www.nature.

com/scientificreports

OPEN Enhancing silicide formation in Ni/

Si(111) by Ag-Si particles at the
interface
Received: 11 July 2018 Cheng-Hsun-Tony Chang   1,2,3, Pei-Cheng Jiang1,2, Yu-Ting Chow1, Hsi-Lien Hsiao4,
Accepted: 31 May 2019 Wei-Bin Su2 & Jyh-Shen Tsay1
Published: xx xx xxxx
Compound formation at a metal/semiconductor interface plays crucial roles in the properties of many
material systems. Applications of Ni silicides span numerous areas and have the potential to be used
as new functionalities. However, the magnetic properties of ultrathin Ni layers on silicon surfaces
and related chemical compositions at the interface are not fully understood and the influence of Ag
additives on the reactivity of Ni/Si(111) remain unclear. We report herein on the fact that the dominant
species produced at the interface is NiSi, which is produced by the spontaneous formation of strong
bonds between Ni and Si atoms. Assuming that a Ni layer is formed over a NiSi layer with the total
coverage as a constraint, we established a chemical shift-related concentration model that, in effect,
represents a practical method for determining the amount of ultrathin Ni silicides that are produced
at the buried interface. The formation of Ag-Si particles provide a viable strategy for enhancing silicide
formation via a specific interaction transfer mechanism, even at room temperature. The mechanism is
related to differences in the enthalpies of formation ΔHAg-Si, ΔHNi-Ag, and ΔHNi-Si, for these phases and
provides insights into strategies for producing ultrathin silicides at a buried interface.

Metal-semiconductor interfaces have attracted considerable interest because of their promising applications as
semiconductor devices and possible use as new functionalities in semiconductor technology1–6. Owing to the
high chemical reactivity of semiconductor surfaces, the formation of compounds at metal/semiconductor inter-
faces plays crucial roles in determining the properties of material systems and open a wide range of applica-
tions5–17. For example, cobalt di-silicide shows intrinsically low noise properties which could be utilized for
developing superconducting circuits and qubits in the future quantum computing8. Metal silicides have been
shown to have the ability of catalyze various reactions, especially hydrogenation, due to their specific crystal and
electronic structures10. For higher conversion efficiencies of the optical absorption spectrum, β-FeSi2-containing
SiO2 composites provide desirable selective absorbing behavior9. Moreover, the formation of compounds at
metal/semiconductor interfaces are induced by impurities16–19. At elevated temperatures, the interaction transfer-
ring for Si atoms through a ( 3 × 3 )R30o -Ag layer causes a gradual interaction between Si and Co and the
resulting smooth surface is advantageous in terms of stabilizing the easy axis of magnetization16. The distribution
of substitution alloying elements in the γ-Nb5Si3, which serves as a reinforcing phase of the composite based on
Nb–Si18. By implanting nitrogen under the critical conditions, the growth of metal-rich silicide phases is circum-
vented, as the Ni film converts to the amorphous NiSi phase during annealing19. Because of the interest in devel-
oping novel spintronic devices, explorations directed toward attempting to combine the charge and spin degrees
of freedoms have increased dramatically12–28. Based on a successful combination of a solution process and the
efficient control of the electric potential for magnetism, a novel concept of electric-potential-tuned magnetic
recording has been developed, resulting in the development of stable recording media with a high degree of writ-
ing ability20. The formation of CoSi2 compounds at the interface on a Si(111) surface occurs and the easy axis of
magnetization of Co/Si films is canted out-of-plane due to interfacial effects14. By tuning the contact areas of Ag
and Ni at the Ag/Ni interface, it is possible to change the coercive force of the films by modifying the magnetic
anisotropy energy13. By controlling interface band alignment, the functionality of the EuO/Si spin contact shows
a conduction band offset of 1.0 eV, a value that is competitive with charge electronics24.

1
Department of Physics, National Taiwan Normal University, Taipei, 116, Taiwan. 2Institute of Physics, Academia
Sinica, Taipei, 11529, Taiwan. 3Department of Electronic Engineering, Minghsin University of Science and Technology,
Hsinchu, 30401, Taiwan. 4Department of Physics, Tunghai University, Taichung, 407, Taiwan. Correspondence and
requests for materials should be addressed to J.-S.T. (email: jstsay@phy.ntnu.edu.tw)

Scientific Reports | (2019) 9:8835 | https://doi.org/10.1038/s41598-019-45104-3 1

www.nature.com/scientificreports/ www.nature.com/scientificreports

Nickel is widely used as catalyst, including for fabricating various nanostructures, and in water splitting,
hydrogen production, and sulfurization processes29–32. Nickel is also widely used in steel alloys and electroplat-
ing33–38. As a magnetic material, nickel has an advantage of a relatively low Curie temperature (627 K), which
permits it to be used in studies of critical phenomenon near room temperature39–41. The relatively small coercive
force of nickel allows Ni-based thin films to be studied under relatively low external fields42,43. Silicon is the most
important substrate that is used in fabricating microelectronic components. Because of the low resistivity and
low fabrication temperature, Ni/Si systems are widely used in the electronics industry as ohmic contacts and
interconnects44,45. Applications of Ni silicides span numerous areas, including their use in silicon complementary
metal-oxide semiconductors5,12, field effect transistors11, batteries46,47 and floating gate memory22. Ni2Si, NiSi and
NiSi2 all appear to be present at Ni/Si interfaces and the composition is dependent on the temperature of the
sample and the preparation procedure6,48,49. There are relatively few reports dealing with the magnetic proper-
ties of ultrathin Ni layers on silicon surfaces and chemical compositions of these materials at the interface. In
additional, the influence of Ag additives on the reactivity of Ni/Si(111) remain unclear. In this study, we report
on an investigation of the morphologies, chemical states and related magnetic properties of Ni/Si(111). NiSi is
the relatively dominant species found at the Ni/Si interface because of the strong bonding between Ni and Si
atoms. Assuming that a Ni layer is formed over a NiSi layer with the total coverage as a constraint, we established
a chemical shift-related concentration (CSRC) model that represents a practical method for determining the
amount of ultrathin Ni silicides that are produced at the buried interface. For a submonolayer Ni deposited on a
few monolayers of Ag/Si(111), the chemical state of Ni was found to be closer to that for Ni silicides rather than
for Ni-Ag bonding. This is the first observation to confirm that Ag-Si particles serve as a catalyst to promote the
chemical interaction of Ni and Si to form Ni silicides. The mechanism is related to the differences in the enthalpies
of formation ΔHAg-Si, ΔHNi-Ag, and ΔHNi-Si, and provide insights into strategies for producing ultrathin silicides
at a buried interface.

Results and Discussion

All experiments were conducted in an ultrahigh vacuum (UHV) chamber to avoid possible contamination
from the residual gases. The Si(111) surface was cleaned by Ar+ ion bombardment and annealed at 1250 K. The
sputtering-annealing cycles followed by slowly cooling to room temperature were continued until a well-ordered
7 × 7 structure could be obtained by low-energy electron diffraction (LEED) and scanning tunneling microscopy
(STM) techniques15,16. The cleanliness of the specimen was checked by Auger electron spectroscopy (AES). Ni
atoms were evaporated by passing an electronic current through a resistively heated Ni coil. The detailed infor-
mation about the sample preparations are described in the method section as well as in our previous reports13–17.
During the deposition of Ni on Si(111)-7 × 7, the morphological evolution of Ni/Si interfaces was investigated
using an STM technique. STM images for 0.8, 2.4, and 5 monolayer (ML) Ni/Si(111) are shown in Fig. 1a–c,
respectively. For imaging the silicide related defects on the Si(111)-7 × 7 substrate, a negative bias potential (Vbias)
at −1.5 V was used. As shown in Fig. 1a for 0.8 ML Ni/Si(111), dark defects can be seen on the rhombic unit cell
of the Si(111)-7 × 7 substrate. The dark defects are similar to that in Co/Si(111) for which the presence of Co sili-
cides have been reported14. For 0.8 ML Ni/Si(111), the dark defects are related to the formation of Ni silicides. The
dark defects have different sizes, which can be attributed to different chemical states of Ni silicides. For the case
of 2.4 ML Ni/Si(111) in Fig. 1b, small clusters with oval shapes can be seen. This is due to the accumulation of Ni
atoms to form clusters. For the case of the thicker Ni/Si(111) in Fig. 1c (5 ML), the surface morphology is rather
smooth indicating the formation of a continuous film. These structural findings are important for the further
analysis of magnetic properties of Ni/Si(111) ultrathin films.
Using the surface magneto-optic Kerr effect (SMOKE) technique at room temperature, Kerr signals versus the
magnetic field in both the longitudinal and polar configurations are shown in Fig. 1d. At the initial stage of the
Ni deposition (3 ML), no hysteresis is detectable in either of the configurations, but hysteresis clearly occurs at
thicker Ni/Si(111) (6 ML). As the Ni coverage increases (9 ML), both the saturated Kerr intensities and coercive
forces become larger. The coercive force in the case of the polar configuration is ten times larger than that in the
longitudinal configuration. This result shows that the preferred easy axis of magnetization for Ni/Si(111) lies on
the surface plane. Since the in-plane component dominates the magnetic anisotropy, in the following discussion,
we focus on the magnetic properties only in the longitudinal configuration. Figure 1e shows the saturated Kerr
intensity and coercive force versus Ni coverage in the longitudinal configuration. At the initial stage of Ni dep-
osition, the Kerr intensity is zero for the first 4 ML while the Kerr intensity is nonzero at a thickness of around
5 ML. For Ni/Si(111) thicker than 5 ML, the Kerr intensity increases linearly with increasing Ni coverage. This
shows that ferromagnetic films were formed with a Curie temperature well above room temperature where the
SMOKE measurements were taken. In a straight-line extrapolation of the data for Ni thicker than 5 ML, the fitting
line passes the transverse axis of Ni coverage at 1.8 ML. This indicates that the first-1.8-ML of Ni is nonmagnetic
due to the formation of Ni silicides. This method for insure nonmagnetic layer is developing in our group and
reported in many previous reports14–17. For Ni/Si(111) with a coverage between 1.8 and 5 ML, the zero value of the
Kerr intensity can be attributed to the finite size effect resulting from the formation of Ni clusters39,50. The thermal
agitation of the magnetization diminishes the exchange coupling between atomic magnetic moments in Ni clus-
ters13,15. Therefore, Ni/Si(111) adopts a phase comprised of paramagnetic clusters. On the other hand, the coercive
force increases rapidly from 7.5 to 30 Oe for 5 to 7 ML Ni and reaches a steady value of 30 Oe for thicknesses of
up to 11 ML. This is due to the effects of reduced dimensionality, reflecting the evolution of the magnetic aniso-
tropy energy for thin films21,39,50,51. The results of SMOKE measurements with three phases in different coverage
regimes for ultrathin Ni/Si(111) films are shown at the bottom of Fig. 1e and include (I) nonmagnetic silicides,
(II) clusters with lowered Curie temperatures, and (III) ferromagnetic films.
To obtain further information related to silicide formation for Ni adatoms on Si(111)-7 × 7, the morpholog-
ical evolution of Ni/Si interfaces were explored using the STM technique. As an example, Fig. 2a shows an STM

Scientific Reports | (2019) 9:8835 | https://doi.org/10.1038/s41598-019-45104-3 2

www.nature.com/scientificreports/ www.nature.com/scientificreports

D E F

Longitudinal Polar

Kerr signals (arb. units)

G
9 ML

6 ML

3 ML

-0.8 -0.4 0.0 0.4 0.8 -0.8 -0.4 0.0 0.4 0.8
Magnetic field (kOe)

4
Saturated Kerr intensity (arb. unit)

I II III 80

Coercive force (Oe)

3
60

2
40

1 20

H
0 0
0 2 4 6 8 10 12

Ni coverage (ML)

Ni Ni
Ni Ni 1L
1L6L 1L6L 1L6L
6L 6L 6L

Figure 1.  STM images of (a) 0.8, (b) 2.4, and (c) 5 ML Ni/Si(111). The images sizes are 50 × 50 nm2. (d) Kerr
signals versus the magnetic field for 3, 6 and 9 ML Ni/Si(111) in both the longitudinal and polar configurations.
(e) Saturated Kerr intensity and coercive force versus Ni coverage in the longitudinal configuration. The different
regimes are characterized by different magnetic behaviors. They are composed of nonmagnetic silicides, clusters
with lowered Curie temperature, and ferromagnetic films, as illustrated at the bottom of the plot.

image for 0.02 ML Ni/Si(111) at a negative Vbias. Different sized dark defects are clearly observed on the surface.
This phenomenon is different from the Co silicide formation process for Co deposition on Si(111)-7 × 7, where
only double-dark spots are detected, indicating that the dominant species in this case is CoSi214. The appearance
of different sized, dark defects for Ni deposited on Si(111)-7 × 7 suggests that different species of Ni silicides are
produced. At the initial stage of Ni deposition on Si(111)-7 × 7, the number of defects increases with increasing

Scientific Reports | (2019) 9:8835 | https://doi.org/10.1038/s41598-019-45104-3 3

www.nature.com/scientificreports/ www.nature.com/scientificreports

D
G
1.0
B1
H
Areal densities (arb. units)

B2
0.8
B3

0.6

0.4

0.2

0.0
0.00 0.01 0.02 0.03 0.04
Ni coverage (ML)

Figure 2. (a) STM images of 0.02 ML Ni/Si(111). Enhanced STM images showing (b) B1, (c) B2, and (d) B3.
The image sizes are 50 × 50 nm2 for (a), and 1.0 × 1.0 nm2 for (b–d). (e) Statistics for the areal densities of B1,
B2, and B3 calculated from STM images in 50 × 50 nm2 area for Ni adatoms on Si(111).

Ni coverage. In order to carry out a quantitative analysis, the defects were categorized according to the number
of dark spots in a unit cell, B1, B2, and B3, as shown in Fig. 2b–d, respectively. The areal densities for B1, B2,
and B3 are defined as the ratios of B1, B2, and B3 unit cells per total unit cells, respectively. The statistics for the
areal densities of B1, B2, and B3 are shown in Fig. 2e, calculated from STM images of 50 × 50 nm2 areas for small
amounts of Ni atoms on Si(111). By increasing the coverage of Ni, the areal densities of B1, B2 and B3 increase
while the slopes for these increases are different. After examining the STM images, single-dark spots (B1) occur
randomly on the Si(111) surface. Ni adatoms have no particularly preferred site for their bonding on the rhombic
unit cells of the Si(111)-7 × 7 substrate. The B1 spot is related to the formation of NiSi and can be attributed to the
presence of strong bonding between Ni and Si atoms. In addition, the areal density of B1 is much larger than those
for B2 and B3. This shows that NiSi is the relatively dominant species at the Ni/Si interface during the deposition
of Ni. Because of the lower enthalpy of formation of NiSi compared to that for NiSi252, it is reasonable to conclude
that NiSi is the dominant species at the interface for the Ni coverage from submonolayer to continuous film.
Spectroscopic evidence shows that the Ni silicides consist of only NiSi and NiSi2 for the case of Ni deposition on
a Si substrate at room temperature53. We therefore conclude that the increases in the areal densities of B2 and B3
are due to an increased level of NiSi2, the accumulation of NiSi, and a mixture of NiSi and NiSi2.
Because of the finite inelastic mean free path (IMFP) of Auger electrons54,55, AES is sensitive to chemical
interactions that occur at the Ni/Si interface. Figure 3a shows Auger signals N(E) near the Ni M23M45M45 Auger
transition versus the kinetic energy (E) for Ni/Si(111) for different levels of Ni coverage; where N(E) corresponds
to the counts of the AES measurements at kinetic energy E. For the case of 10 ML Ni/Si(111), it is sufficiently
thick compared to the IMFP of Ni M23M45M45 Auger electrons (~0.47 nm)55 and therefore the peak position
of the Auger signals N(E) located at 57.0 eV is close to that of bulk Ni (grey solid line). For the case of thinner
Ni/Si(111), the Ni M23M45M45 Auger transition line shifts to a lower kinetic energy and the peak position of
the Auger signals N(E) reaches 55.7 eV for 0.3 ML Ni/Si(111). Because Si is more electronegative than Ni56, the

Scientific Reports | (2019) 9:8835 | https://doi.org/10.1038/s41598-019-45104-3 4

www.nature.com/scientificreports/ www.nature.com/scientificreports

Ni M23M45M45
for x ML Ni/Si(111) 2.0 2.0
measured result E
D

Amount of Ni silicides (ML)

bulk Ni

AES N(E) (arb. units)

1.5 1.5

Chemical shift (eV)

10 ML

1.0 1.0

4 ML

0.5 0.5
0.3 ML

0 ML
0.0 0.0
0 5 10
50 55 60 65
Kinetic energy (eV) Ni coverage (ML)

F
ymixed =yαα yαβ
yαβ yαα Ni
NiSi
Si
ϕ yαβ

Cover decay
yαβ

Figure 3. (a) Auger signals N(E) near the Ni M23M45M45 Auger transition versus kinetic energy for 0, 0.3, 4 and
10 ML Ni/Si(111). (b) Chemical shift (black squares) and amount of Ni silicides (blue circles) versus Ni coverage
for Ni/Si(111) thinner than 12 ML. (c) Schematic plots for simulated Auger peaks by assuming α-α and α-β
bonds with a layered structure.

lowered kinetic energy of the Ni Auger transition line confirms the formation of Ni-Si compounds at the interface
due to a change in the chemical environment of the Ni atoms from Ni-Ni to Ni-Si (grey dash line). We define the
chemical shift of Ni M23M45M45 as the difference in the position of the peak for the Auger signals N(E) respective
to that for pure Ni. Figure 3b (black squares) shows the chemical shift for Ni M23M45M45 versus Ni coverage for
Ni/Si(111) thicknesses less than 12 ML. For 0.3 ML Ni/Si(111), the chemical shift is as large as 1.3 eV, indicating
that Ni silicide is formed at the interface. The chemical shift decreases with increasing Ni coverage. In order to
explore the amount of Ni silicides at the interface, we propose a CSRC model based on analyses of the Auger peak
position, as discussed below.
Auger signals N(E) for an adsorbate in the elemental form are located at a certain value. When there is a chem-
ical interaction between the adsorbate and substrate atoms, the change in chemical state is accompanied by a shift
in the position of the Auger signals N(E). We attempted to correlate the chemical shift with the composition of
the compounds that were formed using the proposed CSRC model, as illustrated as a schematic plot in Fig. 3c.
We simulated the Auger signal N(E) as a Gaussian function. The kinetic energy of such compounds differ from
one another and can be simulated by a shift in the position in the Gaussian function. For element α with an α-α
bond, the Auger signal can be expressed as
2
yαα(E ) = Iαα ⋅ e−E (1)
where Iαα is the intensity related to the amount of element α with an α-α bond. Chemical interactions between
elements α and β may result in a different in the energy φ and the related Auger signal can be expressed as
2
yαβ (E ) = Iαβ ⋅ e−(E+φ) (2)
where Iαβ is the intensity related to the amount of element α with an α-β bond. During the process of compound
formation, both the elemental state and the compound state are present and the shift of the Auger transition line
depends on the relative compositions of each. If compound formation occurs at the interface, we assume that the
α-α and α-β regions are distributed in a stacking arrangement, as shown in the Fig. 3c. The Auger intensity of α-α
layers follows a homogeneous attenuation model54 and can be expressed as

Iαα = I0(1 − e−dαα/λ ) (3)

Scientific Reports | (2019) 9:8835 | https://doi.org/10.1038/s41598-019-45104-3 5

www.nature.com/scientificreports/ www.nature.com/scientificreports

where dαα is the layer thickness; λ is the escape depth of the Auger electrons characterizing their IMFP in the
solid; I0 is the Auger sensitivity. We assume that the Auger sensitivity (I0) is the same for both the α-α layers and
α-β layers. By considering an α-β compound layer covered by an α-α layer, an e−dαα/λ term can be added to
Equation 3. The intensity Iαβ is then expressed as

Iαβ = I0(1 − e−dαβ /λ ) ⋅ e−dαα/λ (4)

The resulting Auger signal related to the thickness dαα for α-α layers and dαβ for α-β layers can be represented
as
yS = yαα + yαβ
2 2
= I0(1 − e−dαα/λ )e−E + I0(1 − e−dαβ /λ ) ⋅ e−dαα/λ e−(E+φ) (5)
As shown in Equation (5), the Auger peak position (Ep) can be obtained from the maxima value of the mixed
Auger signal (ys) within the critical thickness of α-α and α-β bonds.

dyS 2
= −2I0 ⋅ [E ⋅ (1 − e−dαα/λ )e−E + (E + φ) ⋅ (1 − e−dαβ /λ ) ⋅ e−dαα/λ
dE E=E p
2
⋅ e−(E+φ) ]|E=E p = 0 (6)
The Auger peak position Ep follows the Equation

(1 − e−dαα/λ ) Ep + φ
−d αβ / λ −d αα/ λ
=− e−(2E p+φ)φ
(1 − e )⋅e Ep (7)
and is related to the chemical shift in AES measurements associated with compound layers with thickness dαβ.
Based on Equation (7) with the constraint of the total coverage of Ni, we simulated the thicknesses of Ni-Ni layers
and Ni-Si layers to match the chemical shift obtained in AES measurements as shown in Equation 7. The thick-
ness of the NiSi layer can be assumed to represent the amount of Ni silicides. The simulated results for the amount
of Ni silicides are shown in Fig. 3b as indicated by blue circles. The calculated amount of Ni silicides increases
rapidly with increasing Ni coverage and reaches a saturated value around 1.8 ML. By assuming the existence of a
layered structure of a Ni-Ni layer over a NiSi layer as illustrated in Fig. 3c, the simulated results for the amount of
Ni silicides for a 1.8 ML thickness is in good agreement with the experimentally obtained thickness of the mag-
netic dead layer shown in Fig. 1e.
After summarizing the STM, AES and SMOKE results regarding the morphologies, chemical states and related
magnetic properties, we can now revisit the schematic plots in Fig. 1e where three phases are resolved for different
coverage regimes. For regime I (0 to 1.8 ML), a nonmagnetic behavior is observed, as indicated by the nonzero
value on the coverage axis from the straight-line extrapolation of the SMOKE data, and is confirmed by both dark
spots in the STM images and NiSi bond states by AES. In regime II (1.8 to 5 ML), no Kerr intensity is detectable
(Fig. 1e) while the chemical state is transformed from Ni-Si to Ni-Ni as demonstrated by the AES findings in
Fig. 3. The observation of nano-sized clusters with oval shapes by STM (Fig. 1b) is indicative of the formation of
clusters with lowered Curie temperatures. In Regime III for a Ni coverage above 5 ML, ferromagnetic Ni films are
produced. This is due to the increasing size of clusters, which are large enough to cross the superparamagnetic
limit, thus forming a continuous film. The Curie temperature is well above room temperature.
Because of the high reactivity of a fresh Si surface, one possible route to passivate the Si surface so as to prevent
chemical reactions between overlayers with the substrate is the insertion of an immiscible element. As an exam-
ple of Co/Si(111), nonmagnetic silicide formation occurs at the interface while the insertion of Ag at Co/Si(111)
functions to modify the interfacial conditions, thus preventing the formation of silicides at room temperature15,17.
From the alloy phase diagram, each combination of Ag/Ni and Ag/Si is bulk immiscible57. We expected to see a
similar behavior for the reduction of silicide for Ni/Si(111) by the insertion of Ag. However, with respect to Ag
insertion, Co/Si(111) and Ni/Si(111) behaved differently. To explore this further, we examined the chemical states
of Ni atoms at the initial stage of the deposition where the corresponding Auger spectra near the Ni M23M45M45
transition line are presented in the left panel of Fig. 4a. For 0.3 ML Ni/Si(111), the peak position of the Auger
signals N(E) is located at 55.7 eV, which is related to Ni silicide states (black dash line), as discussed in Fig. 3. After
the insertion of Ag, the Auger transition line shifts to a higher kinetic energy (blue dash line). The chemical shift
of Ni M23M45M45 versus Ag coverage is summarized in Fig. 4b (black squares). For zero Ag coverage, the chemical
shift for Ni M23M45M45 is 1.3 eV, indicative of the silicide state for Ni adatoms. For inserting Ag into layers thicker
than 5.6 ML, the Ag layer is sufficiently thick that it blocks chemical interactions between Ni and Si at room
temperature. Therefore, the chemical shift of 0.5 eV for Ni M23M45M45 corresponds to interactions of Ni and Ag
atoms for approximately 0.3 ML of Ni at 5.6 and 8.4 ML Ag/Si(111). At the intermediate state for the 0.3 ML Ni
at 2.8 ML Ag/Si(111), the chemical shift of Ni M23M45M45 at around 1.3 eV is close to that for Ni on pure Si(111).
This suggests that the chemical state of Ni is closer to that for Ni silicides rather than Ni-Ag bonding.
The right panel of Fig. 4a shows the saturated Kerr intensities versus Ni coverage for Ni/Ag/Si(111) with a
Ag layer thinner than 8.4 ML. As the Ni coverage increases, the Kerr intensities are initially zero followed by a
linear increase for thicker Ni layers. The amounts of nonmagnetic layers are determined from the straight-line
extrapolation of the data within the linear parts to a zero signal, and their values are summarized in Fig. 4b (blue
circles). For inserting Ag in layers thicker than 5.6 ML, the amounts of the nonmagnetic layers are 2.0 ML. This is

Scientific Reports | (2019) 9:8835 | https://doi.org/10.1038/s41598-019-45104-3 6

www.nature.com/scientificreports/ www.nature.com/scientificreports

D
Ni M23M45M45
for ~0.3 ML Ni/y ML Ag/Si(111) 4
Ni-Ag alloy 3 8.4 ML
Ni silicide 2
bulk Ni 1

Saturated Kerr intensities (arb. unit)

0
0 2 4 6 8 10 12
8.4 ML 4
3 5.6 ML

AES N(E) (arb. units)

2
1
5.6 ML 0
0 2 4 6 8 10 12
4
3 2.8 ML
2.8 ML 2
1
0
0 2 4 6 8 10 12
4
3 0 ML
0 ML 2
1
0
50 55 60 65 0 2 4 6 8 10 12
Ni coverage (ML)
Kinetic energy (eV)

Amount of nonmagnetic layers (ML)

2.0 4
Ni-silicide
Ni-Ag alloy
1.5 3
Chemical shift (eV)

1.0 2

0.5 1

0.0 0
0 2 4 6 8 10

Ag coverage (ML)

Figure 4. (a) Left panel: Auger spectra near the Ni M23M45M45 transition line for approximately 0.3 ML of Ni
on Si(111) and Ag/Si(111) with an Ag layer thinner than 8.4 ML; right panel: saturated Kerr intensities versus
Ni coverage for Ni/Ag/Si(111) with the Ag inserting layers being 0, 2.8, 5.6, and 8.4 ML. (b) The chemical shift
(black squares) and the amount of nonmagnetic layers (blue circles) versus the Ag coverage.

consistent with the quenched magnetic moments of the first layer due to electronic coupling effects as reported
for Ni/Ag(111)48. For Ni/Si(111) without a Ag inserted layer, the thickness of the nonmagnetic layer is 1.8 ML.
Because a 2.8 ML layer of Ag cannot completely cover the Si(111) substrate17, the nonmagnetic layer is predicted
to be between 1.8 and 2.0 ML for Ni deposited on 2.8 ML Ag/Si(111) if we consider the areal contributions of the
Ni silicide and the Ni/Ag interface. In the case of Ni on the Si(111) surface that is not completely covered by Ag,
it was surprising to find that the amount of nonmagnetic layer is significantly enhanced to 2.4 ML, as shown in
Fig. 4b. Because the position of the Auger transition line for a submonolayer of Ni on 2.8 ML Ag/Si(111) is close
to that on pure Si(111), the nonmagnetic layer is related to the formation of Ni silicides. The enhancement in the
amount of the nonmagnetic layer shows that the Ag atoms serve as a catalyst to accelerate the chemical interac-
tion of Ni and Si atoms to form Ni silicides.
From the experimental evidence showing a large chemical shift for submonolayer Ni on a few ML Ag/Si(111)
(Fig. 4a), the formation of Ni silicides (Figs 2, 3 and 4a), and the enhanced dead layer (Fig. 4b), an interaction
transferring mechanism for silicon atoms across the Ag layer is proposed to explain the enhanced silicide forma-
tion that occurs at room temperature. Schematic plots to elucidate the distribution of different species after Ni
deposition showing an enhanced silicide formation are depicted in Fig. 5. From the discussions of formation
enthalpies ΔHAg-Si, ΔHNi-Ag, and ΔHNi-Si, the formation of Ag-Si particles plays a key role in enhancing silicide

Scientific Reports | (2019) 9:8835 | https://doi.org/10.1038/s41598-019-45104-3 7

www.nature.com/scientificreports/ www.nature.com/scientificreports

D G J

Ag-Si
Si Si Ag-Si
E H K
Ag-Si
Si Si Ag-Si
F I L
Ag-Si
Si Si Ag-Si

Ag Ni NiSi Ni-Ag Ag-Si

Figure 5.  Schematic plots showing distribution of different species after Ni deposition with enhanced silicide
formation.

formation. Details of this are as follows. The rationale starts with the deposition of Ag on Si(111), as shown in
Fig. 5a. A few MLs of Ag on the top of the Si(111) accumulate, with clusters being formed, as shown in Fig. 5b. The
enthalpy of formation ΔHAg-Si is a negative value (−5.9 kJ/mol)58. From the thermodynamics point of view, the
formation of Ag-Si bonding at the interface as well as the edges of the Ag islands is preferred after the deposition
of Ag on Si(111) (Fig. 5c). The formation of Ag-Si particles plays a key role in enhancing silicide formation. For
Ni deposited on the top of the submonolayer Ag/Si(111), Ni atoms can be adhered either on Si(111) patches or on
the top of the Ag islands (Fig. 5d,e,g). Because of the high reactivity of the Si(111) surface, Ni silicide formation
occurs on the Si(111) patches (Fig. 5f,h). On the top of the Ag islands, Ni-Si bonding is dominant as compared to
Ni-Ag bonding because of the large negative enthalpies of formation for Ni silicides (ΔHNiSi 2  = −29.3 kJ/mol,
ΔHNiSi  = −38.7 kJ/mol)52. The interaction transfer occurs for Si atoms via Ag-Si bonding, un-bonded from Ag-Si,
and finally bonding with Ni to form Ni silicides. This scenario causes the formation of Ni silicide on Ag clusters
to be substantially enhanced (Fig. 5f,h,i) as evidenced by the large chemical shift shown in Fig. 4b.

Conclusion
At the initial stage of Ni deposition on a Si(111) surface, dark defects with different sizes are observed and are related to
the different chemical states of Ni silicides. This can be attributed to the strong bonding between Ni and Si atoms, NiSi is
the relatively dominant species at the Ni/Si interface. Assuming that a Ni layer is formed over a NiSi layer with the total
coverage as a constraint, we established a CSRC model that represents a practical method for determining the amount
of ultrathin Ni silicides that are produced at the buried interface. Based on the morphologies, the chemical states and
related magnetic properties of Ni/Si(111), the phases of nonmagnetic Ni silicides, Ni clusters with lowered Curie tem-
peratures and ferromagnetic Ni films were resolved for different coverage regimes. For a submonolayer Ni deposited
on a few monolayers of Ag/Si(111), the chemical state of Ni was found to be closer to that for Ni silicides rather than
for Ni-Ag bonding. The finding that the amount of the nonmagnetic layer is enhanced shows that the Ag-Si particles
serve as a catalyst that promotes the chemical interaction of Ni and Si with the formation of Ni silicides. An interaction
transferring mechanism for silicon atoms across the Ag layer is proposed for the enhanced silicide formation. Based
on the formation enthalpies ΔHAg-Si, ΔHNi-Ag, and ΔHNi-Si, Ag-Si particle formation plays a key role in enhancing sil-
icide formation via a specific interaction transfer mechanism at room temperature. The data and related mechanisms
reported herein provide insights into strategies for producing ultrathin silicides at a buried interface.

Methods
All experiments were performed under ultrahigh vacuum (UHV) conditions with a base pressure of around 1 × 10−10
torr. The Si(111) substrate was cleaned by repeated Ar+ ion bombardment and annealing treatments at 1250 K until
a well-ordered 7 × 7 structure was obtained, as evidenced by STM and LEED. The LEED pattern and STM image for
Si(111)-7 × 7 structure can be found in our previous report15. The purity of the surface was checked using AES. Ni
atoms were evaporated from a resistively heated, high purity Ni coil (99.997%). Ag atoms were deposited on the surface
from a well collimated evaporator using Ag rods with a high purity (99.999%) as the Ag source. The coverage of an over-
layer was determined from the ratio of the intensities of the Auger signals of the overlayer and substrate atoms, and was
double checked using a SYCON thickness monitor of a quartz balance. For overlayers on a Si(111) surface, one ML is
equal to 0.08 nm as defined by the atomic density of substrate surface14–16. A He-Ne laser with a wavelength of 632.8 nm
was used as the light source for the SMOKE measurements. The experimental components have been described in
previous reports13–17,22,23.

Scientific Reports | (2019) 9:8835 | https://doi.org/10.1038/s41598-019-45104-3 8

www.nature.com/scientificreports/ www.nature.com/scientificreports

References
1. Kim, J. et al. Chemically homogeneous and thermally robust Ni1-xPtxSi film formed under a non-equilibrium melting/quenching
condition. ACS Appl. Mater. Interfaces 9, 566–572 (2017).
2. Jeon, K. R. et al. Voltage tuning of thermal spin current in ferromagnetic tunnel contacts to semiconductors. Nature Mater. 13,
360–366 (2014).
3. Taniyama, T., Wada, E., Itoh, M. & Yamaguchi, M. Electrical and optical spin injection in ferromagnet/semiconductor
heterostructures. NPG Asia Mater. 3, 65–73 (2011).
4. Chou, Y.-C. et al. Effect of Elastic Strain Fluctuation on Atomic Layer Growth of Epitaxial Silicide in Si Nanowires by Point Contact
Reactions. Nano Lett. 15, 4121–4128 (2015).
5. Kittl, J. A. et al. Ni- and Co-based silicides for advanced CMOS applications. Microelectron. Eng. 70, 158 (2003).
6. Cheng, S. L., Lai, R. H., Huang, Y. D. & Lin, H. C. Interfacial reactions and microstructural evolution of periodic Ni nanodot arrays
on N2+-implanted amorphous Si substrates. Appl. Surf. Sci. 399, 313–321 (2017).
7. Cassidy, C. et al. Endotaxially stabilized B2-FeSi nanodots in Si (100) via ion beam co-sputtering. Appl. Phys. Lett. 104, 161903
(2014).
8. Chiu, S.-P. et al. Ultralow 1/f Noise in a Heterostructure of Superconducting Epitaxial Cobalt Disilicide Thin Film on Silicon. ACS
Nano 11, 516–525 (2017).
9. Okuhara, Y. et al. Solar-selective absorbers based on semiconducting β-FeSi2 for efficient photothermal conversion at high
temperature. Sol. Energy Mater. Sol. Cells 161, 240–246 (2017).
10. Chen, X. et al. Structure Investigation and Dibenzothiophene Hydrodesulfurization Properties of Fe-Substituted Ni−Si
Intermetallics. J. Phys. Chem. C 119, 29052–29061 (2015).
11. Abbes, O., Melhem, A., Boulmer-Leborgne, C. & Semmar, N. Establishment of optimized metallic contacts on silicon for
thermoelectric applications. Adv. Mater. Lett. 6, 961–964 (2015).
12. Tripathi, J. K. et al. Self-organized growth and magnetic properties of epitaxial silicide nanoislands. Appl. Surf. Sci. 391, 24–32
(2017).
13. Chow, Y. T., Jiang, B. H., Chang, C. H. T. & Tsay, J. S. Enhancing magnetic anisotropy energy by tuning the contact area of Ag and Ni
at the Ag/Ni interface. Phys. Chem. Chem. Phys. 20, 1504–1512 (2018).
14. Tsay, J. S. et al. Microscopic interfacial structures and magnetic properties of ultrathin Co/Si(111) films. Appl. Phys. Lett. 88, 102506
(2006).
15. Tsay, J. S. et al. Magnetic properties and microscopic structures of ultrathin Co/√3 × √3 − R30°-Ag/Si(111) films. J. Korean Phys.
Soc. 62, 1792 (2013).
16. Chang, C. H. T., Fu, T. Y. & Tsay, J. S. Interaction transfer of silicon atoms forming Co silicide for Co/√3 × √3R30° -Ag/Si(111) and
related magnetic properties. J. Appl. Phys. 117, 17B733 (2015).
17. Tsay, J. S. et al. Effect of Ag Buffer Layer to Ultrathin Co Films on Si(111) Surface. IEEE Trans. Magn. 35, 3028 (1999).
18. Kuzmina, N. A., Svetlov, I. L. & Karachevtsev, F. N. Distribution of Substitutional Alloying Elements and Interstitial Impurities in In
Situ Multicomponent Composites Based on the Nb–Si System. Inorganic Materials: Applied Research 9, 757–762 (2018).
19. van Stiphout, K. Impurity-enhanced solid-state amorphization: the Ni-Si thin film reaction altered by nitrogen. J. Phys. D: Appl.
Phys. 52, 145301 (2019).
20. Chang, C. H. T., Kuo, W. H., Chang, Y. C., Tsay, J. S. & Yau, S. L. Tuning coercive force by adjusting electric potential in solution
processed Co/Pt(111) and the mechanism involved. Sci. Rep. 7, 43700 (2017).
21. Mangen, T., Bai, H. S. & Tsay, J. S. Structures and magnetic properties for electrodeposited Co ultrathin films on copper. J. Magn.
Magn. Mater. 322, 1863–1867 (2010).
22. Chen, W. R. et al. Formation of stacked Ni silicide nanocrystals for nonvolatile memory application. Appl. Phys. Lett. 90, 112108
(2007).
23. Chang, C. H. T., Chang, S. C., Tsay, J. S. & Yao, Y. D. Enhanced exchange bias fields for CoO/Co bilayers: influence of
antiferromagnetic grains and mechanisms. Appl. Surf. Sci. 405, 316–320 (2017).
24. Lev, L. L. et al. Band structure of the EuO/Si interface: justification for silicon spintronics. J. Mater. Chem. C 5, 192–200 (2017).
25. Lin, C. L., Wu, A. W., Wang, Y. C., Tseng, Y. C. & Tsay, J. S. Spin reorientation transitions and structures of electrodeposited Ni/
Cu(100) ultrathin films with and without Pb additives. Phys. Chem. Chem. Phys. 15, 2360–2367 (2013).
26. Hsu, H. C., Jhou, M. K., Lin, W. C. & Fu, T. Y. Thermal evolution of Fe on Ge(111)–c(2 × 8) surface and the effect of (√3 × √3)
R30◦Ag–Ge buffer layer. Appl. Surf. Sci. 355, 778–783 (2015).
27. Fu, T. Y., Wu, J. Y., Jhou, M. K. & Hsu, H. C. The role of Ag buffer layer in Fe islands growth on Ge (111) surfaces. J. Appl. Phys. 117,
17B724 (2015).
28. Shern, C. S., Ho, H. Y., Lin, S. H. & Su, C. W. Structure and magnetic properties of ultrathin Ni films on Pt(111) with Co buffer layers.
Phys. Rev. B 70, 214438 (2004).
29. Zhou, H. Q. et al. Efficient hydrogen evolution by ternary molybdenum sulfoselenide particles on self-standing porous nickel
diselenide foam. Nature Commun. 7, 12765 (2017).
30. Wang, X. D. et al. Large-Area Synthesis of a Ni2P Honeycomb Electrode for Highly Efficient Water Splitting. ACS Appl. Mater.
Interfaces 9, 32812–32819 (2017).
31. Gutic, S. J. et al. Improved catalysts for hydrogen evolution reaction in alkaline solutions through the electrochemical formation of
nickel-reduced graphene oxide interface. Phys. Chem. Chem. Phys. 19, 13281–13293 (2017).
32. Park, S. C. et al. Facile Synthesis of Highly Crystalline and Large Areal Hexagonal Boron Nitride from Borazine Oligomers. Sci. Rep.
7, 40260 (2017).
33. Liu, J. et al. Iron isotopic fractionation between silicate mantle and metallic core at high pressure. Nature Commun. 8, 14377 (2017).
34. Schuler, J. D. & Rupert, T. J. Materials selection rules for amorphous complexion formation in binary metallic alloys. Acta Materialia
140, 366–374 (2017).
35. Isern, L. et al. Structure zone diagram and particle incorporation of nickel brush plated composite coatings. Sci. Rep. 7, 44561 (2017).
36. Franco, B. E. et al. A Sensory Material Approach for Reducing Variability in Additively Manufactured Metal Parts. Sci. Rep. 7, 3604
(2017).
37. Miracle, D. B. & Senkov, O. N. A critical review of high entropy alloys and related concepts. Acta Materialia 122, 448–511 (2017).
38. Kang, J.-H., Noh, H.-S., Kim, K.-M., Lee, S. C. & Kim, S.-J. Modified Ni equivalent for evaluating hydrogen susceptibility of Cr-Ni
based austenitic stainless steels. Journal of Alloys and Compounds 696, 869–874 (2017).
39. Jiles, D. Introduction to Magnetism and Magnetic Materials, CRC Press, London, 3rd ed. (2015).
40. Bovensiepen, U., Poulopoulos, P., Farle, M. & Baberschke, K. The Curie temperature in ultrathin Ni/Cu(001) films determined by ac
susceptibility and MOKE. Surf. Sci. 402-404, 396–400 (1998).
41. Kamalakar, M. V. & Raychaudhuri, A. K. Critical phenomena in magnetic nanowires. Journal of Nanoscience and Nanotechnology 9,
5248–5253 (2009).
42. Kolmychek, I. A. et al. Anisotropy of magnetic properties in 2D arrays of permalloy antidots. J. Magn. Magn. Mater. 420, 1–6 (2016).
43. Zink, B. L. et al. Efficient spin transport through native oxides of nickel and permalloy with platinum and gold overlayers. Phys. Rev.
B 93, 184401 (2016).
44. Tengeler, S., Kaiser, B., Chaussende, D. & Jaegermann, W. 001) 3C SiC/Ni contact interface: In situ XPS observation of annealing
induced Ni2Si formation and the resulting barrier height changes. Appl. Surf. Sci. 400, 6–13 (2017).

Scientific Reports | (2019) 9:8835 | https://doi.org/10.1038/s41598-019-45104-3 9

www.nature.com/scientificreports/ www.nature.com/scientificreports

45. Dubin, V. M. et al. Invar Electroplating for Controlled Expansion Interconnects. ECS Trans. 75, 33–40 (2016).
46. Lund, I. N. et al. Influence of catalyst layer thickness on the growth of nickel silicide nanowires and its application for Li-ion
batteries. J. Power Sources 246, 117 (2014).
47. Li, F. et al. Synthesis of core–shell architectures of silicon coated on controllable grown Ni-silicide nanostructures and their lithium-
ion battery application. Cryst. Eng. Comm. 15, 7298 (2013).
48. Känel, H. V. Growth and characterization of epitaxial Ni and Co-silicide. Mater. Sci. Rep. 8, 193–269 (1992).
49. Du, Z., Ellis, S. N., Dunlap, R. A. & Obrovac, M. N. NixSi1-x alloys prepared by mechanical milling as negative electrode materials
for lithium ion batteries. J. Electrochem. Soc. 163, A13–A18 (2016).
50. O’Handley, R. C. Modern Magnetic Materials: Principles and Applications, Wiley, New York (2000).
51. Johnson, M. T., Bloemen, P. J. H., den Broeder, F. J. A. & de Vries, J. J. Magnetic anisotropy in metallic multilayers. Rep. Prog. Phys.
59, 1409–1458 (1996).
52. Lindholm, M. & Sundman, B. A thermodynamic evaluation of the nickel-silicon system, Metal. Mater. Trans. A 27A, 2897–2903
(1996).
53. Hinkel, V. et al. Evidence for Si diffusion through epitaxial NiSi2 grown on Si(111). Appl. Phys. Lett. 50, 1257–1259 (1987).
54. Ertl, G. & Küppers, J. Low Energy Electrons and Surface Chemistry, 2nd ed., VCH, Weinheim (1985).
55. Tanuma, S., Powell, C. J. & Penn, D. R. Calculations of electron inelastic mean free paths. III. Data for 15 inorganic compounds over
the 50–2000 eV range. Surf. Interface Anal. 17, 911 (1991).
56. Lide, D. R. CRC Handbook of Chemistry and Physics, CRC Press, New York, (2003).
57. Moffatt, W. G. The Handbook of Binary Phase Diagram, Genium Press, New York (1990).
58. Hassam, S., Gaune-Escard, M. & Bros, J. P. Enthalpies of Formation of Ag - Si, Au – Si and Ag-Au-Si Liquid Alloys at 1423 K. Ber.
Bunsenges. Phys. Chem. 87, 785–792 (1983).

Acknowledgements
The authors wish to acknowledge financial support from Ministry of Science and Technology of ROC under
Contract Nos. MOST 105-2112-M-003-007 and MOST 106-2112-M-003-010. This article was subsidized by the
National Taiwan Normal University (NTNU), Taiwan.

Author Contributions
C.H.T.C., P.C.J. and Y.T.C. set up the measurement apparatus. C.H.T.C., P.C.J. and Y.T.C. carried out the
experiments. J.S.T. planed and supervised the study. C.H.T.C. and J.S.T. wrote the manuscript with reviewing by
H.L.H. and W.B.S. All authors participated in discussing the results and commented on the manuscript.

Additional Information
Competing Interests: The authors declare no competing interests.
Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and
institutional affiliations.
Open Access This article is licensed under a Creative Commons Attribution 4.0 International
License, which permits use, sharing, adaptation, distribution and reproduction in any medium or
format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Cre-
ative Commons license, and indicate if changes were made. The images or other third party material in this
article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the
material. If material is not included in the article’s Creative Commons license and your intended use is not per-
mitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the
copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.

© The Author(s) 2019

Scientific Reports | (2019) 9:8835 | https://doi.org/10.1038/s41598-019-45104-3 10