PHYSICAL REVIEW B 99, 235151 (2019)

Crystal field and hyperfine structure of 167 Er3+ in YPO4 :Er single
crystals: High-resolution optical and EPR spectroscopy
M. N. Popova,1 S. A. Klimin,1,* S. A. Moiseev,2 K. I. Gerasimov,2 M. M. Minnegaliev,2 E. I. Baibekov,2,3
G. S. Shakurov,4 M. Bettinelli,5 and M. C. Chou6
1
Institute of Spectroscopy, Russian Academy of Sciences, 5, Fizicheskaya Str., Troitsk, Moscow 108840, Russian Federation
2
Kazan Quantum Center, Kazan National Research Technical University named after A.N. Tupolev-KAI, 10 K. Marx Str.,
Kazan 420111, Russia
3
Kazan (Volga Region) Federal University, 18 Kremlyovskaya Str., Kazan 420008, Russia
4
Zavoisky Physical Technical Institute, FRC Kazan Scientic Center of the Russian Academy of Sciences,
ul. Sibirskii trakt 10/7, Kazan, 420029, Russia
5
Dipartimento di Biotecnologie, University of Verona and INSTM, Strada Le Grazie 15, Verona 37134, Italy
6
Department of Materials and Optoelectronic Science, Center of Crystal Research,
National Sun Yat-Sen University, 70, Lien-Hai Rd., Kaohsiung 80424, Taiwan

(Received 29 December 2018; published 26 June 2019)

We report on a high-resolution optical and magneto-optical spectroscopy, luminescence, and electron

paramagnetic resonance (EPR) studies of yttrium orthophosphate single crystals doped with erbium, which
are promising telecom-wavelength materials for applications in quantum electronics and quantum information
processing. An observation of the hyperfine structure in optical spectra of 167 Er isotope in Er : YPO4 is presented.
Energies and symmetries of 40 crystal-field levels of Er 3+ in Er : YPO4 and g factors of some of them were
determined and successfully modeled on the basis of crystal-field calculations. The obtained set of crystal-field
parameters was used in modeling the hyperfine structure observed in the optical and EPR spectra of Er : YPO4
single crystals.

DOI: 10.1103/PhysRevB.99.235151

I. INTRODUCTION crystals of large sizes. Recently, a Chinese group from Qing-

dao succeeded in growing good-quality single crystals of
The orthovanadates AVO4 (A = Y, Gd, Lu) and or-
Yb-doped LuPO4 [4,5] and YPO4 [6] single crystals using
thophosphates APO4 (A = Y, Lu) with zircon structure, pure
the high-temperature solution-melt method. Continuous-wave
or doped with rare-earth (RE) ions, exhibit unique physico-
[4] and Q-switched [5] high-power efficient laser operation
chemical and optical properties, which makes them interesting
of a miniature Yb : LuPO4 crystal rod was reported. Efficient
for numerous applications such as laser [1–6] and Raman-
continuous-wave laser action was achieved under diode end-
laser [7] hosts, scintillators for γ - and x-ray detection [8,9],
pumping conditions of a plate-shaped Yb : YPO4 1.0-mm
thermophosphors for remote temperature measurements [10],
thick crystal [6].
up- and down-conversion (quantum cutting) materials for
This success draws attention to the Er : YPO4 crystal,
fluorescent lamps, plasma display panels, solar cells, secu-
which could be a good candidate for lasing at the telecom
rity markers [11–14], biolabels, drug carriers, and agents in
wavelength 1.5 μm. Using Er : YPO4 in quantum memory
photodynamic therapy [15], etc. All the vanadate crystals devices to increase the range of cryptographic communication
can be grown by the Czochralski method and large single lines [16–18] could be another attractive application. It is
crystals of good optical quality are available [1]. The most important to note that an optical quantum memory has already
well-developed vanadate Nd : YVO4 crystal is among the best been successfully realized using hyperfine levels of Nd3+ in
commercial materials for diode-pumped continuous-wave, Q- Nd : YVO4 crystals [19,20]. Unlike vanadium, the most com-
switched, and mode-locked lasers but Nd3+ - and Yb3+ -doped mon (99.7%) isotope of which 51 V has a large nuclear spin
GdVO4 , LuVO4 , and mixed Gdx Y1−x VO4 and Lux Gd1−x VO4 I = 7/2, phosphorus is a monoisotopic element with nuclear
crystals are intensively studied for different laser applica- spin I = 1/2 (as in yttrium). Due to this circumstance, YPO4
tions, including in the high-power laser field [1]. Tm3+ -doped could turn out to be a better matrix for quantum memory than
GdVO4 and LuVO4 crystals also demonstrate an efficient laser YVO4 . In addition, the resolved hyperfine structure (HFS) was
performance [2,3]. Orthophosphates melt incongruently and observed in the absorption spectra of Ho : YPO4 crystals [21].
cannot be grown by the conventional Czochralski method, The resolved HFS is also favorable for the implementation
and it is extremely difficult to produce high-quality single of the off-resonant Raman-echo [22] and gradient-echo [23]
protocols of optical quantum memory.
For applications in quantum memory devices, the knowl-
* edge of HFS of the crystal-field (CF) levels is essential. We
Corresponding author: [email protected]

2469-9950/2019/99(23)/235151(10) 235151-1 ©2019 American Physical Society

M. N. POPOVA et al. PHYSICAL REVIEW B 99, 235151 (2019)

are not aware of any experimental information on the HFS in

the spectra of Er : YPO4 . The only stable odd isotope 167 Er

PMT Monochromator
Digital

Laser Systems
M833-SOLAR
has the nuclear spin I = 7/2 and the natural abundance of Multimode
Oscilloscope
22.87%. Other five stable isotopes, the most abundant of them fiber
being 166 Er (33.503%), are even ones with I = 0 and, hence,
have no HFS of electronic levels. The HFS can be calculated
with the help of wave functions of CF levels obtained from
CF calculations. However, CF parameters available in litera- D
ture are contradictory [24–27]. We decided to perform high-
resolution optical absorption and luminescence spectroscopy
measurements of Er : YPO4 single crystals, with the aims Glass filter
(i) to look for the HFS in the spectra and (ii) to determine
reliable CF parameters for modeling the HFS. 4K cryostation
The paper is organized in the following way. In Sec. II Montana Instruments
we describe the crystal growth and provide information on
B
the equipment and procedures used to measure the EPR and
optical spectra. Experimental data on energies, symmetries, Lock-in
AWG
g factors, and hyperfine structure of the crystal-field levels amplifier ADC
of Er 3+ in Er : YPO4 obtained from the analysis of high-
resolution transmission, luminescence, and EPR spectra are Reference laser
interferometer Laser
presented in Sec. III. Section IV reports on the crystal-field
controller
calculations and the spectra modeling on this basis. Section V AOM
briefly summarizes the results.

90/10 Laser
II. EXPERIMENTAL DETAILS
FIG. 1. Experimental setup for recording the absorption and
Yttrium orthophosphate single crystals YPO4 doped with luminescence spectra and kinetics of the luminescence (including
Er 3+ ions with concentrations 0.005, 0.01, 0.1, 0.2, 0.4, and in a magnetic field B). AOM – acousto-optic modulator, ADC –
0.7 at.% were grown by the flux method using Pb2 P2 O7 analog-to-digital converter, AWG – arbitrary-waveform generator,
as a high-temperature flux [28]. The procedure involves the PMT – photomultiplier, D – detector (avalanche photodiode Thorlabs
dissolution of the rare-earth oxides Er 2 O3 and Y2 O3 in molten APD110C/M), Laser – dye TekhnoScan DYE-SF-077 or Ti:Sapphire
Pb2 P2 O7 at high temperature with spontaneous nucleation (TIS-SF-777) or diode (CTL 1500 - TOPTICA Photonics AG) lasers.
and crystal growth of YPO4 achieved by slow cooling of the Green dashed lines denote USB2.0 connections and black dashed
solution. High purity Y2 O3 and Er 2 O3 , (NH4 )2 HPO4 and PbO lines are for electrical 50- connections between devices.
were employed as starting materials. The melt was heated in
the platinum crucible to a maximum temperature of 1300 ◦ C
and then cooled to 950 ◦ C with a rate of 2 ◦ C/h. In all cases, k denote the electric field and the wave vector of the incident
the flux was dissolved using hot diluted HNO3 . Single crystals radiation, respectively, c is the C4 axis of the crystal).
of good optical quality elongated in the direction of the c axis The spectra and kinetics of the luminescence excited by a
of the tetragonal structure were obtained. The oriented plates dye laser TekhnoScan DYE-SF-077 tuned to the 4 I15/2 (71 ) →
cut from the single crystals with the fixed direction of the c 4
F 9/2 (61 ) (15279.49 cm −1 ) transition of Er 3+ were regis-
axis had thicknesses from 0.025 to 0.07 cm. tered. A simplified scheme of the experimental setup is
The grown crystals were characterized by the EPR method. shown in Fig. 1. The intensity of the laser beam was modu-
The measurements were accomplished with a Bruker EMX lated and the pulses were prepared using an acousto-optical
plus spectrometer in the X band at 5 K and a homemade modulator (AOM). The samples were cooled in a Mon-
broadband EPR spectrometer [29] in the frequency range tana Instruments helium-free optical cryostat system. The
36–76 GHz at 4.2 K. In the latter case, generators 4-141 luminescence decay was detected with a Thorlabs avalanche
and 4-142 were used as microwave radiation sources. In the photodiode APD110C/M. Spectra of luminescence were mea-
X band, in addition to erbium, Fe3+ ions were recorded (at sured using M833 Solar Laser Systems monochromator and a
low power level of the microwave generator), as well as weak thermoelectrically cooled photomultiplier (PMT) Hamamatsu
signals from Gd3+ (at a high amplification). H12397-75.
Polarized high-resolution (up to 0.005 cm−1 ) transmission In the high-resolution magneto-optical absorption studies,
spectra were measured in broad spectral (5 000–21 000 cm−1 ) the samples of Er : YPO4 were cooled and subjected to mag-
and temperature (4–300 K) ranges using a Fourier spec- netic fields B||c and B⊥c, the values of which could be set
trometer Bruker IFS 125HR and a closed-cycle cryostat between −0.7 and 0.7 T using an add-on magneto-optical
Cryomech ST 403. The temperature was stabilized within module of the Montana Instruments cryostation. Tunable
±0.2 K. The absolute precision of the wave-number scale single-frequency Ti:Sapphire (TIS-SF-777) and diode (CTL
was 0.002–0.02 cm−1 , depending on the spectral resolution 1500 - TOPTICA Photonics AG) lasers were used to measure
used. The spectra were registered for linearly π -polarized the Zeeman splitting of several lines in the 4 I15/2 → 4 I9/2 and
(E ⊥ c⊥k) or σ -polarized (Ec⊥k) incident radiation (E and 4
I15/2 → 4 I13/2 optical transitions of Er 3+ , respectively.

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The impurity Er 3+ ions in yttrium orthophosphate sub-

stitute for Y3+ ions at the sites with the tetragonal point
symmetry group D2d . The crystal field of the D2d symmetry
splits the energy levels of the free Er 3+ ion characterized
by the electronic total angular momentum J into J + 1/2
Kramers doublets, the wave functions of which transform
according to 6 and 7 irreducible representations of the D2d
point group. Particular numbers of 6 and 7 levels for each J
are indicated in Table I. The Kramers doublets can be further
split by a magnetic field and we discuss this point later in
Sec. III B.
The assignment of the observed spectral lines was based
on the selection rules for electric dipole (ED) and magnetic
dipole (MD) transitions at the sites with D2d symmetry. These
selection rules are given in Table II.
First of all, we check the symmetry of the ground state. At
FIG. 2. High-resolution (0.01 cm−1 ) (a),(c),(e),(g) σ - and 5 K only this state is populated. Whatever the symmetry of
(b),(d),(f),(h) π -polarized transmission spectra of YPO4 single the ground state is, in the σ polarization all transitions are ED
crystal doped with Er 3+ in the regions of optical transitions from allowed (see Table II). For the π -polarized spectrum, the situ-
the ground state to the (a),(b) 4 I13/2 , (c),(d) 4 I11/2 , (e),(f) 4 I9/2 , and ation is different, namely, 6 → 6 and 7 → 7 transitions
(g),(h) 4F 9/2 CF multiplets at 5.3 K. Doping concentrations were are allowed only in the MD approximation. The MD contribu-
(a),(b),(c),(d) 0.2 at.% and (e),(f),(g),(h) 0.4 at.%. tion is, as a rule, weak, with the exception of the MD allowed
in the free Er 3+ ion 4 I13/2 ↔ 4 I15/2 transition. If the symmetry
III. EXPERIMENTAL RESULTS of the ground state were 6 (7 ), one would expect to observe
three (two) absorption lines in the π -polarized spectra of mul-
A. Crystal-field levels of Er3+ in Er : YPO4 tiplets with J = 9/2. Two lines in the π spectra of 4 I9/2 and
High-resolution transmission spectra and luminescence 4
F 9/2 multiplets in Fig. 2 are in favor of the 7 symmetry of
spectra in the earlier not explored infrared (IR) spectral region the ground state. Energies and symmetries of the CF levels in
allowed us to complement the scheme of CF levels. Figures 2 the excited multiplets found directly from the low-temperature
and 3 present several examples of polarized IR transmission polarized absorption spectra are listed in Table I.
and luminescence spectra, respectively. We measured spectra The CF levels of the ground multiplet 4 I15/2 were found
of luminescence from the two lowest-energy CF states in each from the transmission spectra at elevated temperatures and
of the 4 I11/2 and 4 I13/2 multiplets to the CF levels of the from the luminescence spectra. These data are given in Ta-
ground 4 I15/2 multiplet, at excitation wavelength tuned to the ble III, together with the corresponding literature data. As the
4
I15/2 (71 ) → 4F 9/2 (61 ) (15 279.4 cm−1 ) transition. Intensity ionic radii of Er 3+ and Y3+ for coordination number VIII are
of the luminescence from 4 I11/2 was about two orders of close (0.1004 and 0.1019 nm, respectively [30]), CF levels
magnitude lower than from 4 I13/2 . of Er 3+ in Er : YPO4 and ErPO4 vary little. For the ground

FIG. 3. Luminescence spectra of the YPO4 : Er 3+ (0.2 at. %) single crystal in the regions of (a) 4 I13/2 → 4 I15/2 and (b) 4 I11/2 → 4 I15/2
optical transitions at different temperatures indicated above the spectra. Unpolarized (black lines), σ - (red line), and π - (blue line) polarized
luminescence.

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M. N. POPOVA et al. PHYSICAL REVIEW B 99, 235151 (2019)

TABLE I. Energies (cm−1 ) at 5 K and irreducible representations  of CF levels of Er 3+ ions in Er : YPO4 crystals for excited multiplets.
Data from the absorption (Abs.) and luminescence (Lum.) experiments are compared with the results of calculations (Calc.).

This work This work Ref. [24] This work Ref. [24]
 Abs. Lum. Calc.  Abs. Calc. Abs.  Calc. Abs.

4
I13/2 → 46 + 37 4
F9/2 → 26 + 37 4
F5/2 → 26 + 7
61 6531.6 6531.6 6537 71 15241.5 15245 15241.5 61 22161 22162.1
7 1
6542.0 6542 6545 7 2
15270.8 15280 15270.9 71
22193 22191.6
72 6599.9 6600 61 15279.5 15281 15279.4 62 22191 22195.5
62 6616.8 6617 73 15325.1 15324 15325 4
F3/2 → 6 + 7
63 6637.8 6641 62 15367.8 15367 15367.8 61 22520 22517
7 3
6669.5 6676 4
S3/2 → 6 + 7 72
22548 22550.7
64 6692.3 6694 61 18367.3 18373 18367.1 2
H9/2 → 26 + 37
4
I11/2 → 36 + 37 71 18416.7 18409 18416.3 61 24485 24502.7
61 10201.1 10201 10194 2
H11/2 → 36 + 37 62 24548 24539
7 1
10216.3 10216 10209 61 19087.3 19095 19087.1 71
24539 24541.4
62 10239.6 10240 71 19130 19119.7 72 24608 24623.3
72 10245.2 10245 62 19145.8 19157 19145.8 73 24671 24656.2
63 10255. 10258 72 19183.3 19185 19183.4 4
G11/2 → 36 + 37
7 3
10270.4 10272 6 2
19202.2 19184 19201.8 61 26313 26310.3
4
I9/2 → 26 + 37 7 19218 19235.3 71 26337 26332.5
61 12378.2 12371 4
F7/2 → 26 + 27 62 26370 26353.3
62 12432.7 12442 71 20489 20484.7 72 26411 26405.4
7 1
12444.1 12446 61 20496.3 20492 20496.3 62
26455 26466.6
72 12530.6 12527 62 20557.8 20556 20557.6 73 26476 26485.5
73 12582.6 12595 72 20573.7 20569 20573.5

multiplet, the latter were studied also by inelastic neutron band (g0 = 6.42 and g0⊥ = 4.80) is in good agreement with
[31] and resonance Raman [32] scatterings. Table III lists also the values from the literature [35,36].
these data. We now determine the g factors of several excited states
Most of the measured energies of the CF sublevels of from the analysis of the high-resolution absorption spectra of
the ground and excited multiplets of the Er 3+ ion and the the Er : YPO4 crystal placed into the magnetic fields B||c and
corresponding irreducible representations determined from B⊥c. Figure 4(a) shows, as an example, the Zeeman splitting
the polarized spectra (see Tables I and III) coincide with of the absorption line 6531.6 cm−1 in a magnetic field B||c.
the earlier published data [24]. The energy value 138.3 cm −1 The Zeeman splitting of the corresponding Kramers doublets
announced from neutron scattering experiments on ErPO4 and allowed transitions between them are displayed in the
[31] disagrees with other data. scheme of Fig. 4(b). Two (four) transitions are allowed in
Measurements of the luminescence kinetics from the 4 I13/2 the σ (π ) polarization. Of the four π -polarized transitions,
level revealed a single decay time τ = 5.1 ± 0.2 ms at 5 K two are ED transitions and the other two are MD ones
(see details in the Appendix). For a comparison, erbium (we should note that for the 4 I15/2 → 4 I13/2 transition, which
luminescence decay time 2.3 ms was observed in YVO4 :Er is MD allowed in the free Er 3+ ion, the intensity of the
(2.5 at.%) [34]. MD transitions between CF levels can be comparable with
that of the ED transitions). It follows from the observed
Zeeman spectral pattern [see Fig. 4(a)], in which the σ -
B. EPR and magneto-optical spectroscopy: g factors
polarized line splitting νσ coincides with the smallest of
We confirm the values of the ground-state g factors from the two splittings of the π -polarized line, that the g factors
the angular dependences of the EPR spectra measured in the X of the ground and excited states have different signs (if
the signs were the same, the σ -polarized lines would show
TABLE II. Selection rules for the ED and MD optical transitions a coincidence with the largest splitting of the π -polarized
of Kramers ions in the D2d symmetry sites.
line). In this case, νσ = 0 − ex = νπMD ; νπED = 0 +
ex , where 0 = |g0 |μB B and ex = |gex |μB B are the Zee-
D2d 6 7
man splittings of the ground and excited Kramers doublets,
6 σED,MD πMD σED πED,MD respectively, and μB is the Bohr magneton. The inset of
7 σED πED,MD σED,MD πMD Fig. 4(a) shows the field dependences of the Zeeman splitting
in the σ and π polarizations. From a linear fitting of these

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CRYSTAL FIELD AND HYPERFINE STRUCTURE OF … PHYSICAL REVIEW B 99, 235151 (2019)

TABLE III. Energies E (cm−1 ) and symmetries  of CF levels of the Er 3+ ions in Er : YPO4 , Er : LuPO4 , and ErPO4 crystals for the
ground multiplet 4 I15/2 .

Er : YPO4 , this work Er : YPO4 Er: LuPO4 ErPO4 ErPO4 ErPO4

[24] [33] [32] [31] [32]
Lum. Abs. Calc. Abs. Abs. Abs. Neutrons Raman
 E  E  E  E E E  E  E

71 0 71 0 71 0 71 0 0 0 71 0 71 0

61 31 61 32 61 37 61 32 36 33 61 32.9 61 33
72 52 72 50 72 51 72 52.5 53 53 72 52.2 72 53
73 106 73 108 73 111 73 108 98 105 73 138.3 73 105
62 141 62 144 62 141 62 143 145 62 144.3 62 145
63 231 63 63 235 63 232 63 233.9 63 234
74 264 74 74 250 74 244 74 242.3 74 246
64 303 64 64 306 64 64 64 269

dependences, we find values and signs of gex , under an as- C. Hyperfine structure in the EPR
sumption that g0 is positive. A summary of the results is given and optical spectra of Er : YPO4
in Table IV. Figure 5(a) displays high-resolution EPR spectra of
a YPO4 :Er (0.1%) sample obtained with both a Bruker

FIG. 4. (a) Zeeman splitting of the spectral line 6531.6 cm−1 FIG. 5. (a) EPR spectra of the YPO4 :Er (0.1%) single crystal in
corresponding to the 71 (4 I15/2 ) → 61 (4 I13/2 ) optical transition of the B||c orientation of an external magnetic field, at the frequencies
Er 3+ in YPO4 : Er (0.01 at.%) subjected to a magnetic field B||c, (1) 9.4 GHz; (2) 36.3 GHz, (3) 48 GHz, (4) 60.2 GHz. T = 5 K
B = 0.21 T in the σ (red lower trace) and π (blue upper trace) (1), T = 4.2 K (2–4). Inset: spectrum 1 in more detail; blue vertical
polarizations. Inset: Field dependences of the Zeeman splittings νσ lines represent positions of the calculated hyperfine components.
(red symbols) and νπ (blue symbols and line) in the σ and π (b) Calculated hyperfine energy levels corresponding to the ground
polarizations, respectively. T = 5 K. (b) Scheme showing Zeeman 4
I15/2 (71 ) Kramers doublet in a magnetic field. The arrows indicate
splitting of the corresponding Kramers doublets and allowed transi- EPR transitions at the frequency 9.4 GHz. The calculations are
tions between them. detailed in Sec. IV.

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M. N. POPOVA et al. PHYSICAL REVIEW B 99, 235151 (2019)

TABLE IV. Experimental and calculated values of the g factors for Er 3+ in Er : YPO4 . Signs of g were determined relative to the ground
Kramers doublet.

Type of the
transition the ground
g g⊥ state 71 (4 I15/2 )
−1
Multiplet E , cm  Exp. Calc. Exp. Calc. π -pol. σ -pol.
6.42 ± 0.02 4.80 ± 0.02
4
I15/2 0 71 6.438 [35] 6.78 4.803 [35] 4.71 – –
6.42 [36] 4.81 [36]
4
I13/2 6531.6 61 −2.6 ± 0.1 −2.65 6.8 ± 0.1 6.93 ED,MD ED
6542 71 4.5 ± 0.1 4.48 −4.4 ± 0.1 −4.59 MD ED,MD
6600 72 −5.2 ± 0.1 −5.56 3.7 ± 0.1 3.96 MD ED,MD
6617 62 −6.0 ± 0.1 −5.87 −4.3 ± 0.1 −4.12 ED,MD ED
4
I9/2 12378 61 −3.2 ± 0.1 −2.72 3.0 ± 0.1 3.50 ED,MD ED
12432.7 62 1.3 ± 0.1 1.00 −3.0 ± 0.1 −3.50 ED,MD ED

EMX-plus X-band and a homemade broadband spectrometers particular, the spectra of Er : YPO4 with erbium concentra-
in the B||c geometry. Well-resolved hyperfine structure (HFS) tions 0.1, 0.2, and 0.4 at.% [see Fig. 6(c)] did not change
of the 167 Er isotope with nuclear spin I = 7/2 is observed. when the spectrometer’s resolution was lowered from 0.005 to
The inset of Fig. 5(a) demonstrates in more detail the HFS in 0.02 cm−1 . The observed HFS provides a tool for checking the
the EPR spectrum at the frequency 9.4 GHz and the scheme quality of the crystal-field parameters obtained in the crystal-
of Fig. 5(b) illustrates the origin of this HFS. Measurements field calculations based on our high-resolution spectroscopy
at higher frequencies show that the widths of the erbium lines data and described in the next section.
do not change.
In optical spectra, only partly resolved HFS is observed, IV. CALCULATIONS OF ENERGY LEVELS, SPECTRA,
due to relatively large inhomogeneous line broadening. In AND HYPERFINE STRUCTURE
Fig. 6(a), where the 6531.6 cm −1 absorption line of Er 3+ in
YPO4 :Er (0.005 at.%) registered at a low temperature and a The Hamiltonian of the Er 3+ ion operating in the basis of
zero external field by a tunable single-frequency laser with the 364 states of the ground 4 f 11 electronic configuration contains
spectral resolution ∼5 × 10−5 cm−1 is presented, the finest the free-ion standard Hamiltonian HFI and the crystal-field
spectral details have the width ∼0.005 cm−1 . These details Hamiltonian HCF :
smear out with growing erbium concentration in Er : YPO4 ,
H = HFI + HCF . (1)
due to an increasing inhomogeneous line broadening. In
HFI is constructed from the effective operators following
conventional notations of the spectroscopic theory of lan-
thanides [37]:

HFI = H0 + F k fk + ζ ASO + αL(L + 1)
k=0,2,4,6

+ βG(G2 ) + γ G(R7 ) + T i ti
i=2,3,4,6,7,8
 
+ M jmj + Ps ps . (2)
j=0,2,4 s=2,4,6

Here, H0 is spherically symmetric one-electron part of the

Hamiltonian, F k and ζ are electrostatic and spin-orbit inte-
FIG. 6. The 6531.6 cm−1 absorption line of Er 3+ in Er : YPO4
grals, fk and ASO represent the angular parts of the electro-
registered at T = 5 K, B = 0 (a),(b) by a tunable single-frequency static and spin-orbit interaction, respectively. The parameters
laser, Er concentration 0.005 at.% and (c),(d) by a high-resolution associated with the two-body electrostatic correlation terms
Fourier spectrometer, thick solid, dash-dotted, and thin solid spectral are denoted by α, β, and γ ; L is the total orbital angular
traces represent the data for 0.1, 0.2, and 0.4 at.% of erbium, momentum, G(G2 ) and G(R7 ) are Casimir’s operators [38].
respectively. (a),(c) σ and (b),(d) π polarizations. Bars in (a) and Three-body electrostatic interaction terms are parametrized
(b) represent the calculated hyperfine structure in the spectra of by T i (i = 2, 3, 4, 6, 7, 8) [39]. The last two terms in Eq. (2)
167
Er 3+ ; the dashed lines in (c) and (d) show the results of modeling represent magnetically correlated corrections [40]: they in-
(the linewidth of 7 × 10–3 cm−1 was attributed to each hyperfine clude spin-spin and spin-other-orbit relativistic corrections
component of the line, to account for the inhomogeneous broadening, parametrized by M j ( j = 0, 2, 4), and electrostatically corre-
see the text). lated spin-orbit perturbation parametrized by Ps (s = 2, 4, 6).

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TABLE V. Parameters of the free-ion Hamiltonian used in the

present work (standard notations, see Ref. [37]), cm−1 .

F2 F4 F6 ζ α β γ T2 T3 T4
96589 67938 54360 2366.3 17.60 −577 1813 465 52.5 92
T6 T7 T8 M0 M2 M4 P2 P4 P6
−234 275 308 4.01 2.86 1.95 657 434 0

The crystal-field interaction is expressed via Stevens oper-

ators Okp [41]:

HCF = Bkp Okp . (3) FIG. 7. The calculated (B = 0) hyperfine structure schemes of
pk the ground Kramers doublet (left) and of the lowest-energy Kramers
doublet in the 4 I13/2 multiplet (right) of 167 Er in YPO4 , involved in the
In the case of the D2d local symmetry, only the parameters formation of HFS of the spectral line 6531.6 cm−1 . Doublet (singlet)
B20 , B40 , B44 , B60 , and B64 have nonzero values. hyperfine levels are represented by solid (dotted) lines.
Matrices of the effective operators contained in Eqs. (2)
and (3) in the basis of 364 states of 4 f 11 electronic configura- The lower part of the basis of 364 electronic eigenstates
tion have been numerically calculated in our previous studies found by numerical diagonalization of the Hamiltonian (1)
[42,43]. The 364 electronic eigenstates have been found by corresponding to the energy band 0–16 000 cm−1 was used
numerical diagonalization of the matrix of the Hamiltonian to form a truncated space of 62 states (the lowest 5 multi-
(1). The parameters of the free-ion Hamiltonian have been plets). The total Hamiltonian Htot = HFI + HCF + HHFM was
initially set to equal those of Er : LiYF4 crystal [43], while the projected onto the basis of 62 × 8 = 496 electron-nuclear
CF parameters Bkp have been chosen according to Ref. [24]. states and then diagonalized numerically. In such a way, ener-
After that, all 24 parameters of the model Hamiltonian have gies and wave functions of hyperfine sublevels were found.
been varied to achieve the best agreement with the whole set The calculated hyperfine structure of the Kramers doublets
of the experimental data, i.e., the transition energies and g involved in the 6531.6 cm −1 transition is shown in Fig. 7.
factors of the Kramers states in Er : YPO4 crystal. The final Each Kramers doublet breaks into seven doublets and two
set of parameters thus obtained is presented in Tables V and singlets (16 hyperfine states in total). A superposition of wave
VI. The calculated CF energies are given in Tables I and III functions with different values of m (where m is the nuclear
and the calculated g factors are in Table IV, to be compared spin projection, −7/2  m  7/2) corresponds to each hy-
with the experimental data. perfine level (which is a peculiarity of Kramers ions, see,
In order to reproduce the hyperfine structure observed for e.g., Ref. [45]). Because of that, plenty of transitions obeying
the 4 I15/2 → 4 I13/2 transition (see Fig. 6), the magnetic part of the m = 0 selection rule take place. Table VII lists all the
the hyperfine interaction of 167 Er isotope (22.9%) with nuclear allowed transitions.
spin I = 7/2 was taken into account [44]: The transition probabilities were determined by the electric
   dipole and magnetic dipole line strengths, which, for a given
1  hyperfine transition |i → | f , equal
HHFM = μB γN h̄ 3 2Il+O20 (3sz Iz − sI)
r 4f Si(ED) Si(MD)
f ,q = |i|dq | f | , f ,q
= |i|μq | f | ,
2 2

(5)
+ 3O22 (sx Ix − sy Iy )+3O2−2 (sx Iy + sy Ix ) where q and q
denote the polarization of the electric and mag-

+ 6O21 (sx Iz + sz Ix ) + 6O2−1 (sz Iy + sy Iz ) . (4) netic field, respectively, μ = −μB (L + 2S) is the magnetic
moment and d is the effective electric moment of the Er 3+ ion,
The sums above are taken over 4 f electrons, l and s are which contains odd CF operators that admix wave functions
the one-electron orbital and spin moments, respectively, and of different parity to the 4 f wave functions. The calculation
γN /2π = −1.23 MHz/T is the gyromagnetic ratio of the of the magnetic dipole line strengths is straightforward. In
167
Er nucleus. The expectation value of 1/r 3 operator of the our calculations of the electric dipole line strengths, we took
4 f electrons, 1/r 3 4 f , equals 11.07 at. units [44]. into account the 4 f ↔ 5d configuration mixing and followed
TABLE VI. The crystal-field parameters Bkp (cm−1 ) for Er 3+ in Er : YPO4 .

p K Bkp
Present work Ref. [24] Ref. [25]
2 0 112.9 141 185
4 0 10.3 18.1 18
4 4 776 837 800
6 0 −43.0 −40.4 −40.4
6 4 56.1 89 88

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M. N. POPOVA et al. PHYSICAL REVIEW B 99, 235151 (2019)

TABLE VII. Energy levels and allowed i → f transitions between the hyperfine sublevels of the ground 4 I15/2 (71 ) and excited 4 I13/2 (61 )
Kramers states in π and σ polarizations. Values of i are determined by the first column, while the allowed f values are presented in the last
three columns. Energies of the hyperfine sublevels shown in Fig. 7 are given with respect to the mean energy of the Kramers doublet. The
energies of the doublet states are in bold.

Allowed transitions to
Energy of i-th Energy of f -th the excited state f
HF level No. state of 4 I15/2 (71 ), GHz state of 4 I13/2 (61 ), GHz πED πMD σED
1 −1.37 −1.86 4, 6 3, 5, 7 3, 5, 7
2 −1.23 −1.81 3, 7 2, 4, 6, 8 2, 4, 6, 8
3 −1.14 −1.64 2, 8 1, 3, 7, 9 1, 3, 7, 9
4 −1.11 −1.33 9 2, 8 2, 8
5 0.93 −0.70 1 2, 8 2, 8
6 0.96 1.35 2, 8 1, 3, 7, 9 1, 3, 7, 9
7 1.06 1.65 3, 7 2, 4, 6, 8 2, 4, 6, 8
8 1.20 1.81 4, 6 3, 5, 7 3, 5, 7
9 1.37 1.86 5 4, 6 4, 6

the line of Ref. [43]. In Figs. 6(a) and 6(b), the results of orthophosphate single crystals doped with erbium. The
calculations are represented by the bars located at calculated Er : YPO4 samples with Er concentrations 0.005, 0.01, 0.1,
frequencies and of the highs proportional to the calculated 0.2, 0.4, and 0.7 at.% were studied. Zeeman splittings in the
line strengths. In Figs. 6(c) and 6(d), the linewidth (full width 4
I15/2 → 4 I9/2 and 4 I15/2 → 4 I13/2 absorption manifolds
at half height) of 7 × 10−3 cm−1 (200 MHz) was attributed in magnetic fields B||c and B⊥c, as well as X-band
to each hyperfine component of the line, to account for and high-frequency (36–76 GHz) EPR spectra were also
the inhomogeneous broadening. There is a good agreement investigated.
between the experimental and calculated hyperfine patterns Energies and symmetries of 40 crystal-field Kramers dou-
in the optical spectra, which testifies a good quality of the blets and g factors for the levels 6531.6, 6542, 6600, 6617,
crystal-field parameters obtained in our study. 12378, and 12432.7 cm −1 were determined. These data were
In order to account for the hyperfine structure in the EPR taken as a base for the CF calculations. We have observed the
spectra corresponding to microwave transitions within the electron-nuclear hyperfine structure in the EPR and optical
lowest Kramers doublet 4 I15/2 (71 ) (Fig. 5), the hyperfine spectra of Er : YPO4 and were able to successfully model it
interaction operator (4) and Zeeman interaction with the ex- using the wave functions obtained from the CF calculations.
ternal magnetic field B0 , HZ = −μB0 , were projected onto The results of the present study pave the way for potential
the lowest two eigenstates of the Hamiltonian (1): applications in quantum electronics and quantum information
processing at telecom wavelength.
H
= HZ + HHFM = g μB B0z Sz
+ g⊥ μB (B0x S
x + B0y S
y )
+ A Sz
Iz + A⊥ (S
x Ix + S
y Iy ), (6)

where S
= 1/2 is the effective spin, g = 6.78 and g⊥ =
4.71 are the calculated g factors, A = 730 MHz and A⊥ =
509 MHz are the hyperfine parameters, all corresponding
to the lowest Kramers doublet. These calculated values
are in reasonable agreement with the EPR data published
previously [35].
Calculated positions of the hyperfine components in the
EPR spectra of Er : YPO4 (shown in the inset of Fig. 5) prac-
tically coincide with the experimental ones. Based on good re-
sults of modeling the hyperfine patterns in the high-resolution
optical and EPR spectra of Er 3+ in YPO4 , we suggest that
a reliable set of energies of hyperfine levels (necessary for
applications in quantum technologies) can be calculated using
the crystal field and other parameters obtained in this study.

V. SUMMARY
We have performed high-resolution (up to ∼5 × FIG. 8. 4 I13/2 → 4 I15/2 luminescence excitation and decay of
10 cm−1 ) broadband (5 000–21 000 cm−1 ) temperature-
−5
Er in YPO4 :Er (0.1 at.%) at T = 5 K. Inset: Luminescence decay
3+

dependent (5–300 K) polarized transmission and infrared in a logarithmic scale and exponential approximation (red line) with
(0.9–1.6 μm) luminescence measurements of yttrium lifetime 5.1 ± 0.2 ms.

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CRYSTAL FIELD AND HYPERFINE STRUCTURE OF … PHYSICAL REVIEW B 99, 235151 (2019)

ACKNOWLEDGMENTS APPENDIX: LIFETIME OF THE 4 I13/2 STATE

The authors are grateful to B. Malkin for valuable discus- We have measured the decay times of the 4 I13/2 → 4 I15/2
sions. This work was supported by the Russian Foundation for luminescence of Er 3+ in YPO4 at low temperature (5 K) for
Basic Research (Grant No. 18-52-52001) and by the Ministry the sample YPO4 :Er (0.1 at.%). Figure 8 shows the decay
of Science and Technology of Taiwan (Grant No. 107-2923- curve. A single exponent with τ = 5.1 ± 0.2 ms is observed
M-110-001-MY3). (see the inset of Fig. 8).

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