Stabilization of ferroelectricity in doped HfO2 thin film

The initial discovery of ferroelectricity in Si-doped HfO2 thin films

was made in 2011 [1]. Since then, it has been observed that thin films
of HfO2 containing different cationic dopants (including Si, Y, Al,
Gd, Sr, and Zr) can display ferroelectric behaviour when deposited at
specific concentrations and subjected to annealing under certain
conditions. HfO2-based ferroelectric thin films have gained attention
as potential contenders for the next generation non-volatile memory
devices due to their high speed, high endurance, and long retention
characteristics. Currently, the ferroelectric behaviour observed in
HfO2-based films is thought to arise from the non-centrosymmetric,
metastable orthorhombic phase with the space group Pca21[2]. Due to
lack of thermodynamic stability of the orthorhombic phase, HfO2 thin
films grown with chemical solution deposition (CSD) technique tends
to be advantageous compared to other deposition methods [3]. CSD
allows formation of small grains which can enhance orthorhombic
fraction in the film. Moreover, to observe ferroelectricity in HfO2
thin-films, field cycling is generally carried out to increase the o-
phase fraction, which is known as wake-up effect. This article at first
will show an example where secondary ion mass spectrometry
(SIMS) was used to understand elemental composition of a
ferroelectric (FE) La:HfO2 film and secondly, it will discuss about the
visualization of wake-up phenomenon in hafnia thin-films using
scanning transmission electron microscope (STEM).

CSD processed layer-by-layer FE La:HfO2 thin-films

T. Shenk et al. has demonstrated that layer-by-layer (L/L) CSD

growth technique can significantly enhance ferroelectricity in HfO2
thin-films [4]. In L/L route, solution is diluted, and every spin-coating
is followed by crystallization step (11 spin-coatings + crystallization
in this case), unlike the conventional CSD method where
crystallization is carried out at the very end of the growth process.
Purpose of the method is to have heterogenous nucleation of grain
growth that can lead to higher density as well as preferential
orientation, therefore enhancement of ferroelectric property.

a) b)

Figure 1. (a) SIMS intensities of different Hf- and La-related ionic species and
Al to track the sapphire (Al2O3) substrate, (b) zoomed view to compare La and
Hf content

To investigate the composition of the film, low-energy SIMS was

utilized. This technique tracked the evolution of the La+, LaO+, Hf+,
and HfO+ along with Al+ to determine when the sputtering reached the
sapphire substrate. After roughly 1.4 x 104 seconds, the sapphire
substrate was reached (as indicated in Fig. 1(a)). Although there were
no significant differences in the overall trends observed for La and
Hf, periodic variations in intensity were present across all
measurements. Specifically, Fig. 1(b) provides a closer view of the
La-O+ and Hf-O+ signals, where it is clear that the maximum and
minimum values of both curves align. This indicates that the La/Hf
ratio did not vary across the film. Eleven of these periodic
modulations were identified, which corresponds to the number of
spin-coating cycles used for the L/L sample. Therefore, with the help
of SIMS it was not only possible to study the elemental composition,
but also an idea of the individual film layers.
 Wake-up effect in FE HfO2 thin-film

The hysteretic curve is a fundamental characteristic of a ferroelectric

capacitor, illustrating how changes in electric polarization relate to the
electric field. Among the key features of this curve are the remanent
polarization (Pr) and coercive field (Ec), which correspond to the
intercepts on the axes, as demonstrated in Figure 2. The wake-up
effect, which is believed to stem from the repeated cycling of the
device, primarily results in an increase in Pr. Typically, the pristine
state exhibits a pinched hysteresis, which then opens-up upon cycling.
This phenomenon has been observed in ferroelectric materials based
on HfO2, regardless of the deposition technique or dopant employed,
and achieving the maximum Pr requires initial cycling.

P1 [uC/cm2]

20
P1 [uC/cm2]
20 15

DHM 1
15
10 PR
10
P1 [uC/cm2]

15

5
P1 [uC/cm2]

10
5
5
0 0
P

-5
-5
-5
EC
-10 -10

-15 -15
-10
-4 -3 -2 -1 0 1 2 3 4
V -20 -15
-15 -10 -5 0 5 10 15
V+ [V]
-20

-15 -10 -5 0 5 10 15
V+ [V]

Figure 2. Evolution of Pr and Ec in ferroelectric HfO2 thin film cycled 1000 time
at 3kHz.

Due to the Pr increase caused by the wake-up effect during cycling,

the use of ferroelectric capacitors in memory circuits can result in
misreading of stored information, and it can also harm the endurance
of devices. Therefore, it is essential to study the wake-up effect not
only to enhance device reliability but also to uncover the mechanism
of ferroelectricity. The wake-up effect observed in HfO2-based
ferroelectric films is widely believed to originate from the
redistribution of defects, particularly oxygen vacancies. These defects
tend to accumulate at the dielectric electrode interface. The defects
create a built-in field bias in accordance with their original
distribution, which suppresses the polarization of ferroelectric dipoles
near the field and may even cause dipoles to polarize in opposite
directions. Consequently, the overall polarization intensity is lower
than the maximum achievable. During cycling, the defects
redistribute, leading to a reduction in the built-in field bias and the
polarization of dipoles in the same direction.

E.D. Grimley et al. has investigated the wake-up effect using

STEM[5]. The HAADF-STEM images (Figure 3) reveal that the
interfacial HfO2 layer experiences alterations in both interfacial strain
and phase presence upon field cycling. These changes lead to a
reduction in the tetragonal phase presence in the cycled (woken-up
and fatigued) samples compared to the pristine ones. Furthermore, the
lattice parameter maps obtained from these regions provide a more
detailed understanding of the complex interface environments and aid
in visualizing strain and phase presence. To better visualize the
details, the color-scale ranges in these maps were set manually.

The modifications in the interface structure during cycling are most

probably caused by the redistribution of defects and changes in the
phase or orientation of grains, both of which modify the strain
environment and occur simultaneously with field cycling [6].
Furthermore, advanced characterization techniques like STEM enable
us to perform such in—depth structural analysis.
 Figure 3. HAADF-STEM images of the Gd:HfO2 sample at pristine state,
woken-up and fatigued state.

Ref:

1. T. S. Boescke, J. Mueller, D. Braeuhaus, U. Schroeder, and U. Boettger, “Ferroelectricity in Hafnium Oxide thin films,” Applied
Physics Letters, 99, 102903 (2011)

2. Q. Luo, H. Ma, H. Su, K. Xue, R. Cao, Z. Gao, J. Yu, T. Gong, X. Xu, J. Yin, P. Yuan, L. Tai, D. Dong, S. Long, Q. Liu, X.
Miao, H. Lv, M. Liu, IEEE Electron Device Lett. 2019, 40, 570.

3. T. Schenk, N. Godard, A. Mahjoub, S. Girod, A. Matavz, V. Bobnar, E. Defay, and S. Glinsek, “Toward thick piezoelectric
HfO2-based films,” Phys. Status Solidi Rapid Res. Lett. 14, 1900626 (2020)

4. T. Schenk, A. Bencan, G. Drazic, O. Condurache, N. Valle, B. El Adib, N. Aruchamy, T. Granzow, E. Defay, and S. Glinsek ,
"Enhancement of ferroelectricity and orientation in solution-derived hafnia thin films through heterogeneous grain nucleation",
Appl. Phys. Lett. 118, 162902 (2021)

5. Everett D. Grimley , Tony Schenk , Xiahan Sang , Milan Pešic´ , Uwe Schroeder , Thomas Mikolajick , and James M. LeBeau
Adv. Electron. Mater. 2016, 2, 1600173

6. M. Pešic´ , F. P. G. Fengler , L. Larcher , A. Padovani , T. Schenk , E. D. Grimley , X. Sang , J. M. LeBeau , S. Slesazeck , U.

Schroeder , T. Mikolajick , Adv. Funct. Mater. 2016, 26, 4601