 − 4 T2)
x=
Dq (7)
E(2 E) = 3.05C + 7.9B − 1.8B2 /Dq (8)
The Dq and B values obtained based on the experimental
results with use of the above equations are 1531 and 695 cm−1,
respectively. Taking the energy of ZPL at 680 nm as the energy
of the 2E state, the C parameter can be estimated as 3208 cm−1.
Thereupon, the value of Dq/B is determined as 2.20, indicating
that Mn4+ experiences an intermediate crystal field in the CGGG
lattice. The calculated values for Dq/B, B, and C are 2.24, 685,
and 3265 cm−1, respectively, showing good agreement with
those determined from experimental data.
The nephelauxetic parameter β1 = (B/B0)2 + (C/C0)2 (B0 =
1160 cm−1and C0 = 4303 cm−1 are the Racah parameters of the
free Mn4+ ion) was introduced by Brik and Srivastava35,36 in the
spectroscopy of d3 ions to describe the relationship between the
2
E → 4A2 transition and the Racah parameters B and C. This
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parameter takes simultaneously into account the reduction of
both B and C parameters. The calculated β1 of 0.9564 can be
used to predict the energy position of 2E in a linear relation:
E(2E) = 16261.92β1 − 880.49 ± σ,37 where σ = 332 cm−1 is the
root-mean-square deviation of the data points from the linear fit.
Therefore, the energy of E(2E) can be estimated to be in the
range of 14333.91−14997.91 cm−1, in reasonable agreement
with the experimental value of 14705 cm−1.
The lowest calculated and observed energy levels, which are
located in the spectral range corresponding to the experimental
absorption/excitation/emission spectra, are listed in Table 4.
Although the concentration of Mn4+ ions is only a small
fraction of that of Mn3+, they still have a significant influence on
the luminescence properties of CGGG:Mn single crystals in the
low-temperature range (4.5−100 K). The streak camera images
(Figure S6) of the CGGG:Mn single-crystal luminescence at low
temperature (7 K) under 425 nm excitation, together with
TRES, reveal that the shape of the Mn4+ emission spectrum
changes over time. The intensity of the peak at 714 nm decreases
relatively faster with time than that of the peak around 702 nm,
which implies the presence of inequivalent Mn4+ luminescent
centers in CGGG, with different lifetimes. Both calculated and
experimental results show that Mn4+ experiences a relatively
weak crystal field when situated at Ga-octahedral sites in the
CGGG host. Replacing Ga3+ with Mn4+ ions in the CGGG
crystal does not significantly deform the host lattice due to their
comparable ionic radii. The other Mn4+ center, in addition to the
dominant Mn4+ centers in Ga3+ octahedral sites, is most
probably associated with substitution at Ca2+ dodecahedral sites.
In this case, the excess charge is usually compensated by the
formation of structural defects, as observed in many garnets,
such as GGG:Cr3+,38,39 LGG:Cr/Nd3+,40 and CGGG:Cr3+.11
3.5. High-Pressure PL Spectra of the CGGG/Mn Single
Crystal. Due to the large radius of the 3d orbitals and the lack of
shielding by outer filled shells, the electronic states of 3d ions are
very sensitive to the local crystalline environment, that is,
symmetry, bond lengths, their angles, and coordination
polyhedra.41 It is therefore interesting to study the luminescence
properties of the CGGG:Mn single crystal under high
hydrostatic pressure. Figure 7a displays the pressure evolution
of the PL spectra under 532 nm excitation. Consisted with the
Tanabe−Sugano diagram for Mn3+ (3d4), a blue shift of Mn3+
emission bands is observed as the pressure increases up to 100
kbar. The PL spectra can be deconvoluted into two Gaussian
bands assigned to 5T2 → 5E′/5E″ transitions. Peak positions in
respective pressure dependences of the two components are
presented in Figure 7b, and the scatter plots demonstrate a linear
increase with pressure at a rate of 10.5 cm−1/kbar in the pressure
range up to about 72 kbar. Thus, the dependence of the 5T2 →
5
E transition energy on pressure can be described by d(ΔE)/dP
= 10.5 cm−1/kbar. The blue shift of observed broad-band PL
also provides a strong support for its assignment to the Mn3+
dopant as a d4 system. Indeed, should this luminescence be
associated with 4T1 → 6A1 transitions of Mn2+, a red PL shift
should have been seen, in accordance with Tanabe−Sugano
diagrams for d5 systems as well as several experimental results, as
for example, shown in refs 42 and 43.
This dependence can be applied to determine the pressure at
which the crossing between the 5T2 and 3E levels occurs as ΔE =
ΔE0 + Pd(ΔE)/dP, where ΔE0 = −665 cm−1, evaluated from the
absorption spectrum, is the difference between the energies of
the 5T2 and 3E levels under ambient conditions (room
temperature). Since the 3E energy is almost independent of
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crystal field strength, the crossing ΔE = 0 takes place at a
pressure equal to 75 kbar. The increase of crystal field strength
under high pressure results in the reduction (at lower pressures)
and eventual elimination (above 100 kbar) of the population of
the 5T2 level of the Mn3+ ion because of the pressure-derived
increase of the 5T2 level energy. Therefore, application of
pressure induces a significant luminescence quenching and
eventually leads to the absence of the 5T2 → 5E transition. After
decompression to ambient pressure, the same PL spectrum was
obtained, suggesting that no pressure-induced phase transition
occurs in the pressure range up to 144 kbar. This was further
confirmed by high-pressure Raman spectra of CGGG/Mn
under 532 nm laser excitation. As shown in Figure S7,
application of pressure to the crystal results in an increase of
Raman shifts, whereby the higher energy modes shift toward
higher frequencies at faster rates than the low energy modes. The
spectrum, however, remains the same after pressure release.
Interestingly, a new PL band peaked at about 717 nm emerges
above 80 kbar and dominates the room-temperature PL spectra
above 100 kbar. We assign it to the 2E → 4A2 transition of Mn4+
for the following reasons: as already mentioned, the 5T2 level of
Mn3+ cannot be populated by 532 nm light due to its very high
location under high pressure, but radiative transitions from the
lower-lying levels 1T2 and 3E may, in principle, take place.
According to the Tanabe−Sugano diagram, the 1T2 state should
exhibit a large red shift with increasing pressure. Therefore, the
1
T2 → 5E transition of Mn3+ appears unlikely because the
observed peak is almost pressure-independent. Since the
emitting levels of Mn3+-5T2 and Mn4+-2E have different crystal
field dependences, their luminescence can be distinguished by
changing temperature under high pressure. Figure 8a shows
Figure 8. (a) Pressure-dependent PL spectra at 150 K and (b)
temperature-dependent PL spectra of CGGG:Mn under a pressure of
89 kbar.
high-pressure PL spectra at 150 K. A very fast quenching of Mn3+
luminescence with increasing pressure is observed, and the new
band featuring sharp lines dominates in the PL spectrum already
under a pressure of 45 kbar instead of 100 kbar. This PL band is
identical with the one observed at 5 K at ambient pressure and
assigned to the 4T2 → 4A2 and 2E → 4A2 transitions of the Mn4+
ion. The strong quenching of Mn3+ luminescence can be
explained by the decrease of the 5T2 state population compared
to that at room temperature. In addition, energy transfer from
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Figure 9. (a) Temperature-dependent PL spectra and (b) integrated PL intensities of Mn3+ and Mn4+ in a CGGG/Mn single crystal in the 5−120 K
range. (c) Ratio of integrated emission intensities of Mn4+ and Mn3+ as a function of temperature. The solid line in the inset is calculated with the
equation written in the figure. (d) Relative sensitivity in the 5−75 K range.
the Mn3+ ion to Mn4+ may take place and thus enhance the Mn4+
luminescence under high pressure. The temperature-dependent
PL spectra (Figure 8b) under a pressure of 89 kbar show that the
Mn3+ emission recovers at 260 K and dominates in PL spectra
until room temperature, but the Mn4+ emission around 717 nm
still remains strong. Thus, we are more inclined to ascribe it to
the 2E → 4A2 transition of Mn4+.
There is also a possibility that at pressures above 70 kbar, the
5
T2 → 5E Mn3+ transitions are gradually replaced with 3E → 3T1
ones (see Figure 7a and Tanabe−Sugano plot Figure 2c). High-
pressure decay kinetics measurements could help to distinguish
between above-mentioned explanations; however, they are
difficult to perform due to relatively low luminescence intensity
at high pressures. Further attempt to conduct such measure-
ments is planned.
3.6. Cryogenic Luminescence Ratiometric Thermom-
etry of CGGG/Mn. Cryogenic luminescence ratiometric
thermometry can be realized due to the distinct luminescence
of Mn3+ and Mn4+ and their diverse thermal quenching
behaviors in the low-temperature range, as shown in Figure
9a. Figure 9b shows the temperature dependence of the
integrated intensities of Mn3+ (600−690 nm) and Mn4+
(700−750 nm) luminescence as the temperature increases
from 5 to 120 K. To further characterize the temperature
performance of the CGGG/Mn single crystal, the fluorescence
intensity ratio (FIR) of integrated emission intensities of Mn4+
and Mn3+ as a function of temperature can be deduced from eq 3
and expressed as follows
I(Mn 4+)max 1 + AMn3+ exp( −ΔEMn3+ /kBT )
IMn 4+
FIR = = Cooling to 50 K empties the 5T2 level by virtue of multiphonon
IMn3+ I(Mn3+)max 1 + AMn 4+ exp( −ΔEMn 4+ /kBT )
≈ B + C exp( −ΔE /kBT )
(9)
where B, C, and ΔE are parameters related both to Mn and to 4+
Mn3+. For the purpose of practical applications, the relative
sensitivity, Sr, which is considered as a critical parameter for the
temperature sensing performance, can be written by the
following expression
1 ∂FIR FIR − B ΔE
Sr = × 100% = × 100%
FIR ∂T FIR kT 2
(10)
The experimental data of temperature-dependent FIR can be
well fitted with eq 9 in the range from 5 to 75 K, as displayed in
the inset of Figure 9c. The values of Sr calculated with use of eq
10 are plotted in Figure 9d. It can be seen that Sr continuously
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increases and reaches its maximum of 6% K−1 at 33 K, revealing a
comparable sensing performance in the 5−75 K range to
reported optical thermometry in the cryogenic temperature
range.44,45 Most lanthanide and transition-metal ions used as
optical temperature sensors are based on thermally coupled
energy levels (TCELs) and work usually in a relatively high-
temperature range. It is a challenge to develop luminescence
thermometry operating at cryogenic temperatures (<100 K)
with high sensing performance because the large energy gap
between TCELs and thus the Boltzmann-related thermal
population are not significant at low temperatures. In view of
the superior performance under 532 nm excitation reported
here, the garnet-type CGGG/Mn single crystal can be employed
as an outstanding luminescence thermometric material in the 5−
75 K cryogenic temperature range.
4. CONCLUSIONS
In this work, both theoretical and experimental studies of the
luminescence properties of Mn-doped garnet-type
Ca3Ga2Ge3O12 single crystals are reported, with emphasis on
the temperature and high-pressure effects on Mn luminescence
quenching. At ambient pressure, the optical spectroscopy results
reveal a much larger Jahn−Teller splitting in the 5E ground state
than in the 5T2 excited state of Mn3+. Above 75 K, the emission
spectra under 532 nm excitation are dominated by a broad band
at 670 nm arising from the spin-allowed 5T2 → 5E transition of
Mn3+. The temperature dependences of PL spectra and time
decays reveal strong thermalization in 5T2 and 1T2 levels.
transition to the lower-lying 1T2 level. As a result, the 1T2 →
3
T1/5E electric-dipole transitions are induced by coupling to
odd-parity phonons. The existence of Mn4+ can be ascertained
by lowering the temperature or applying high pressure. Upon
increasing the pressure up to 100 kbar, the 5T2 → 5E transition of
Mn3+ undergoes a blue shift at a rate of ∼10.5 cm−1/kbar. The
Jahn−Teller distortion in the 5E ground state is manifested to be
nearly independent of pressure. Cryogenic luminescence
ratiometric thermometry based on the diverse thermal
quenching behaviors of Mn3+ and Mn4+ was explored.
Furthermore, the theoretical calculations employing the
exchange-charge model of crystal field for Mn3+ and Mn4+ ions
in Ga3+ octahedral sites in garnet-type Ca3Ga2Ge3O12 remain in
perfect agreement with the experimental data. The result
provides a new insight into the luminescence quenching
mechanism of Mn3+-doped garnet-type materials.
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■
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.jpcc.0c09845.
Preparation of Ca3Ga2Ge3O12:2%Mn4+ powder samples,
XRD patterns, and Rietveld refinement; band structure
calculations, temperature-dependent decay lifetime, and
temperature-dependent absorption spectra of the
CGGG:Mn single crystal; temperature-dependent PL
spectra of CGGG:2%Mn4+ powder; streak camera images
and TRES; high-pressure evolution of Raman spectra and
temperature-dependent Raman spectra of the CGGG:Mn
single crystal; and EPR spectrum of the CGGG:Mn single
crystal at room temperature (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
Yongjie Wang − College of Sciences, Chongqing University of
Posts and Telecommunications, Chongqing 400065, China;
Institute of Physics, Polish Academy of Sciences, Warsaw 02-
668, Poland; orcid.org/0000-0002-5580-8555;
Email: wangyj@cqupt.edu.cn
A. Suchocki − Institute of Physics, Polish Academy of Sciences,
Warsaw 02-668, Poland; orcid.org/0000-0001-7126-
1951; Email: suchy@ifpan.edu.pl
Authors
Damian Włodarczyk − Institute of Physics, Polish Academy of
Sciences, Warsaw 02-668, Poland; orcid.org/0000-0002-
5923-7569
Mikhail G. Brik − College of Sciences, Chongqing University of
Posts and Telecommunications, Chongqing 400065, China;
Institute of Physics, University of Tartu, Tartu 50411, Estonia;
Institute of Physics, Jan Dlugosz University, Czestochowa PL-
42200, Poland
Justyna Barzowska − Institute of Experimental Physics,
University of Gdańsk, 80-952 Gdańsk, Poland
A. N. Shekhovtsov − Institute for Single Crystals, NAS of
Ukraine, Kharkov 61001, Ukraine
K. N. Belikov − Institute for Single Crystals, NAS of Ukraine,
Kharkov 61001, Ukraine
Wojciech Paszkowicz − Institute of Physics, Polish Academy of
Sciences, Warsaw 02-668, Poland
Li Li − College of Sciences, Chongqing University of Posts and
Telecommunications, Chongqing 400065, China;
orcid.org/0000-0003-1163-5733
Xianju Zhou − College of Sciences, Chongqing University of
Posts and Telecommunications, Chongqing 400065, China;
orcid.org/0000-0002-8050-9688
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.jpcc.0c09845
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was partially supported by grant nos. 2019/33/B/
ST8/02142 and 2018/31/B/ST8/03390 and PRELUDIUM
no. DEC-2017/25/N/ST5/02285 of the Polish National
Science Center. Y.W. acknowledges financial support from the
National Natural Science Foundation of China (12004062).
M.G.B. thanks the support from the Chongqing Recruitment
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pubs.acs.org/JPCC Article
Program for 100 Overseas Innovative Talents (grant no.
2015013), the Program for the Foreign Experts (grant no.
W2017011) and Wenfeng High-end Talents Project (grant no.
W2016-01) offered by Chongqing University of Posts and
Telecommunications (CQUPT), Estonian Research Council
grant PUT PRG111, the European Regional Development Fund
(TK141), and NCN project 2018/31/B/ST4/00924.
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