Supporting Information for

Real-time Investigation of Sulfur Vacancy

Generation and Passivation in Monolayer

Molybdenum Disulfide via in situ X-ray

Photoelectron Spectromicroscopy

Theresa Grünleitner,a Alex Henning,a,* Michele Bissolo,a Marisa Zengerle,a Luca Gregoratti,b

Matteo Amati,b Patrick Zeller,b,†,‡ Johanna Eichhorn,a Andreas V. Stier,a Alexander W.

Holleitner,a Jonathan J. Finleya, and Ian D. Sharpa,*

a
Walter Schottky Institute and Physics Department, Technical University of Munich, Am

Coulombwall 4, 85748 Garching, Germany

b
Elettra - Sincrotrone Trieste SCpA, AREA Science Park, Strada Statale 14 km 163.5, 34149,

Trieste, Italy

† present address: Helmholtz-Zentrum Berlin für Materialien and Energie GmbH, BESSY II,

Albert-Einstein-Straβe 15, 12489 Berlin, Germany

‡
present address: Fritz-Haber-Institut der Max-Planck-Gesellschaft, Dept. Inorganic Chemistry,

Faradayweg 4-6, 14195 Berlin, Germany

*
Corresponding authors: sharp@wsi.tum.de, alex.henning@wsi.tum.de
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Figure S1. Si/SiO2 substrate coated with transparent conductive film (TCF) consisting of

nanocrystalline carbon (nc-C) capped with a 1 nm thin aluminum oxide (AlO x) layer. This

conductive support is suitable for direct CVD of MoS2. Adapted from ref.1

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Figure S2. Raman spectra of MoS2 around 150 cm-1 for (a) pristine MoS2 flakes, (b) low X-ray

doses, (c) high X-ray doses, and (d) oxygen passivated SV in MoS2 flakes. The lack of a spectral

feature around this wavenumber indicates 2H- and not 1T-MoS2. Measurement points from cosmic

background radiation are not depicted.

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Figure S3. (a) SV integrated area extracted from S 2p core level spectra (green, left axis) and S 2p

integrated area (blue, right axis). (b) Normalized Mo 3d area over dose shows no Mo loss upon X-

ray exposure and no carbon deposition during defect generation.

The absolute concentration of SVs cannot be extracted due to an unknown mixture of VS and

V2S, where photoemission from 6 neighboring S atoms in the same plane are affected by the

presence of a single VS and 12 S atoms are affected by the presence of a single V2S (accounting

for 6 S atoms in the upper and 6 S atoms in the lower S plane).2 This agrees well with the linear

increase of the SV component extracted from the S 2p spectrum because photoemission from 6

additional S atoms is affected upon formation of one V2S out of an existing VS. This leads to the

same increase of the SV component of the S 2p signal for generation V2S and for VS, assuming

that V2S are only generated from VS sites. The final concentration of SV extracted from the S 2p

spectrum therefore lies between ~6% (only V2S) and ~12% (only VS).

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Figure S4. Difference between VB spectra after X-ray exposure and with VB spectrum with

minimal dose without correcting for dose-dependent spectral shifts.

In previous studies, calculations of the change of VB photoemission with defect generation did

not correct for spectral shifts that occur due to the change of Fermi level position.2–4 Using that

approach, we observe similar spectral changes near the VB onset with increasing dose (Figure

S4). This analysis shows a saturation characteristic at high doses that is consistent with the shift of

the VB towards the Fermi edge. However, we want to note that using this method, one cannot

exclude that the difference spectrum is dominated by VB onset shift, which would give the

appearance of additional intensity at the VB edge even in the absence of newly generated occupied

states. Therefore, the data presented in the main manuscript (Figure 3d) were first aligned along

the energy axis using the Mo 3d core level positions before calculating the difference spectra.

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Figure S5. Schematic representation of the electronic states associated with SV defect states,

adapted from the prior report of ref.5 and with qualitative energetic positions and occupancies

consistent with the present study.

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Figure S6. Mo 3d and S 2p XPS spectra of X-ray exposed MoS2 flakes before (a,d) and after (b,e)

exposure to ambient air and (c,f) after additional in situ annealing. As we observe no peak shift or

changed intensity of the SV related peaks after annealing, we assume the vacancies to be stable in

air for several minutes.

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Figure S7. O 1s XPS core level spectra of (a) pristine MoS2, (b) SV in MoS2 after 5 min. air

exposure showing a drastic increase of the contribution of O-H, organic and defect oxygen, but no

additional O-Mo feature. (c) SV in MoS2 after oxygen in situ showing newly formed O-Mo bonds,

and (d) nc-C/AlOx substrate.

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Figure S8. Raman spectra of MoS2 around 227 cm-1, 754 cm-1, 784 cm-1, and 820 cm-1 for (a,e)

pristine MoS2 flakes, (b,f) low SV concentration, (c,g) high SV concentration, and (d,h) oxygen

passivated SV in MoS2 flakes. The vertical dotted lines are a guide for the eye and are at the

respective wavenumbers.

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Figure S9. PL spectra of MoS2 (black) with PL spectra of the substrate (green) for (a-c) different

doses and (d) after oxygen passivation. Although extremely weak PL emission is observed from

the substrate, it differs from the PL signal measured on MoS2. Thus, the PL signals discussed in

the main text can be unambiguously assigned to MoS2.

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