IEEE TRANSACTIONS ON MAGNETICS, VOL. 53, NO.

11, NOVEMBER 2017 2501604

Impact of Tungsten Sputtering Condition on Magnetic and

Transport Properties of Double-MgO Magnetic Tunneling
Junction With CoFeB/W/CoFeB Free Layer
H. Honjo1,7 , S. Ikeda1–3,7, H. Sato1–4 , K. Nishioka1,7, T. Watanabe1,7, S. Miura1,7 , T. Nasuno1,7, Y. Noguchi1,7 ,
M. Yasuhira1,7, T. Tanigawa1,7, H. Koike1,7 , H. Inoue1,7, M. Muraguchi1,5,7 , M. Niwa1,7 ,
H. Ohno1–4,6, and T. Endoh1–3,5,7
1 Center for Innovative Integrated Electronic Systems, Tohoku University, Sendai 980-0845, Japan
2 Center for Spintronics Integrated Systems, Tohoku University, Sendai 980-8577, Japan
3 Center for Spintronics Research Network, Tohoku University, Sendai 980-8577, Japan
4 Laboratory for Nanoelectronics and Spintronics, Research Institute of Electrical

Communication, Tohoku University, Sendai 980-8577, Japan

5 Graduate School of Engineering, Tohoku University, Sendai 980-8579, Japan
6 WPI-Advanced Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan
7 Japan Science and Technology Agency (JST) ACCEL, Saitama 332-0012, Japan

We investigated an effect of sputtering gas species (Ar, Kr, and Xe) for deposition of a W insertion layer in the CoFeB/W/CoFeB
free layer on magnetic properties of the free layer and tunnel magnetoresistance (TMR) ratio of magnetic tunnel junctions (MTJs)
stacks using the free layer annealed at 400 °C for 1 h. As the W insertion layer thickness tW increased, we found the degradation of
perpendicular anisotropy and larger reduction of saturation magnetic moment per unit area m S in the free layer using Ar compared
to those using Kr and Xe. We also found a smaller TMR ratio for the MTJ stack using Ar compared to those using Kr and Xe.
Energy-dispersive X-ray spectrometry line analysis revealed more significant interdiffusion between W and CoFeB layers in the free
layer using Ar than those using Kr and Xe, that could result in the smaller m S and perpendicular anisotropy in the free layer and
smaller TMR ratio for the MTJ stack using Ar than those using Kr and Xe. We also investigated concentration of Ar, Kr, and Xe
in W layers deposited using Ar, Kr, and Xe, respectively, by high-resolution Rutherford backscattering spectrometry, revealing that
0.2 at% Ar was detected in the W layer using Ar, while Kr and Xe were not detected in W layers using Kr and Xe. Such a difference in
concentration of inert gas atoms in the W layer could be one possible reason for the difference about degree of interdiffusion between
W and CoFeB layers.
Index Terms— CoFeB–MgO, double interfaces structure, interfacial anisotropy, magnetic tunnel junction (MTJ), perpendicular
anisotropy, spin-transfer-torque magnetoresistive random access memory (STT-MRAM).

I. I NTRODUCTION layer underneath them is generally dependent on sputtering gas

S PIN-TRANSFER-TORQUE magnetoresistive random
access memories [1]–[7] using CoFeB–MgO-based
magnetic tunnel junctions with perpendicular (p-MTJs)
easy axis are attracting much attention owing to their high
potential in offering both low power consumption and high
performance [8]. Double CoFeB–MgO interface structure
was proposed [9], [10] to achieve high thermal stability
and low switching current. Thermal tolerance for annealing
at 400 °C required for CMOS back-end-process compatibility
was also demonstrated in the p-MTJ with the structure [11].
In the double CoFeB–MgO interface structure, a thin metal
layer such as Ta or W was inserted to absorb boron from
CoFeB layers, MgO/CoFeB/insertion layer/CoFeB/MgO, for
high tunnel magnetoresistance (TMR) ratio and perpendicular
anisotropy [9]–[13]. It was reported that a degree of damage
caused by the deposition of heavy metals (Ta or W) on the
Manuscript received March 9, 2017; revised April 27, 2017; accepted
May 3, 2017. Date of publication May 5, 2017; date of current version
October 24, 2017. Corresponding author: H. Honjo (e-mail: hr-honjo@cies.
tohoku.ac.jp).
Color versions of one or more of the figures in this paper are available
online at http://ieeexplore.ieee.org.
Digital Object Identifier 10.1109/TMAG.2017.2701838
0018-9464 © 2017 IEEE. Personal use is permitted, but republication/redistribution requires IEEE permission.
See http://www.ieee.org/publications_standards/publications/rights/index.html for more information.
species [14]–[16]. In fact, we have revealed that perpendicular
anisotropy of CoFeB–MgO system enhances by using Kr
instead of Ar for Ta-capping layer deposition [17]. Because
it is important to suppress damage during film deposition
for realization of high-performance p-MTJs, it is required to
engineer a deposition process for insertion layer resulting in
high TMR ratio and high perpendicular anisotropy.
In this paper, we investigated how the sputtering gas
species (Ar, Kr, and Xe) for the deposition of W inser-
tion layer affects magnetic properties of the free layer with
MgO/CoFeB/W/CoFeB/MgO structure and transport proper-
ties of the MTJ stacks with the free layer. We also discuss
the possible reason for dependence of the properties on the
sputtering gas species.
II. E XPERIMENT
The following MTJ stacks schematically shown in Fig. 1(a)
were deposited onto 300 mmφ thermally oxidized Si wafer
using dc and RF magnetron sputtering system; from substrate
side, bottom electrode/[Co/Pt]-multilayer-based synthetic fer-
rimagnetic reference layer/MgO barrier/CoFeB(t)/W insertion
layer (tW = 0.2, 0.3, or 0.5)/CoFeB(1)/MgO capping layer/top
electrode. The nominal thickness for each layer in nanometer
2501604
Fig. 1. (a) Schematic of the stack structure employed in this study.
W insertion layer tW in free layer and bottom CoFeB thickness t was varied
from 0.2 to 0.5 and 0.6 to 1.4 nm, respectively. (b)–(d) Minor magnetic
moment per unit area versus magnetic field curves of the stacks with tW = 0.2,
0.3, and 0.5 nm with W insertion layer deposited using Ar (W (Ar)),
Kr (W (Kr)), and Xe (W (Xe)) in which t was fixed to be 1 nm, respectively.
(e) Spontaneous magnetic moment per unit area m S as a function of tW for
the stacks with W(Ar), W(Kr), and W(Xe) insertion layer.
is given by the numbers in parenthesis. The W insertion layer
was sputtered with argon (Ar), krypton (Kr), or xenon (Xe)
gas, and hereafter we called W(Ar), W(Kr), and W(Xe),
respectively. In all cases, the gas pressure for W deposition
was kept to be ∼0.03 Pa. After the deposition, the MTJ stacks
were annealed at 400 °C for 1 h in a vacuum without
applying magnetic field. Magnetic moment per unit area versus
magnetic field (m–H ) curves and transport properties of the
MTJ stacks were measured by vibrating sample magnetometer
and current-in-plane tunneling method, respectively.
III. R ESULTS AND D ISCUSSION
First, we measured minor m–H curves of the MTJ stacks
[see Fig. 1(a)] with various tW for W (Ar, Kr, and Xe) insertion
layer. Fig. 1(b)–(d) shows minor m–H curves of the stacks
with W (Ar), W (Kr), and W (Xe) where tW varied from
0.2 to 0.5 nm. For the stacks with W (Ar), although abrupt
switching was observed in m–H curve at tW = 0.2 nm,
the switching was gradually done in m–H curve at tW =
0.3 and 0.5 nm and squareness was significantly reduced with
increase of tW . In contrast, the stacks with W (Kr and W) show
opposite trend with respect to tW ; the shape of m–H curve
became more squares with the increase of tW and squareness
increased as tW increased. The results indicate that, as tW
increased, perpendicular anisotropy degraded in the stacks
with W (Ar), while the perpendicular anisotropy was improved
in those with W (Kr and Xe). Note that, although we did not
observe antiferromagnetic coupling, it could be observed at
a certain W thickness above 0.5 nm [13], which may differ
among W (Ar), W (Kr), and W (Xe). To elucidate the reason
for the behavior, W layer thickness dependence of saturation
magnetic moment per unit area m S from the m–H curves
in Fig. 1(b)–(d) is evaluated, as shown in Fig. 1(e). The
m S of all the stacks reduced with the increase of tW . The
reduction of m S is due to either reduction of saturation
magnetization or effective CoFeB thickness, probably due to
intermixing between W and CoFeB layers. In both cases,
IEEE TRANSACTIONS ON MAGNETICS, VOL. 53, NO. 11, NOVEMBER 2017
Fig. 2. (a) TMR ratio of the stacks with W insertion layer deposited using
Ar (W (Ar)), Kr (W (Kr)), and Xe (W (Xe)) as a function of W insertion
layer thickness tW . Bottom CoFeB thickness t was fixed to be 1 nm. (b) TMR
ratio of the stacks with W (Ar), W (Kr), and W (Xe) as a function of bottom
CoFeB thickness. tW was fixed to be 0.3 nm.
the effective perpendicular anisotropy should increase, because
the reduction of saturation magnetization (effective CoFeB
thickness) results in the decrease of demagnetization energy
(increase of contribution of interfacial anisotropy). Therefore,
the W insertion layer thickness dependence of m S for the
stacks with W (Kr and Xe) is consistent with that of the
m–H curves. On the other hand, the results of the m–H curves
for the stacks with W (Ar) shown in Fig. 1(b) suggested the
degradation of effective perpendicular anisotropy although the
m S for the stacks decreased with the increase of tW . The results
indicate that the interfacial anisotropy is degraded by the
increase of tW in the stacks with W (Ar).
These results can be explained by that there is more signif-
icant intermixing between W and CoFeB layers in the sample
with W (Ar) compared to the others, because the interfacial
anisotropy could be reduced when the W atoms reach at
CoFeB–MgO interface. The proposed scenario is consistent
with the W insertion layer thickness dependence of m S for the
stacks with W (Ar), W (Kr), and W (Xe); a larger reduction
of m S was observed in the stacks with W (Ar) compared to
those with W (Kr and W).
In order to verify the hypothesis, we studied W insertion
layer thickness tW and bottom CoFeB thickness t depen-
dence of TMR ratio for the stacks with W (Ar), W (Kr),
and W (Xe). Fig. 2(a) shows W insertion layer thickness
dependence of TMR ratio for the stacks where bottom CoFeB
thickness was fixed to be 1 nm. TMR ratio for the sample with
W (Ar) increased with reducing tW , while that with W (Kr)
and W (Xe) shows almost constant value. Fig. 2(b) shows
bottom CoFeB thickness t dependence of TMR ratio for the
stacks where tW was fixed to be 0.3 nm. TMR ratio for the
sample with W (Ar) starts to decrease at thicker bottom CoFeB
thickness than that for the samples with W (Kr and Xe). Those
results support our hypothesis mentioned above that the more
significant interdiffusion between W and CoFeB took place in
the stacks with W (Ar) compared to the others.
HONJO et al.: IMPACT OF TUNGSTEN SPUTTERING CONDITION
Fig. 3. Depth profile of W and Mg elements in MgO/CoFeB/W/CoFeB/MgO
structure measured by EDX for stacks with W insertion layer deposited using
(a) Ar (W (Ar)), (b) Kr (W (Kr)), and (c) Xe (W (Xe)) after annealing
at 400 °C.
In order to confirm the difference about degree of the inter-
mixing among the stacks with W (Ar), W (Kr), and W (Xe),
we evaluated composition depth profile for the stacks using
energy-dispersive X-ray spectrometry (EDX) line analysis for
W and Mg elements. Fig. 3(a)–(c) shows the W and Mg depth
profiles for the MTJ stacks with W (Ar), W (Kr), and W (Xe)
annealed at 400 °C for 1 h, respectively.
The W line profile for the stack with W (Ar) was broader
than those for the stacks with W (Kr) and W (Xe). This indi-
cates that the length that interdiffusion between W and CoFeB
layers takes place is larger in the stacks with W (Ar) than that
with W (Kr) and W (Xe). Those results support our hypothesis
mentioned before. It should be noted that the degree of inter-
diffusion could be dependent on annealing conditions. One of
the possible reasons for the difference of degree of intermixing
between W and CoFeB could be related to the difference of
concentration of inert gas atoms in the W layer. In general,
recoiled Ar atoms from W sputtering target have higher energy
than Kr and Xe atoms due to smaller atomic mass of Ar [14],
leading to the higher concentration of Ar atoms in the W layer
compared to Kr and Xe atoms in the W layer. The larger
concentration of Ar atoms in the W layer results in larger stress
and more defects in the W layer [17]. We have also checked
this point experimentally. We measured concentration of Ar,
Kr, and Xe atoms in the single W layer using Ar, Kr, or Xe
gas by high-resolution Rutherford backscattering spectrometry
(HR-RBS). The 50 nm-thick the W films were deposited
on Si substrate using Ar, Kr, or Xe gas after cleaning a
substrate surface by Ar plasma. As shown in Fig. 4(a),
0.2 at% Ar was detected in W film using Ar. In contrast,
as shown in Fig. 4(b) and (c), Kr and Xe were not detected
in W films using Kr and Xe, respectively. Note that in all the
W films, Ar was detected near Si substrate due the penetrated
Ar atoms during Ar sputter etching for cleaning the substrate
sruface. Those structural differences could result in more
significant intermixing between W (Ar) and CoFeB compared
2501604
Fig. 4. Depth profile of W, Ar, Kr, Xe, and Si atoms measured by HR-RBS
for 50 nm-thick W films using (a) Ar, (b) Kr and, (c) Xe. The detected Ar
near Si substrate observed in all the films is penetrated Ar atoms during Ar
sputter etching for cleaning.
to W (Kr) and W (Xe) after 400 °C annealing. The diffused
W atoms at the interface between CoFeB and MgO barrier
in the free layer cause degradation of TMR ratio as well as
reduction of magnetization and anisotropy of the free layer
with W (Ar).
IV. C ONCLUSION
We have investigated magnetic properties of the free layer
with double CoFeB–MgO interface structure using W insertion
layer sputtered using Ar, Kr, and Xe, and TMR ratio of the
MTJ stacks using the free layer. As the W insertion layer
thickness increased, the reduction of effective perpendicular
anisotropy was observed in the free layer with W (Ar) whereas
the increase of it was observed in the free layer with W
(Kr and Xe). We also observed larger reduction of m S in the
free layer with W (Ar) compared to those with W (Kr and Xe)
as W insertion layer thickness increased. TMR ratio for the
MTJ stack with W (Ar) is lower than those with W (Kr)
and W (Xe). Those results can be explained by the larger
interdifussion between W and CoFeB layers in the free layer
with W (Ar) than that with W (Kr) and W (Xe). A larger
interdiffusion between W and CoFeB layers in the free layer
with W (Ar) compared to that with W (Kr and Xe) was
confirmed by cross-sectional EDX line analysis. We proposed
difference of concentration of inert gas atoms in the W layer
2501604
as possible reason for the difference of degree of interdiffu-
sion dependent on the sputtering gas species, that was also
checked by HR-RBS in 50 nm-thick W films using Ar, Kr,
and Xe gases.
ACKNOWLEDGMENT
This work was supported in part by the Center for Innovative
Integrated Electronic Systems Industrial Affiliation on STT
MRAM program and in part by the Japan Science and Tech-
nology Agency ACCEL, Japan, under Grant JPMJAC1301.
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