Thin Solid Films

Molybdenum (Mo) layer effect on electrical properties of MoSi2 films using Mo/MoSi2
stack structures
--Manuscript Draft--

Manuscript Number: TSF-D-20-01445

Article Type: Full Length Article

Section/Category: B. Surfaces, Interfaces, and Colloidal Behaviour

Keywords: Thin Film Deposition; Molybdenum Silicide; Sheet Resistance; Rapid Thermal
Annealing

Corresponding Author: Hi-Deok LEE

Chungnam National University
Daejeon, KOREA, REPUBLIC OF

First Author: Hi-Deok LEE

Order of Authors: Hi-Deok LEE

Sunil Babu Eadi

Ki-Woo Song

Hyun-jin Shin

Hyun-Woong Choi

Abstract: In this report, the effect of Mo/MoSi2 stack structure on the structural and electrical
properties of MoSi2 film grown by using RF Sputtering machine are investigated. The
Sheet resistance (Rsh) verse quasi Mo and MoSi2 top structures were measured with
varying temperature using Rapid Thermal Annealing Process (RTA) in the range of RT-
950°C respectively. The lowest Rsh were obtained at RTA temperature of 950 °C with
Rsh values 30.8, 18.5, 27.7 and 25.2 Ω/sq. for M-1 (MoSi2 top (10 nm)), M-2 (Mo top
(10 nm)), M-3 (Mosi2 top (20 nm)) and M-4 (Mo top (20 nm)) respectively. The
enhancement of interfacial properties by introduction of Mo interlayer are investigated.

Suggested Reviewers: Nersusyan Hayk

haykrasom@hotmail.com
Material scientist

Murali Banavoth
murali.banavoth@uohyd.ac.in
Material Scientist

Thambidurai M
phy_thambi@rediffmail.com
Material Scientist

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Cover Letter

Please reply to :
Prof. Hi-Deok Lee
Dept. of Electronics Engineering
Chungnam National Univ., Gung-dong,
Yuseong-Gu, Daejeon, 305-764, Korea
TEL : +82-42-821-6868
FAX : +82-42-823-9544
E-mail : hdlee@cnu.ac.kr

Nov. 25, 2020

Dear Editor,

We wish to submit an article for publication in Thin Solid Films, titled

“Effect of Mo layer on electrical properties of MoSi2 films using Mo/MoSi2 stack
structures” the paper was coauthored by Sunil Babu Eadi, Ki-Woo Song, Hyun Jin Shin,
Hong Woong Choi, and all the authors are aware of the content and approve this
submission. There are no conflicts of interest to declare.

Here in, we demonstrated effective way for Mo and MoSi2 reaction using Rapid thermal
annealing process for low contact resistance. The results confirms, the reduction in sheet
resistance under RTA operating temperature from RT-950 °C.

We believe that our study makes a significant contribution to the literature because we
demonstrate that the Mo/MoSi2 interaction depends on the stack formation with respect
to Mo top or MoSi2 top structure.

Further, we believe that this paper will be of interest to the readership of your journal
because this study can serve as a basis for developing high heating elements based on
MoSi2.

This manuscript has not been published or presented elsewhere in part or in entirety and
is not under consideration by another journal. We have read and understood your
journal’s policies, and we believe that neither the manuscript nor the study violates any of
these. There are no conflicts of interest to declare.
Thank you for your consideration. I look forward to hearing from you.

Sincerely,
Hi-Deok Lee
Highlights (for review)

Highlights

 Demonstrated the Mo/MoSi2 interaction using rapid thermal annealing process

(RTP).
 Low sheet resistance values of 18.5, 27.7 Ω/sq. were achieved using Mo top stack
structures.
 Successfully achieved low resistive contacts using Mo/MoSi2 s stack.
 RTP process enabled contacts shown high stability
Manuscript Click here to view linked References

Molybdenum (Mo) layer effect on electrical properties of

MoSi2 films using Mo/MoSi2 stack structures
Sunil Babu Eadi1, Ki-Woo Song1, Hyun-jin Shin1, Hyun-Woong Choi1 and Hi-Deok Lee1*
1
Department of Electronics Engineering, Chungnam National University, Daejeon, Korea.
*Correspondence author: hdlee@cnu.ac.kr; Tel.: (+82-042-821-7702)

Abstract: In this report, the effect of Mo/MoSi2 stack structure on the structural and electrical
properties of MoSi2 film grown by using RF Sputtering machine are investigated. The Sheet
resistance (Rsh) verse quasi Mo and MoSi2 top structures were measured with varying
temperature using Rapid Thermal Annealing Process (RTA) in the range of RT-950°C

respectively. The lowest Rsh were obtained at RTA temperature of 950 °C with Rsh values

30.8, 18.5, 27.7 and 25.2 Ω/sq. for M-1 (MoSi2 top (10 nm)), M-2 (Mo top (10 nm)), M-3

(Mosi2 top (20 nm)) and M-4 (Mo top (20 nm)) respectively. The enhancement of interfacial
properties by introduction of Mo interlayer are investigated.

Keywords: Thin Film Deposition, Molybdenum Silicide, Sheet Resistance, Rapid Thermal
Annealing

Introduction
Molybdenum disilicide (MoSi2) owing its unique properties, such as high melting

point (2030°C), oxidation resistance by forming thin SiO2 layer on the surface, and high

electrical conductivity, low density (~6.24 g/cm3), is widely used in many industrial
applications like furnace heating parts, airplane’s turbines, engines plugs and non air
combustions chambers and high temperature appliances materials [1-4].
In recent years, Making of MoSi2 was demonstrated by various techniques for different
application. Kim et al., reported the MoSi2 making using Ball milling process for the
application of high temperature induction heating [5]. Hayk et al., studied the preparation of
MoSi2 fine power using rapid combustion process using MoO3 and SiO2 precursors in sodium
chloride medium [6]. Timothy et al., reported the metalothermic reduction technique using
chlorine transfer reaction [7]. However, all this methods introduces impurities to the chemical
precursors and ununiformed particles sizes. Thus for preparation of uniform thin films of MoSi2,
physical vapor deposition such as sputtering is most advantageous [8-10].
Electrical properties of MoSi2 films are important factor for various application such as
heating elements and electrical contacts. Various groups have reported the increase in electrical
conductivity of MoSi2 using additives materials. Rujie et al., reported MoSi2 mixing with ZrB2-
20 vol% SiC improve the electrical properties for using as high heating elements [11]. Gunes
et al., studied the electrical properties of MoSi2 with Al2O3 composites materials with

conductivity of 126-12 S/cm at 900 °C [12]. However, MoSi2-Mo stack structures with low

resistivity under different annealing temperature are not fully explored. In this report, uniform
MoSi2 films with various stack structures with Mo were investigated with respect to Rapid
thermal annealing process (RTP) and electrical characteristics were measured.

Experimental Procedure
Furnace grown SiO2 with thickness of 150 nm on Silicon was used as substrate materials.
Prior to deposition, the substrates were cleaned using Acetone and Iso propyl alcohol (IPA) and
dried using N2 gas purge and inserted in the sputtering chamber. The sputtering chamber was
evacuated until the vacuum level reached to 10-7 Torr. Then Ar gas was flown in to chamber
and pressure was controlled at 2 mTorr through out the deposition process. Pre-Sputtering time
was fixed to 5 min. MoSi2 target with RF power of 80W was used for sputtering for 10 min to
obtain 20 nm MoSi2 film. Prior to deposition, deposition test was conducted for precise
thickness of MoSi2 films. Different MoSi2 films were deposited by Mo/MoSi2 layers and their
structural and electrical properties were investigated with respect the Rapid thermal annealing
process (RTP).

Results and Discussion

Initially, MoSi2 thin film with an average thickness of 20 nm was treated with RTP
process. The temperature of the RTA chamber was raised in 8s and maintained for 30 s and
cooled. All the annealing process was performed under vacuum condition. The schematics of
the RTP can be seen in the Fig.1 (a). Fig.2 (a) shows the Raman Spectrums of the MoSi2 films
done treatment using RTP. It is seen that, no characteristic peaks of MoSi2 were seen till the

temperature of 600 °C. The peaks started to appear after RTA temperature of 700 °C and

intensity of the peaks increase with temperature. MoSi2 characteristic peaks appears at 320.7
and 428.2 cm-1 position which confirms the phase change phenomenon in the MoSi2 film with
temperature, the results coincides with the pervious reported [13,14]. To check the change,
Sheet resistance (Rsh) of the RTA treated samples were measured. Fig.2 (b) shows the change
in Rsh of the MoSi2 film with change in the operating temperature. The effect of RTP can be

clearly seen the plot, as the Rsh increased from the 300 °C till 600 °C implying the hexagonal

phase of the MoSi2 film. The Rsh see a sudden drop after RTP temperature raised to 700 °C,

which indicated the change in the structural phase from hexagonal to tetragonal phase. The

Rsh decreased further with increase in temperature and lowest Rsh was obtained at 900 °C.

The Rsh of 0.97, 0.82 and 0.34 kΩ/Sq. were obtained for As-deposited (RT), at 600 °C and

900 °C respectively.

Further, multi stack structures of Mo and MoSi2 with different combinations were fabricated
to check there effect on the electrical characteristics. The RTA process was performed as done
for the single MoSi2 film. Fig.3 (a-d) shows the schematics of different Mo/MoSi2 structures
with Mo or MoSi2 with 10 nm and 20 nm thickness. The combinations were deposited with
controlled deposition test for both Mo and MoSi2. For reference, all the structures are named
M-1 (MoSi2 top (10 nm)), M-2 (Mo top (10 nm)), M-3 (Mosi2 top (20 nm)) and M-4 (Mo top
(20 nm)) respectively. The Rsh with respect to RTA temperatures measured are shown in Fig.
3(e). In the case of multi stack structures the trend of the films Rsh show downward trends
with increase in the RTA temperature. The Rsh values of the As deposited sample were 1106,

49.3, 61.8 and 74 02 Ω/sq. for M-1, M-2, M-3 and M-4 respectively. Table.1 shows the Rsh

values of all the four different Mo/MoSi2 stack combinations. The lowest Rsh was obtained at

RTA temperature of 950 °C with Rsh values 30.8, 18.5, 27.7 and 25.2 Ω/sq. respectively. The

trends from the table shows stack structures with Mo (M-2 and M-3) on top shows lower Rsh
values which could be beneficial for MoSi2/Mo contacts. Fig.4 (a) shows the cross sectional
FESEM images of M-2 and M-3 respectively. The average thickness were measured to be ~
50 and 40 nm respectively. The SEM images clearly shows the before and after effect of RTA
annealing on the samples. The samples before RTA show uniform film thickness throughout,

however the film surface show uneven roughness after annealing at the 950 °C. Also, it is

noticed that, color of the sample surface changed from pale gray to light blue with RTA
 temperature as shown in Fig.5 (a) for M-2 structures. This change in color can be attributed
to reaction between the Mo and MoSi2 from initial gray metallic color with increase in the
RTA temperature. Further, Atomic force microscopy images of M-2 are shown in Fig.5 (b,c),

the images are taken for samples at room temperature and final 950 °C RTA samples. The

surface morphology clearly indicates the change in the grain size and shape from RT to 950 °

C. The RMS values obtained are 1.58 and 4.19 nm for RT and 950 °C respectively.

Fig.7 (a) shows the X-ray diffraction (XRD) studies of the M-2 sample with various RTA
temperatures. The peaks corresponding to MoSi2 and Mo can be clearly seen in as deposited
sample with (110) and (200) peaks at 40° and 58° respectively. The intensities of the peaks
increased with temperature until 600 °C. At this temperature, sharp peak at 40° become broad.
Other peaks related to MoSi2 are (101), (103), (112) and (604) which appeared 27°, 34° and
27° respectively. Also at this temperature, new peaks (221), (400) and (321) corresponding to
Mo5Si3 stared appearing at 27°, 34° and 27° respectively and with peak intensities increased
with temperature [14]. Also Fig.7 (b) shows Raman spectrums of M-2, It is noticed that, here
also as MoSi2 film in Fig.2 (a), no characteristic peaks of MoSi2 were seen until the RTA

temperature of 600 °C. Peaks starts to appear after RTA temperature between 600-700 °C

and peak intensity increased with temperature till 950 °C. This confirms the interaction

between the Mo and MoSi2 above 600 °C is very high. However, to evaluate the effect still
investigations are needed. Thus, rapid thermal process could be way for selective Mo and
MoSi2 interaction for low resistive contacts film can be formed for high heating element
applications.

Conclusions
This paper reports the successful formation of MoSi2/Mo stack structures using RF-

sputtering process. The low sheet resistance of Rsh of 0.97, 0.82 and 0.34 Ω/Sq. were

measured under RTP process in the temperature range of RT-950 °C. The results demonstrate

the Mo top structures show lower sheet resistance under RTP temperature of 950 °C in

comparison to MoSi2. This structure could be a new template for high conductive elements
applications using MoSi2 materials.
Acknowledgments
This research was supported by Ministry of Science and ICT, the National Research
Foundation of Korea (NRF) (2019M3F3A1A01074449) and support program for the
development of intelligent semiconductor leading technology.

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Figures

Fig.1. Schematics of the Rapid Thermal process (RTP) machine and process flow of RTP done
in this experiments.

Fig.2 (a) shows the Raman Spectrums of the MoSi2 films done treatment using RTP under

operating range of RT-950 °C and Fig.2 (b) Rsh of the MoSi2 film with change in the operating

temperature.

Fig.3 (a-d) Schematics of different Mo/MoSi2 structures with Mo or MoSi2 with 10 nm and 20
nm thickness and Fig.3 (e) Sheet Resistance verses RTA temperature for different Mo/MoSi 2
stack structures respectively. .

Fig.4 (a-d) shows the cross sectional FESEM images of M-2 and M-3 at RT and RTP operating

temperature of 950 °C before and after respectively.

Fig.5 (a) shows the pictures of RTP processes M-2 samples with different operating

temperature form RT-950 °C respectively and Fig.5 (b,c) AFM images of M-2 at RT and RTP

operating temperature of 950 °C respectively.

Fig.6 (a, b) X-ray diffraction (XRD) and Raman spectrums of the M-2 sample with various
RTA temperatures.
Fig.1. Schematics of the Rapid Thermal process (RTP) machine and process flow of RTP done
in this experiments.
Fig.2 (a) shows the Raman Spectrums of the MoSi2 films done treatment using RTP under

operating range of RT-950 °C and Fig.2 (b) Rsh of the MoSi2 film with change in the operating

temperature.
Fig.3 (a-d) Schematics of different Mo/MoSi2 structures with Mo or MoSi2 with 10 nm and 20
nm thickness and Fig.3 (e) Sheet Resistance verses RTA temperature for different Mo/MoSi 2
stack structures respectively. .
Fig.4 (a-d) shows the cross sectional FESEM images of M-2 and M-3 at RT and RTP operating

temperature of 950 °C before and after respectively.

Fig.5 (a) shows the pictures of RTP processes M-2 samples with different operating

temperature form RT-950 °C respectively and Fig.5 (b,c) AFM images of M-2 at RT and RTP

operating temperature of 950 °C respectively.

Fig.6 (a, b) X-ray diffraction (XRD) and Raman spectrums of the M-2 sample with various
RTA temperatures.
Declaration of Interest Statement

Declaration of interests

☒ The authors declare that they have no known competing financial

interests or personal relationships that could have appeared to influence
the work reported in this paper.

Date: November 25, 2020