Supporting Information for

Mechanism of Alkali Metal Compounds-Promoted

Growth of Monolayer MoS 2: Eutectic Intermediates

Peng Wang, 1 Jiayu Lei, 1 Jiafan Qu, 1 Shengyong Cao, 1 Hu Jiang, 1 Mengci He,1

Hongyan Shi, 1,2 Xiudong Sun, 1,2 Bo Gao, 1,2,* and Wenjun Liu 3

1Institute of Modern Optics, Department of Physics, Key Laboratory of Micro-Nano

Optoelectronic Information System, Ministry of Industry and Information Technology,

Key Laboratory of Micro-Optics and Photonic Technology of Heilongjiang Province,

Harbin Institute of Technology, Harbin 150001, China

2Collaborative Innovation Center of Extreme Optics, Shanxi University, Taiyuan

030006, China

3Department of Physics, Harbin Institute of Technology at Weihai, Weihai 264209,

China

*E-mail: [email protected]
 T (°C)

680

4 20 12 Time (min)

Figure S1. Temperature programming process used for MoS 2 growth. The CVD

system was purged with 300 sccm Ar (99.999% purity) for 4 min. The furnace was
heated from room temperature to 680 °C in 20 min, and MoS 2 was synthesized at

680 °C for 12 min under atmospheric pressure. After growth, the system was quickly

cooled down to room temperature with 105 sccm of Ar flow.

 (a) (b)

nm
0.65 nm

10 μm
μm

Figure S2. (a) AFM image of a monolayer MoS 2 flake on SiO 2/Si substrate and (b)
the height profile along the blue line in (a). The thickness of the MoS 2 layer is 0.65

nm, indicating monolayer.

 (a) E1
(b) E1
2g 2g

Intensity (a.u.)

Intensity (a.u.)
A1g
A1g

360 390 420 360 390 420

Raman shift (cm-1) Raman shift (cm-1)

Figure S3. Typical Raman spectra of MoS 2 flakes grown (a) with and (b) without

promoter. The frequency differences between E 12g and A1g modes were 19-20 cm -1,

indicating monolayer.
 NaOH Na2SO4 NaCl EDTA-4Na
E12g E12g

Intensity (a.u.)

Intensity (a.u.)

Intensity (a.u.)
Intensity (a.u.)

E12g E12g 20 μm 20 μm
25 μm 25 μm

A1g A1g
A1g A1g

360 380 400 420 360 380 400 420 360 380 400 420 360 380 400 420
Raman shift (cm-1) Raman shift (cm-1) Raman shift (cm-1) Raman shift (cm-1)

CH3COONa
1
C6H5Na3O7 KH2PO4 KI
E2g
40 μm E12g E12g 45 μm

Intensity (a.u.)

Intensity (a.u.)
Intensity (a.u.)

Intensity (a.u.)

1 40 μm 30 μm
E2g

A1g A1g A1g

A1g

360 380 400 420 360 380 400 420 360 380 400 420 360 380 400 420
Raman shift (cm-1) Raman shift (cm-1) Raman shift (cm-1) Raman shift (cm-1)

KCl KBr KOH LiCl

Intensity (a.u.) E12g 20 μm

Intensity (a.u.)
Intensity (a.u.)

Intensity (a.u.)

20 μm 1 25 μm 20 μm
E12g
E 2g E12g
A1g
A1g A1g A1g

360 380 400 420 360 380 400 420 360 380 400 420 360 380 400 420
Raman shift (cm-1) Raman shift (cm-1) Raman shift (cm-1) Raman shift (cm-1)

Figure S4. Raman spectra and optical images (inset) of MoS 2 synthesized with Na-,

K-, Li-based alkali metal compounds as promoter. All materials show promoting
effect for monolayer MoS 2 growth. More details of the Raman peaks are shown in

Table S1.
Table S1. Parameters of E 12g and A1g modes extracted from Figure S4.

E 12g FWHM_E 12g A1g FWHM_A1g A1g − E 12g

Promoter
(cm -1) (cm -1) (cm -1) (cm -1) (cm -1)

NaOH 382.18 2.57 403.51 5.34 21.33

CH 3COONa 382.28 2.34 403.26 4.79 20.98

NaCl 382.41 2.64 403.24 4.17 20.83

C 6H 5Na3O 7 382.44 2.24 403.38 4.19 20.94

Na2SO 4 382.26 2.22 402.31 4.90 20.05

EDTA-4Na 382.28 2.36 402.44 4.84 20.16

KCl 382.31 2.38 403.31 4.27 21.00

KBr 382.66 2.41 403.44 4.47 20.78

KOH 382.20 2.45 401.75 5.23 19.55

KH 2PO 4 382.54 2.33 402.97 4.74 20.43

KI 382.51 2.33 403.34 4.40 20.83

LiCl 383.14 2.66 403.33 4.54 20.19

It can be seen that all of the frequency difference between the two characteristic

Raman peaks is about 20 cm -1, which demonstrates a monolayer feature of MoS 2.

 NaNO3 NaOH Na2SO4 NaCl

200 μm 200 μm 200 μm 200 μm

NaAc EDTA-4Na C6H5Na3O7 KH2PO4

200 μm 200 μm 200 μm 200 μm

KI KBr KCl KOH

200 μm 200 μm 200 μm 200 μm

Figure S5. Large-area optical images of as-grown MoS 2 associated with alkali metal

compounds, while the insets show the images from control experiments without alkali

metal compounds. The scale bar of the insets is 50 μm.

 AgF CuCl2
AgF 25.9 cm-1
CuCl2

Intensity (a.u.)

Intensity (a.u.)
26.2 cm-1

50 μm 50 μm
360 390 420 360 390 420
-1
Raman shfit (cm ) Raman shift (cm-1)
MgCl2 ZnCl2
MgCl2 ZnCl2
21.7 cm-1

Intensity (a.u.)
Intensity (a.u.)

26.3 cm-1

50 μm 50 μm
360 390 420 360 390 420
Raman shfit (cm-1) Raman shfit (cm-1)

BaCl2 24.5 cm-1 BaCl2 CaCl2 CaCl2

26.3 cm-1
Intensity (a.u.)

Intensity (a.u.)
50 μm 50 μm
360 390 420 360 390 420
-1
Raman shift (cm ) Raman shift (cm-1)
PbI2 AlCl3
PbI2 AlCl3
20.4 cm-1
Intensity (a.u.)

Intensity (a.u.)

25.2 cm-1

50 μm 50 μm
360 390 420 360 390 420
Raman shift (cm-1) Raman shfit (cm-1)

Figure S6. Optical images and corresponding Raman spectra of MoS2 when using

non-alkali metal salts as promoters. Inhomogeneous and irregular MoS 2 flakes were

obtained on the substrates. All of those non-alkali metal salts did not show promoting
effect for MoS 2 growth.
 100
1.0

Deriv. Weight (%/°C)

80
Pure MoO3

Weight (%)
60
0.5
40

20
0.0
0
0 200 400 600 800 1000
Temperature (°C)

Figure S7. TG-DTG curves of pure MoO 3 in Ar with a temperature ramping rate of

10 ℃/min.
 ● ■ MoO3
(a) (b) ◆MoO2
● SiO2

Intensity (a.u.)
★ K2MoO4
◆ ◆
★
◆
★◆
◆ ◆ ◆ ■★

30 μm
200 400 600 800 1000
Raman shift (cm-1)

(c) (d)

30 μm
Energy (keV)

Figure S8. Two-step growth experiment using KCl as promoter. (a) Eutectic

intermediates synthesized from MoO 3 and KCl. The corresponding Raman spectra

and EDS are shown in (b) and (d), respectively. There are multiple Raman peaks for
MoO 3-x and K 2MoO 4 from eutectic intermediates.1 From EDS, we did not observe

peak of chlorine. The high volatile metal oxychlorides are not a constituent

component of the intermediates after high temperature annealing. (c) Triangular MoS 2
flakes were obtained after the substrate with randomly distributed eutectic particles

was loaded back to CVD system for sulfurization. Impurities are marked by red arrow

lines as references. The location of the formed MoS 2 flakes does not match eutectic

particles.
 Intermediate products Intermediate products
synthesized by ZnCl2 synthesized by Cu(NO3)2

Intensity (a.u.)

Intensity (a.u.)
40 μm 40 μm
300 600 900 300 600 900
Raman shift (cm ) -1 Raman shift (cm-1)

A1g A1g
After sulfurization After sulfurization
Intensity (a.u.)

Intensity (a.u.)
ZnCl2 E1
2g
Cu(NO3)2
E1
2g

40 μm 40 μm
360 380 400 420 360 380 400 420
Raman shift (cm-1) Raman shift (cm-1)

Figure S9. Two-step growth experiment using ZnCl 2 and Cu(NO 3)2 as promoter was

performed. Irregular islands composed of small particles were observed from OM

images of intermediate products synthesis. The Raman peaks of ZnMoO 42 and

CuMoO 43 rarely detectable. Large amount of stacked MoS 2 particles rather than

tringle flakes were obtained after sulfurization. Moreover, the optical images after

sulfurization match pretty well with those before sulfurization, indicating no

migration in the sulfurization process.
 NaNO3 500℃ NaNO3 480℃

50 μm 50 μm

E12g E12g

A1g

Intensity (a.u.)
Intensity (a.u.)

A1g

360 380 400 420 360 380 400 420

Raman shift (cm-1) Raman shift (cm-1)

Figure S10. MoS2 growth with NaNO 3 at lower temperature. We still got triangular

MoS2 flakes, but dense, small and thick compared to those at 680 ℃.
 Table S2. Thermodynamic data and the Gibbs free energy

Eutectic ΔGS2 ΔGS2 ΔGS3 ΔGS3

Element Alkali/Salt 4-7 4-7 4-7
Point/℃ 298.15K 1000K 298.15K 1000K4-7

LiOH
Li 5288, 5299 -1054.69 -781.314 -1848.871 -1448.324
LiCl
NaOH

NaNO3
Na 52510 -1049.418 -785.3 -1592.201 -806.342
CH3COONa
Na2SO4
NaCl
KOH
KCl
KBr
K KI 462~4929 -1010.291 -1072.928 -1384.913 -941.232

KH2PO4

KNO3

Ag AgF 49611, 12 -1342.5 -1270.406

Pb PbI 2 74413 -1195.181 -927.292 -1273.438 167.572

CuCl 2
Cu 70014, 71015 -1293.085 -1031.818 -1664.327 -387.878
Cu(NO3) 2
Mg MgCl 2 75016 -1095.241 -832.692 -2089.795 -1305.73

72617
Ca CaCl 2 -1082.454 -821.922 -1879.856 -1108.806
726±318

Ba BaCl 2 63517 -1065.499 -809.046 -95.19 1786.328

Zn ZnCl 2 71019

Al AlCl 3 74020

We propose the formation of alkali metal molybdates during growth as follow:

M a X  MoO3-x  M 2 MoO 4  M 2 Mo 2O 7 + byproduct  (S1)

Two main reactions may occur between alkali metal molybdates and sulfur. ΔG S2 and

ΔG S3 represent the Gibbs free energy in Equations S2 and S3, respectively.

 2M 2 MoO4 + 7S → 2MoS2 + 2M 2O + 3SO2 (S2)

M 2 MoO4 + 5S → MoS2 + M 2S + 2SO2 (S3)

The negative value of Gibbs free energy (ΔG) in each equation imply the reaction can

occur positively. The eutectic point is significantly low for alkali metal molybdates
with molybdenum oxide. Eutectic intermediates are at melting state at growth

temperature and have high mobility on SiO 2/Si. So they tend to collide with each

other and joint together to promoter MoS 2 growth in the presence of sulfur vapor.
Eutectic points of non-alkali metal molybdates and molybdenum oxides are higher

than growth temperature, except for AgF. There are more nuclei and hence dense

flakes, along with smaller size and more layers. We think that decomposable AgF into
pure silver, rather than silver molybdates, did not catalyze triangular MoS 2 growth.
Figure S11. MoS2 growth at 800 ℃ associated with ZnCl 2 (left) and Cu(NO 3)2 (right)，

respectively. A large amount of white fibrous silicon sulfide with pungent smell was

formed due to the SiO 2/Si substrate.

REFERENCES

(1) Saraiva, G. D.; Paraguassu, W.; Freire, P. T. C.; Maczka, M.; Mendes, J.

Temperature-Dependent Raman Scattering Study of K 2MoO4. Vib. Spectrosc., 2012, 58, 87-94.

(2) Hu, D. Q.; Wang, Y.; Huan, W. L. Structural and Photoluminescent Properties of

BaxZn1-xMoO4:Eu3+ Phosphors Synthesized by Solid-State Reaction Method. J. Mater. Sci.: Mater.

Electron., 2015, 26, 1311-1315.

(3) Frost, R. L.; Bouzaid, J.; Butler, I. S. Raman Spectroscopic Study of the Molybdate

MineralSzenicsiteand Comparison with Other Paragenetically Related Molybdate Minerals.

Spectrosc. Lett., 2007, 40, 603-614.

(4) Reddy, K. J.; Drever, J. I. Geochemical Modeling Research Related to the Surface Disposal of

Processed Oil Shale Solid Waste.[Elements and Compounds in Oil Shale Wastes]. Western

Research Inst., Laramie, WY (USA), 1987.

(5) Barin, I. Thermodymamical Data of Pure Substances (3rd edit.), 1995.

(6) Chase Jr, M. W.. NIST-JANAF thermochemical tables fourth edition. J. Phys. Chem. Ref. Data,

Monograph, 1998, 9.

(7) Physico-chemical properties of substance, http://chemister.ru/Database/search-en.php

(accessed September 4th, 2018).

(8) Parmentier, M.; Reau, J. M.; Fouassier, C. and Gleitzer, C.. Polymolybdate und

Polywolframate von Lithium. Bull. Soc. Chim. Fr., 1972, 5, 1743-1746.

(9) Hoermann, F. Beitrag zur Kenntnis der Molybdate und Wolframate. Die binären Systeme:

Li 3MoO4-MoO3, Na2MoO4-MoO3, K3MoO4-MoO3, Li 2WO4-WO3, Na2WO4-WO3, K2WO4-WO3,

Li 2MoO4-Na2MoO4, Li 2WO4-Na2WO4, Li 2MoO4-K2MoO4. Z. Anorg. Allg. Chem., 1929, 177,

145-186.

(10) Singh Mudher, K. D.; Keskar, M.; Krishnan, K.; Venugopal, V. Thermal and X -Ray

Diffraction Dtudies on Na2MoO4, Na2Mo2O7 and Na2Mo4O13. J. Alloys Compd., 2005, 396,

275-279.

(11) Wenda, E. Phase Diagram of the V 2O5-MoO3-Ag2 O System. J. Therm. Anal. Calorim., 1990,

36, 1417-1427.

(12) Wenda, E. High Temperature Reactions in the MoO 3-Ag2O System. J. Therm. Anal. Calorim.,
1998, 53, 861-870.

(13) Nihtianova, D. D.; Shumov, D. P.; Angelova, S. S.; Dimitriev, Y. B.; Petrov, L. L.

Investigation of Pb 5MoO8 Crystal Growth in PbOMoO3 System. J. Cryst. Growth, 1997, 179,

161-167.

(14) Nassau, K.; Shiever, J. W. Cupric Oxide-Molybdenum Oxide Phase Diagram in Air and in

Oxygen. J. Am. Ceram. Soc., 1969, 52, 36-40.

(15) Machej, T.; Ziołkowski, J. Phase Diagram of the CuO-MoO3 System. Mater. Chem., 1979, 4,

113-121.

(16) Tsuzuki, A.; Kani, K.; Watari, K.; Torii, Y. Phase Relations in the MoO 3-MgMoO4 System. J.

Mater. Sci. Lett., 1992, 11, 334-335.

(17) Ropp, R. C. Group 9 (Co, Rh and Ir) Alkaline Earth Compounds. 2013, 961-1004.

(18) Yanushkevich, T. M.; Zhukovskij, V. M. Phase Diagram of MoO3-CaO System. Zh. Neorg.

Khim., 1973, 18, 2234-2237.

(19) Kohlmuller, R.; Faurie, J. P. Etude Des Systemes MoO3-Ag2MoO4 et MoO3-MO (M-Cu, Zn,

Cd). Bull. Soc. Chim. Fr., 1968, 11, 4379-4382.

(20) Dąbrowska, G.; Tabero, P.; Kurzawa, M. Phase Relations in the Al 2O3-V 2O5-MoO3 System in

the Solid State. The Crystal Structure of AlVO4. J. Phase Equilib. Diff., 2009, 30, 220-229.