Core-level x-ray photoemission and Raman spectroscopy studies on electronic structures in

Mott-Hubbard type nickelate oxide NdNiO2

Ying Fu,1, 2, ∗ Le Wang,1, ∗ Hu Cheng,1 Shenghai Pei,1 Xuefeng Zhou,1 Jian Chen,1
Shaoheng Wang,1 Ran Zhao,3 Wenrui Jiang,1 Cai Liu,1 Mingyuan Huang,1 XinWei
Wang,3 Yusheng Zhao,1 Dapeng Yu,1 Fei Ye,1 Shanmin Wang,1, † and Jia-Wei Mei1, ‡
1
Shenzhen Institute for Quantum Science and Engineering, and Department of Physics,
Southern University of Science and Technology, Shenzhen 518055, China
2
Institute of Applied Physics and Materials Engineering, University of Macau, Macau 999078, China
3
School of Advanced Materials, Shenzhen Graduate School Peking University, Shenzhen 518055, China
arXiv:1911.03177v2 [cond-mat.supr-con] 22 Mar 2020

(Dated: March 24, 2020)

We perform core-level X-ray photoemission spectroscopy (XPS) and electronic Raman scattering studies of
electronic structures and spin fluctuations in the bulk samples of the nickelate oxide NdNiO2 . According to Nd
3d and O 1s XPS spectra, we conclude that NdNiO2 has a large transfer energy. From the analysis of the main
line of the Ni 2p3/2 XPS, we confirm the NiO2 planes in NdNiO2 are of Mott-Hubbard type in the Zaanen-
Sawatzky-Allen scheme. The two-magnon peak in the Raman scattering provides direct evidence for the strong
spin-fluctuation in NdNiO2 . The peak position determines the antiferromagnetic exchange J = 25 meV. Our
experimental results agree well with our previous theoretical results.

Introduction – Nickel has the formal valences Ni3+ , Ni2+
and Ni+ with electronic configurations of of 3d7 , 3d8 and
3d9 , respectively, in the transition-metal oxides. The nickelate
compounds exhibit lots of strongly correlated electronic prop-
erties, such as the metal-insulator transitions, unusual mag-
netic order, charge order and even superconductivity [1–17].
The recent discovery of the superconductivity in the thin film
Nd0.8 Sr0.2 NiO2 [16] has the similar crystal and 3d9 electronic
structures to the cuprate superconductors [18], and motivates
the experimental [17] and lots of theoretical works [19–35] to
explore its electronic properties. The recent superconductivity
dome spanning the doping concentration 0.125< x <0.25 in
thin-film Nd1−x Srx NiO2 infers the remarkable similarity to
cuprate superconductors [36].
Reduced form of perovskite nickelate LaNiO3 and NdNiO3
leads to the infinite layered phase LaNiO2 and NdNiO2 [6–
8, 11, 12, 14, 15]. Several experimental studies have been car-
ried out on the parent superconducting nickelate oxides. Mag-
netization measurements and powder neutron diffraction were
performed on LaNiO2 and NdNiO2 to study the magnetic
properties [7, 8]. Electric transport measurements have been
performed on the thin film samples LaNiO2 and NdNiO2 , and
the resistivity exhibits the insulator or semiconductor behavior
depending on the samples [11, 12, 14–16]. The Ni-K edge X-
ray absorption spectroscopy (XAS) was implemented to char-
acterize the LaNiO2 samples [6, 11]. Recently, with the help
of density functional theory within LDA+U scheme, Hepting
et. al. [17] has used XAS and X-ray emission spectroscopy
(XES) to unveil a large charge-transfer energy, and catego-
rized LaNiO2 and NdNiO2 to the Mott-Hubbard type accord-
ing to the Zaanen-Sawatzky-Allen (ZSA) scheme [1]. The
Mott-Hubbard scenario is still under debate, and the charge-
transfer type is also proposed for NdNiO2 [35].
In this paper, the main purpose to study electronic struc-
tures in NdNiO2 is twofold. Firstly, we perform the core-
level x-ray photoemission spectroscopy (XPS) to examine the
existence of the Zhang-Rice singlet [37] to address the ZSA
classification issue for NdNiO2 . Ni+ has higher chemical po-
tential and hence a larger transfer energy in NdNiO2 as ob-
served in XAS and XES [17]. We implement the XPS mea-
surement to further disprove the large-∆ charge-transfer (a
charge-transfer insulator with a large transfer energy ∆) sce-
nario for NdNiO2 . The main line of the transition-metal 2p
XPS spectrum has the doubly peaked structure in the cuprate
parent compound [38, 39] and NiO [40] due to the non-local
screening effects [40–42], related to the Zhang-Rice singlet
in charge-transfer insulators [37]. In the XPS measurements,
from Nd 3d and O 1s XPS, we find NdNiO2 has a larger trans-
fer energy ∆, comparing to a small/negative charge-transfer
insulator NdNiO3 . The non-local screening doubly peaked
structure of the main line of Ni 2p3/2 is significantly sup-
pressed in NdNiO2 , confirming the Mott-Hubbard scenario
for NdNiO2 [17].
Secondly, as the NiO2 planes in NdNiO2 is in the Mott-
Hubbard regime in the ZSA scheme, we are concerned with
the spin dynamics in the system. The strong antiferromag-
netic spin fluctuation is generally accepted as a key ingredient
for the unconventional superconductivity in the cuprate ox-
ides, due to the proximity to a Mott insulator [43, 44]. Raman
spectroscopy probes spin fluctuations in the transition-metal
compounds, even without a long-range magnetic order [45].
The exchange interaction J for cuprates is very large, and
J was determined from the two-magnon peak to be of order
125 meV [45–56]. The absence of long-range magnetic order
in LaNiO2 and NdNiO2 in Refs. [7] may be due to poor sam-
ple qualities, or due to the “self-doping” effects of the Nd 5d
electron pockets [10, 17, 25]. We perform Raman measure-
ments to explore spin fluctuations, and observe a broad two-
magnon peak in NdNiO2 . The antiferromagnetic exchange is
determined as J = 25 meV in NdNiO2 , close to our previous
theoretical estimation [25].
Experimental setup. – We carried out the XPS investiga-
 2

( a ) N d N iO 3 ter calcining the precursor powder capsuled in h-BN at 1073

K under high pressure of 2 GPa, the crystals of NdNiO3 with

0 2 0
high quality were successfully obtained, as shown in Fig. 1.
In te n s ity ( a .u .)

The reduction of NdNiO3 was performed at low temperature

using CaH2 as the reducing agent, as reported in refs [11, 16],

2 2 0
1 1 0 and finally, the P 4/mmm phase of NdNiO2 was obtained.

1 3 2

2 4 0
We observe the broadening of the peak width in the XRD

0 4 0
0 2 2
1 1 1
pattern for NdNiO2 , especially in the peak indexed by hhkli
with nonzero value for l. The anisotropic broadening of the
Bragg peaks was also observed in both thin films and poly-
crystals [7, 8, 11, 12, 16, 58], and could be ascribed to the
( b ) N d N iO 2 anisotropic crystal size or stacking disorder. NdNiO2 has in-
tensive peaks along hh00i direction in XRD pattern as shown
In te n s ity ( a .u .)

in Fig. 1 (b), probably due to the preferred a-axis of crystal

grains. The orientation preference was reported for the thin-
film LaNiO2 where the preferred orientation changes from c-
2 0 0
1 0 0

axis to a-axis for the over-time reduction [12, 13].

We performed the Rietveld profile refinement for NdNiO3
0 0 1
1 1 0

and NdNiO2 using the Fullprof suite of programs [59]. The

1 0 1

0 0 2

3 0 0
2 1 1

1 1 2
2 0 1

1 0 2

NdNiO3 has the space group of P bnm with lattice parameters

a = 5.38500 Å, b = 5.38400 Å, and c = 7.61314 Å (Rwp =
8.83% and RB = 13.25%), consistent with the previous re-
1 0 2 0 3 0 4 0 5 0 6 0 7 0 8 0 9 0 port [60]. The refinement results for NdNiO2 is a = b =
2 q (d e g ) 3.93110 Å and c = 3.30200 Å ( with Rwp = 11.6% and
RB = 7.35% ), which is in agreement with previous results
FIG. 1. Refined XRD patterns collected at ambient conditions using which used NaH as reduction agent [8]. It is worth noting
a Cu Kα radiation. (a) NdNiO3 . (b) NdNiO2 . The observed and that the metal nickel phase usually appears in NdNiO2 after
calculated patterns are shown in black and red, respectively. The po- reduction, as reported in refs [7, 8, 11, 58]. Although the
sitions of allowed Bragg reflections are denoted by green tick marks.
metal nickel phase is almost invisible in our PXRD result,
The bottom profiles are the difference between the observed and cal-
culated results. Insets of each panel are crystal pictures and the poly- we observed the metal nickel impurities embedded in surface-
hedral view of the corresponding crystal structures. polished NdNiO2 crystal by SEM, as shown in inset of Fig. 5.
Electronic structures from XPS. – The core-level x-ray
spectroscopy is a powerful tool to study electronic properties
of transition-metal oxides [62, 63]. It helps to determine the
tions on Thermo Fisher ESCALAB 250Xi using monochro-
mated Al Kα radiation at room temperature, and the elec-
tron flood gun was turned on to eliminate electric charging
∆E b ∼ 1 . 1 e V N d N iO
effect in our insulating samples. The binding energy in XPS N d N iO
3
N d 2O 3
2
was calibrated by 1s spectra of carbon. The Shirley back- N d N iO 3
ground of the XPS spectra has been subtracted in this work.
N d N iO
In te n s ity ( a .u .)

2
The energy dispersive X-ray (EDX) and scanning electron mi-
croscopy (SEM) studies were performed on Phenom ProX d 5 /2
equipped with Backscatter detector at an operating voltage
of 15 kV. X-ray diffraction (XRD) measurements were con-
9 8 5 9 8 0 9 7 5 9 7 0
ducted on Rigaku Smartlab 9 KW using Cu Kα radiation at
room temperature. The Raman spectra were measured in the d 3 /2
quasi-back-scattering geometry on our home-built system us-
ing a HORIBA iHR550 spectrometer and the 632.8 nm exci-
tation line of a He-Ne laser. The power of the laser is about
400 µW, and we set 1200 grooves/mm grating and 30 min in-
tegral time. The samples were placed in a He-flow cryostat
which evacuated to 2.0 × 10−6 Torr.
Single crystal synthesis. – The NdNiO3 polycrystals were 1 0 1 0 1 0 0 0 9 9 0 9 8 0 9 7 0
synthesized by a combination precursor method with high B in d in g E n e r g y ( e V )
pressure technique. The precursor was prepared by sintering
the sol-gel with stoichiometric ratio of Ni and Nd [57]. Af- FIG. 2. Nd 3d core-level XPS spectra of NiO, NdNiO3 and NdNiO2 .

FIG. 3. O 1s core-level XPS spectra of NiO (a), NdNiO3 (b) and
NdNiO2 (c) powder samples.
on-site Coulomb interaction and the charge-transfer energy,
and classify materials as charge-transfer or Mott-Hubbard in-
sulators in the Zaanen-Sawatzky-Allen scheme [1, 64–67].
Figure 2 is the Nd 3d core-level XPS spectra for Nd2 O3 ,
NdNiO3 and NdNiO2 . The similar overall pattern indicates
the trivalent Nd3+ with the 4f 3 ground state in the three com-
pounds. There is a blue shift of the binding energy around
∆Eb ' 1.1 eV for NdNiO2 , comparing to NdNiO3 as shown
in the inset. Thus the formal chemical valence is Ni3+ and
Ni1+ in NdNiO3 and NdNiO2 , respectively. In the Nd3+ 3d
XPS, the spectral structure is mainly determined by the ef-
fect of the covalency hybridization, and the two peaks of the
3d XPS correspond to the bonding and antibonding states be-
tween the 3d9 4f 3 and 3d9 4f 4 L configurations ((L is the hole
in the ligand) in the final states [62]. The ground state of
Nd2 O3 is in the almost pure 4f 3 configuration, and hence the
main peak at around 981-983 eV in the Nd 3d5/2 XPS spectra
is the unscreened 3d9 4f 3 final state. The screened 3d9 4f 4 L
final state has a lower binding energy around 977 eV.
Figure 3 compares the O 1s XPS spectra in NiO, NdNiO3
and NdNiO2 . The O 1s XPS has often used in the experi-
ments for the transition-metal oxides, however, the nature of
the 531 eV O 1s spectral peak in NiO is unclear [68, 69],
and has been proposed to be due to defective sites within the
oxide crystal [70, 71], adsorbed oxygen [72], or hydroxide
species [73], and also attributed to an intrinsic feature [68, 74].
We can’t exclude the contaminant origin for the 530.9 eV fea-
ture, however, we have measure the O 1s XPS spectra on both
different samples and different XPS instruments and obtain
the consistent similar results, which is hardly attributed to an
extrinsic feature. In O 1s XPS spectra, NiO and NdNiO2 have
the best-screened states at around 529 eV. In NdNiO3 , an extra
peak appears at the lowest binding energy 528.3 eV, indicat-
ing the concentration of the oxygen holes in the ground state,
3
due to a negative charge transfer energy [75–78].
As depicted in the inset of Fig. 2, NdNiO2 has a higher
binding energy than NdNiO3 in the Nd 3d XPS by around
∆Eb ' 1.1 eV. The Nd3+ binding energy blue shift ∆Eb in-
dicates the increasing of the Fermi energy in NdNiO2 . Since
Nd3+ has a weaker hybridization than Ni+ with the oxygen,
the Fermi energy increasing is mainly due to the increas-
ing chemical potential of Ni+ in NdNiO2 , assuming the un-
changed chemical potential of oxygen. Hence NdNiO2 has a
larger charge-transfer energy ∆. Taking account for the co-
valency of the transition-metal ions and ligands, the effec-
tive charge transfer energy is ∆0 = ∆ − (W + w)/2 [79],
where W and w are the bandwidths for the transition-metal
3d-band and oxygen 2p-band, respectively. NdNiO2 has the
nearly two-dimensional transition-metal 3d-band and oxygen
2p-band which are narrower than the three-dimensional ones
in NdNiO3 ; then it has has a larger effective charge trans-
fer energy ∆0 . From the comparison between NdNiO2 and
NdNiO3 , the former has a large charge-transfer energy than
the latter, and is not a negative/small charge-transfer insulator.
NdNiO2 has the quite similar pattern of O 1s XPS to NiO,
but the covalence peak is significantly suppressed as shown in
Fig. 3. Since NiO is a three-dimensional charge-transfer in-
sulator, NdNiO2 could have a larger effective charge-transfer
energy ∆0 than NiO, and is likely to be a Mott-Hubbard type
as suggested in Ref. [16, 17, 21, 25], which need further con-
firmation in the Ni 2p XPS as demonstrated below.
Next, we examine the Ni 2p XPS spectra to confirm
whether NdNiO2 is a charge-transfer or Mott-Hubbard type.
Figure 4 displays Ni 2p XPS spectra of NiO, NdNiO3 and
NdNiO2 . The Ni 2p spectrum is composed of 2p3/2 and 2p1/2
components due to the large spin-orbit coupling in the Ni 2p
core level. The main line region of the 2p3/2 spectra around
852-859 eV corresponds to the screened final states, and can
FIG. 4. Ni 2p1/2 and 2p3/2 core-level XPS spectra of NiO (a),
NdNiO3 (b) and NdNiO2 (c) powder samples.
 4

be fitted by two peaks. The removal of the 2p core electron 8 0 0 0

1 2 0 K N d N iO
leads to the creation of a strong local potential on the nickel 3 0 0 K 3
4 0 0
site, and an electron is transferred from the environment to 6 0 0 0

'' ( )
the Ni site. The different types, i.e., small/negative charge-
0

w
transfer, charge-transfer and Mott-Hubbard types according 4 0 0 0
to the ZSA scheme, of the transition-metal compounds have

c
-4 0 0
different non-local screening effects in the main line of the 2p
2 0 0 0
transition-metal XPS spectra [40, 41].
The perovskite NdNiO3 has a negative effective charge- -8 0 0
0
transfer energy, giving rise to “self-doped” holes on the lig- 1 0 0 0
ands [79]. It mainly has a local Ni 3d8 configuration, a pre- 1 2 0 K N d N iO 2
dominant O 2p character across the Fermi level and a con- 8 0 0 3 0 0 K

'' ( )
sequent ground state of mainly Ni 3d8 L in the metallic state

w
at the room temperature. The two peaks in the main lines 6 0 0

c
correspond to the 2p5 3d8 L and 2p5 3d9 L2 final states [77].
4 0 0
NdNiO2 has a larger transfer energy ∆ than NdNiO3 as
demonstrated above according to Fig. 2 and Fig. 3, and hence
2 0 0
displays a different shape of the main line of Ni 2p3/2 XPS.
Again, we confirm NdNiO2 is not a negative charge-transfer 0
insulator. 1 0 0 2 0 0 3 0 0 4 0 0 5 0 0 6 0 0 7 0 0

In the charge-transfer insulator NiO, the main line have the R a m a n s h i f t (c m - 1 )

double-peak structure. The higher binding energy peak corre-
sponds to the 2p5 3d9 L final state, where an electron is trans-
ferred from the neighboring oxygen atoms (local screening)
leaving a hole in the oxygen ligand orbital L. The peak at
the lowest energy corresponds to the final state where an elec-
tron is transferred from oxygen in the neighboring NiO6 oc-
tahedron, thereby creating a Zhang-Rice singlet in the farway
octahedron (non-local screening) [37, 40, 41].
The non-local screening peak is a signature for the presence
of the Zhang-Rice singlet in the charge-transfer insulators, as
observed in the cuprate oxides and NiO [38–41]. Compared
with NiO, the non-local screening peak in NdNiO2 is signif-
icantly suppressed. Hence the NiO2 layer in NdNiO2 is not
a large-∆ charge-transfer type, but a Mott-Hubbard one. The
initial ground state and the final screened state are mainly 3d9
and 3d10 L, respectively.
Two-magnon mode in Raman spectroscopy. – Figure 5 is
the Raman spectra of NdNiO3 and NdNiO2 at 300 K and
120 K measured on the sub-millimeter sizable single crystals.
The Raman susceptibility χ00 (ω) deduced from the Raman in-
tensity I(ω) according to the fluctuation-dissipation theorem,
I(ω) = (1 + nB (ω))χ00 (ω) where nB (ω) is the boson factor.
The Raman spectra for NdNiO3 agrees well with the previ-
ous measurements on the thin-film single crystal [80], imply-
ing the high-quality for our bulk NdNiO3 samples. There are
more phonon peaks at low temperatures due to the structure
distortion during the metal-insulator transition around 200 K
in NdNiO3 . The dramatically increasing of the phonon inten-
sity is due to the metal-insulator transition in NdNiO3 .
The surface contaminant due to the formation of fluorite
NdNiOx Hy reported in the previous thin-film NdNiO2 [81,
82] is nearly invisible in our Nd 3d XPS. To remove the pos-
sible contaminant, we polish the NdNiO2 single crystal as
shown in the inset of Fig. 5. During the synthesis process,
some pure nickel metal are embedded in NdNiO2 crystal due
FIG. 5. Raman susceptibility in NdNiO3 (upper plane) and NdNiO2
(lower plane) at 300 K and 120 K, respectively. The inset is the SEM
picture of a surface-polished single crystal. The metal nickel has
been circled by red lines in the inset.
to the perotectic phenomenon and forms the dark gray spots
(marked by red circles) in the polished surface of NdNiO2 .
The large light gray area in the SEM image is NdNiO2 as
identified by EDX. We perform the Raman scattering mea-
surements on NdNiO2 in the light gray area.
The ideal stoichiometric NdNiO2 has the space group
P 4/mmm and all the ions can be taken as the inversion cen-
ter of the lattice. Therefore, there is no Raman active phonon
mode in the Raman scattering. There is no sharp phonon
modes in the spectra. A broad peak appears at 122 cm−1 ,
independent of the temperature and its origin is unclear. We
suspect it comes from the defect due to the off-stoichiometry
of NdNiO2 .
We attribute the mode at around 550 cm−1 in the Ra-
man susceptibility spectra of NdNiO2 in Fig. 5 to the two-
magnon peak in the two-dimensional Heisenberg antiferro-
magnet. The broadening of the two-magnon response with
doping and temperature has been studied theoretically in the
cuprate oxides [46–56]. The two-magnon identifies the strong
spin fluctuations in the cuprate even when the long range an-
tiferromagnetic order disappears at high temperatures or upon
doping [45]. In a 2D Heisenberg antiferromagnet, the light in
the Raman process flips two nearby spins on the nearest neigh-
boring bond, leaving behind a locally disturbed antiferromag-
net with 6 broken exchange bonds in the final state. Therefore
the two-magnon has the energy scale at roughly 2.7J [45].
We equal 2.7J to 550 cm−1 , and obtain the antiferromagnetic
exchange strength J = 25 meV.

Discussions and Conclusions. – The discovery of the
superconductivity in the thin film Nd0.8 Sr0.2 NiO2 [16] has
caught lots of attention, however, the recent report of the bulk
Nd1−x Srx NiO2 (x = 0.2, 0.4) reveals an insulating behav-
ior without the presence of the superconductivity [58]. The
reason of the discrepancy is unclear. We suspect that the Sr
substitution of Nd destroys the flat NiO2 plane in the bulk
Nd1−x Srx NiO2 , probably resulting in the insulating behavior
due to the disorder. In the thin film Nd1−x Srx NiO2 , due to
the strain effect of substrate, the NiO2 plane remains flat after
doping.
In our previous theoretical work, we derive the effective
Hamiltonian for nickelate oxides Nd1−x Srx NiO2 with the flat
NiO2 planes [25]. From the the Heyd-Scuseria-Ernzerhof
hybrid density functional and the exact diagonalization of
the three-band Hubbard model for the Ni5 O16 cluster, we
find that the undoped NiO2 plane is a Mott-Hubbard insu-
lator and the doped holes primarily locate on Ni sites. The
Mott-Hubbard scenario is also stressed in Ref. [21]. The
physics of the undoped NiO2 plane is described by the two-
dimensional P Heisenberg antiferromagnet on the square lat-
tice H = J hiji Si · Sj with the exchange strength J =
29 meV [25].
In summary, we perform core-level X-ray photoemission
spectroscopy (XPS) and Raman spectroscopy studies of elec-
tronic structures and spin fluctuations in the bulk NdNiO2 . We
find that the NiO2 planes in NdNiO2 are of Mott-Hubbard
type in the ZSA scheme, consistent with Hepting’s electronic
structure studies on the thin-film NdNiO2 [17]. Two-magnon
peak in the Raman scattering provides direct evidence for the
strong spin-fluctuation in NdNiO2 . The peak position de-
termines the antiferromagnetic exchange J = 25 meV. The
present experimental investigation agrees well with our pre-
vious theoretical description of the electronic structures of
NdNiO2 .
In the last, we make a remark on the three-dimensional elec-
tron pockets of Nd3+ 5d character in NdNiO2 as demonstrated
in Ref. [10, 17]. The presence of 5d electron pocket changes
the hole count in the NiO2 planes, resulting in spin-S = 0
Ni2+ states in the NiO2 planes even without chemical dop-
ing [25]. A weakly-interacting three-dimensional 5d metallic
state hybridizes with the Ni+ local moments in the NiO2 lay-
ers, explaining the resonant inelastic x-ray scattering spectra
in LaNiO2 and NdNiO2 [17]. In our Ni 2p3/2 XPS spectra,
the main line for NdNiO2 has some weight around 853 eV
(Fig. 4). We can’t rule out the minority nickel metal origin for
this weight. However, XRD has the similar penetration depth
as XPS and detect a tiny nickel peak in our samples. So the
853 eV weight in Fig. 4 for NdNiO2 is likely to be intrinsic
and related to the S = 0 Ni2+ states in the NiO2 planes.
Acknowledgments – J.W.M thanks A. Ng and W. Q. Chen
for useful discussions. J.W.M was partially supported by
the program for Guangdong Introducing Innovative and En-
trepreneurial Teams (No. 2017ZT07C062). This work was
also supported by National Science Foundation of China
(No. 11774143).
5
∗
These two authors contributed equally.
†
wangsm@sustech.edu.cn
‡
meijw@sustech.edu.cn
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