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Phys. Status Solidi A 209, No. 10, 1996–2001 (2012) / DOI 10.1002/pssa.201228175

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applications and materials science
Resistive-switching behavior and
mechanism in copper-nitride thin films
prepared by DC magnetron sputtering
1 1 2 3 1 ,1
Wei Zhu , Xin Zhang , Xiaoniu Fu , Yongning Zhou , Shengyun Luo , and Xiaojing Wu*
1
Department of Materials Science, Fudan University, No. 220 HanDan Road, 200433 Shanghai, P. R. China
2
Department of Optical Science and Technology, Fudan University, No. 220 HanDan Road, 200433, Shanghai, P. R. China
3
Department of Chemistry, Fudan University, No. 220 HanDan Road, 200433 Shanghai, P. R. China

Received 16 March 2012, revised 5 May 2012, accepted 14 May 2012

Published online 8 June 2012

Keywords conducting filaments, copper nitrides, magnetron sputtering, resistive switching

* Corresponding author: e-mail wuxj@fudan.edu.cn, Phone/Fax: þ86 021 65643258

Resistive random access memory (RRAM) devices are made by
copper nitride films prepared by DC magnetron sputtering.
After a forming process, the CuxN-based RRAM devices show
bipolar character with low operation voltage and distinguish-
able resistance ratio. The fitting results for the electrical
measurements and the conducting atomic force microscope
(CAFM) analysis indicate that resistive switching mechanism is
consistent with the formation and rupture of conducting
filaments. Simultaneously, the distribution of conducting
filaments measured by CAFM reveals a promising potential
to fabricate high-density RRAM device by using this material.
The mechanism of the formation of conducting filaments is
discussed based on our results.

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1 Introduction Resistive random access memory
(RRAM) is considered as one of the most promising
candidates for the next generation of high-density non-
volatile memory, owing to its simple fabricating process and
compatibility with complementary metal oxide semicon-
ductor (CMOS) technology. The resistive switching beha-
vior has been observed in a number of transition metal oxides
(TM-oxides), such as NiO, TiO2, HfO2, CuxO, ZnO, and
SrTiO3 [1–6], and solid electrolytes, such as GeSe [7], silicon
[8], and some of organics [9]. However, resistive switching
characteristics and physical mechanism in nitrides has not
been fully studied yet, and only few reports on copper nitride
[10], aluminum nitride [11], and silicon nitride [12] have so
far been published on this system. Therefore, it still is an
interesting subject to search for effective methods to improve
resistive switching performance of the nitrides as well as to
investigate their working mechanism.
It is well known that copper nitride has different
combined forms: Cu3N, Cu4N and Cu3N2. The resistivity
of the CuxN thin film may spread in a wide range from 10
3 to
105 V cm [13, 14]. It would attract great interests if RRAM
can be fabricated with CuxN films, due to its compatibility
with Cu interconnection process in CMOS technology.
In this study, we present reproducible resistive switching
behavior in Ni/CuxN/Ni as well as Pt/CuxN/Pt sandwiched
structures. The CuxN thin film with a thickness of about
120 nm was prepared by DC magnetron sputtering, and the
physical mechanism of the CuxN films is discussed in Pt/
CuxN/Pt devices based on the result of electrical measure-
ments.
2 Experiments A Ni film with a thickness of 300 nm
or a Pt film with a thickness of 100 nm was deposited on TaN/
SiO2/Si substrates by DC sputtering as a bottom electrode.
The CuxN films with a thickness of 120 nm were deposited by
direct current magnetron sputtering with copper target
(99.99%) at room temperature on the substrates of Ni/TaN/
SiO2/Si and Pt/TaN/SiO2/Si, respectively. The working gas
was pure N2 and working pressure was 1.8 Pa (background
pressure 2  10
3 Pa). The structure and composition of the
CuxN thin films were characterized by X-ray diffraction
(XRD, CAD4 DIFFACTIS 586) and X-ray photoelectron
spectroscopy (XPS, PHI 5000C ESCA System), respect-
ively.
Subsequently, a Ni or Pt layer was deposited upon the
CuxN/Ni/TaN/SiO2/Si or CuxN/Pt/TaN/SiO2/Si structure as

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Phys. Status Solidi A 209, No. 10 (2012)
Figure 1 XRD patterns of as-deposited CuxN thin films and after
thermal treatment.
the top electrode (TE) with a diameter of 40–100mm
patterned by a shadow mask, respectively. Thus, TE, CuxN
layer and bottom electrode constitute a metal–insulator–
metal (MIM) RRAM device as illustrated in Ref. [15]. I–V
characteristics of CuxN-based RRAM cells were measured
by a Keithley 4200-SCS semiconductor parameter analyzer
with a Tungsten needle probe station. Morphology as well as
in situ electrical property in nanoscale for CuxN/Pt/TaN/
SiO2/Si was measured by using a conducting atomic force
microscope (CAFM, Veeco Multimode Nanoscope V SPM)
with Pt coating conducting tip as TE, as shown in Ref. [16].
3 Results and discussion Figure 1 shows XRD
patterns obtained from the as-deposited and the annealed
CuxN films. The as-deposited CuxN film was amorphous,
whereas after heat treatment at 2008C for 10 min in N2
atmosphere, a peak of Cu3N phase, which has anti-ReO3
structure, appeared. The film was well [111]-oriented,
similar as the result of Kim et al. [17].
The chemical states of Cu and N atoms in the as-
deposited CuxN film was determined by XPS measurement
as shown in Fig. 2a. Comparing the peak positions obtained
from the CuxN and pure-Cu film, a peak shift of about 0.8–
0.9 eV could be identified, which is similar with those
reported by Gao et al. [18] for their Cu3N samples prepared
by RF magnetron sputtering system.
The photoemission peak of N 1s as shown in Fig. 2b
could be separated into three components: main peak at
397.4 eV (peak 2), left shoulder at 398.5 eV (peak 1), and
right shoulder at 396.8 eV (peak 3). According to Ref. [19] as
well as Ref. [20], it is known that peak 2 comes from the
Cu3N phase, while peak 1 comes from the Cu4N phase. The
lowest peak of 396.8 eV fits well with N 1s-binding energy of
N2 molecule as reported by Soto et al. [21]. Compared with
our previous work in which the CuxN film was prepared by
implanting N ions into the cooper film by using plasma
immersion ion-implantation (PIII) [10], the present CuxN
film seems to contain higher proportion of Cu3N phase.
Typical current–voltage (I–V) characteristics of the Ni/
CuxN/Ni memory cell are plotted in Fig. 3. The bias voltage
was applied to TE with the bottom electrode grounded. The
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Paper
1997
Figure 2 XPS results of the as-deposited CuxN thin films (a) Cu 2p
spectra for the CuxN (solid line) and pure-Cu (dashed line); (b) N 1s
peak with three components in CuxN films.
pristine devices exhibit a high resistance of 107 V. After a
forming process with a positive 3.5 V voltage sweep,
counterclockwise bipolar resistance switching character-
istics have been detected with a current compliance of 5 mA,
similar to the results of Kim et al. [22, 23]. A positive voltage
sweep can induce SET process and a negative one for
RESET. As shown in Fig. 3b, when the bias voltage changed
to BE with the TE grounded, similar I–V characteristics have
been detected. A reversed forming voltage would change the
directions of SET and RESET voltage for the current device,
which consists of a symmetrical Ni/CuxN/Ni structure. For
over 100 repeated switching cycles, the device shows very
stable bipolar switching characteristics with a low operating
voltage of about 0.8  0.3 V. The evolution of resistance of
HRS and LRS is plotted in Fig. 4a. The resistance of HRS
has a rather wide distribution of about 103–107 V, while the
resistance of LRS is always in the order of 102 V. The
resistance ratio between HRS and LRS is larger than 10
times, enough to distinguish the storage information (‘‘1’’ or
‘‘0’’) for the present device. The threshold voltage of SET
process (VSET) is distributed in the range of 0.5–1.5 V, while
that of the reset process (VRESET) is ranged from 0.4 to 1 V.
To further study of the leakage conducting mechanism in
LRS and HRS, typical I–V curves are plotted on a
logarithmic scale, as shown in Fig. 4b. The current–voltage
relationship in LRS exhibits an Ohmic conduction behavior
with a slope of 1.0, which is attributed to the formation of
conductive filaments in the device during the SET process.
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18626319, 2012, 10, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/pssa.201228175 by INASP/HINARI - PAKISTAN, Wiley Online Library on [13/11/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
1998 W. Zhu et al.: Resistive-switching behavior and mechanism in copper-nitride thin films

Figure 4 (online color at: www.pss-a.com) (a) Endurance per-

formance of Ni/CuxN/Ni device. The resistance was read out at
Figure 3 (online color at: www.pss-a.com) Typical current– 0.1 V. (b) Typical I–V curves in log–log scale and the corresponding
voltage characteristic of a Ni/CuxN/Ni/TaN/SiO2/Si memory cell slopes for LRS.
in DC voltage sweep mode. (a) The bias voltage was applied to TE
with the bottom electrode grounded; (b) the bias voltage was applied
to BE with the TE grounded.

However, the I–V curves in HRS are rather complicated and

less reproducible. As shown in the fitting results of HRS, the
current–voltage relation consists of three portions: In the
low-voltage region (<0.2 V), it shows linear behavior with a
slope of 1.06–1.11, which is close to Ohmic conduction
(I / V). In medium-voltage region (0.5 V), the slope
increases to 1.72–1.80, a little smaller than that of the
Child’s Law (I / V2). The current of HRS in the third portion
(100th cycle) shows a steep exponential increase with a slope
of about 2.25 in high-voltage region (>0.8 V) until VSET. The
charge transport behavior in HRS is similar to the classical
trap-controlled space charge limited conduction (SCLC)
Figure 5 (online color at: www.pss-a.com) Typical current–
[24] and similar phenomena have been observed in TM- voltage characteristic of a Pt/CuxN/Pt memory cell in DC voltage
oxides RRAM devices [22, 23, 25, 26]. Choi et al. [25] sweep mode.
proposed that the occurrence of linear conduction in both
HRS and LRS indicates metal-like weak filaments through- metal cations, under local high electric fields applied at the
out the insulating film. The formation of conducting forming process. Jung et al. [26] proposed that the current in
filaments attributes to extended defects, such as the HRS could be divided into two parts: the current flowing
migration of oxygen vacancies or lower valence states of through weak filaments (Ifila) and the current in insulating

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Phys. Status Solidi A 209, No. 10 (2012)
film (Ii). Above the temperature of 200 K, Ii is larger than
Ifila and the current in HRS tends to follow the SCLC
mechanism [26].
The same measurements were also taken for the I–V
characteristics for the Pt/CuxN/Pt memory cells as was done
for the Ni/CuxN/Ni memory cells, as shown in Fig. 5.
The resistance of HRS has a wide distribution from about 103
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18626319, 2012, 10, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/pssa.201228175 by INASP/HINARI - PAKISTAN, Wiley Online Library on [13/11/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Paper
1999
to 105 V, while the LRS resistance is close to 102 V.
Comparison between the performance of Pt/CuxN/Pt cells
with that of Ni/CuxN/Ni cells shows that these two cells have
quite similar properties, except that the latter has a slightly
better endurance than the former.
Furthermore, CAFM was employed for a microscopic
measurement of the CuxN/Pt/TaN/SiO2/Si device, and the
Figure 6 (online color at: www.pss-a.com) (a) Morphology and
conductivity 2D and 3D mapping results of different applied
voltages, (b) forming process (3 V), (c) HRS, and (d) LRS at
0.5 V for CuxN/Pt/TaN/SiO2/Si device with Pt coating tip as TE
measured by CAFM (red peaks are measured results, while blue
ones are fitted curve). (e) Typical I–V curve of single point in micro
size using a Pt-coated AFM probe as the TE.
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2000 W. Zhu et al.: Resistive-switching behavior and mechanism in copper-nitride thin films
morphology as well as the in situ microscopic electrical
properties are presented in Fig. 6. The writing and reading
process was carried out by a contact-AFM mode scan in
a 500  500 nm2 square, applying the SET voltage at 1 V
while RESET voltage at
0.5 V on the bottom electrode.
From Fig. 6a, the CuxN film exhibits excellent microscopic
roughness with Ra of 1.60 nm and Rq of 2.06 nm. As shown in
Fig. 6b, 149 current peaks above 1 nA were measured after a
forming process of 3 V, which confirms that a number of
highly conductive paths have taken shape in the pristine
CuxN films during the forming process. Figures 6c and d
show the conductivity mapping result in HRS and LRS at
reading voltage of 0.5 V, respectively. Only 69 current peaks
above 100 pA were obtained in HRS with the maximum
peak of 187.3 pA, while there were 150 current peaks above
200 pA in LRS and the maxim one of 916.9 pA. Obviously,
the formation and rupture of highly conductive filaments
play a key role in resistance switching behavior in micro size.
The conducting filament density of this device in LRS could
be calculated as high as about 40  40 nm2/filament. More-
over, bipolar resistive switching behavior has been detected
at single point in micro size using a Pt-coated AFM probe as
the TE, shown in Fig. 6e. Current in 100 pA level and low
operation voltage with TE in size of CAFM probe provide a
promising potential in scaling for manufacturing high-
density RRAM device using this type of nitride compound.
Similar conducting filaments have also been found in
devices consisting of Ni/CuxN/Cu structure [10]. Due to high
mobility and reactivity of copper ions, it cannot be ruled out
that the formation of filaments in the CuxN layer was due to
the immigration of copper ions, which came from the bottom
electrode in that work. However, for the present device, the
top and the bottom electrodes were Pt, a typical noble
electrode material with extremely low mobility and
reactivity. Obviously, the electrochemical metallization
mechanism (ECM) [15] does not work for this kind of
device. Therefore, we propose that the change in valence
states or migration of ions in the CuxN films would be the
primary mechanism of the formation and rupture of
conducting filaments. It was reported that semiconducting
Cu3N phase could change into metallic Cu4N phase by
inserting a Cu atom into the body center of Cu3N anti-ReO3
structure. The inserted Cu atom would release a free electron
as a carrier, which improved the conductivity of CuxN films
[27]. During the electroforming process with high electric
field, structure or composition of the CuxN film has been
modificated by Joule heating as well as ionic migration.
Similar forming effects have been proved in TM-oxide based
RRAM device with symmetrical structure [28]. The
concentration of Cu4N phase or Cu atom at cathode took
shape in conducting filament in the pristine CuxN film. When
the conducting filaments connected up to the anode, the
device is switched into the ‘‘ON’’ state. In this case the pre-
existed Cu4N phase may play an important role in the
formation of such conducting filaments. When a negative
voltage was applied, the reversed mobility of Cu cations
caused the rupture of conducting filaments at the weakest
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point near anode. Similar mechanism of conducting filament
has been suggested by Yasuhara et al. [29] for the Pt/CuxO/Pt
device as well as Kwon et al. [30] for the Pt/TiOx/Pt device.
Yasuhara et al. [29] proposed that Cu2O or other hypoxia
state of copper oxide formed in the conducting filaments
by analyzing the combined forms of conducting filaments
in Pt/CuxO/Pt devices using PEEM with a synchrotron-
radiation source. Kwon et al. [30] confirmed that conducting
filament in Pt/TiOx/Pt device consists of Magnéli crystallite
(Ti4O7), considered as metal conductivity phase, by in situ
TEM measurement. Structural or compositional modifi-
cation of TM-oxides, mostly caused by electric field assisted
ionic migration, is considered as the major mechanism of the
formation and rupture of conducting filaments [28].
4 Conclusions In summary, we fabricated Ni/CuxN/
Ni and Pt/CuxN/Pt RRAM devices prepared by DC
magnetron sputtering. After a forming process, reproducible
bipolar resistive switching behavior with low operation
voltage was observed. Fitting results for the electrical
measurements and the CAFM analysis show that resistive
switching mechanism is consistent with the formation and
rupture of conductive filaments. The distribution of con-
ducting filaments measured by CAFM reveals a promising
potential in scaling for high-density RRAM applications. It is
proposed that the migration and reduction of cations in CuxN
films might be the reason for the formation of conductive
filaments rather than ECM.
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