Journal Pre-proof

Thinner 2D α-MoO3 makes setting up memristors easier

Yukun Hong, Shangui Lan, Baojun Pan, Zhixiang Zhang, Bingbing Chen, Lijie Zhang,
Peijian Wang

PII: S2352-8478(24)00031-5
DOI: https://doi.org/10.1016/j.jmat.2024.01.012
Reference: JMAT 837

To appear in: Journal of Materiomics

Received Date: 15 November 2023

Revised Date: 8 January 2024
Accepted Date: 28 January 2024

Please cite this article as: Hong Y, Lan S, Pan B, Zhang Z, Chen B, Zhang L, Wang P, Thinner 2D α-
MoO3 makes setting up memristors easier, Journal of Materiomics (2024), doi: https://doi.org/10.1016/
j.jmat.2024.01.012.

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© 2024 Published by Elsevier B.V. on behalf of The Chinese Ceramic Society.

 Thinner 2D α-MoO3 makes setting up
memristors easier
Yukun Hong,#,1 Shangui Lan,#,2 Baojun Pan,3 Zhixiang Zhang,2 Bingbing Chen4, Lijie

Zhang,**,1 Peijian Wang*,1

1
Key Laboratory of Carbon Materials of Zhejiang Province, College of Chemistry and

Materials Engineering, Wenzhou University, Wenzhou 325035, Zhejiang, China

f
2
ZJU-Hangzhou Global Scientific and Technological Innovation Center, Zhejiang

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University, Hangzhou 311215, China

pr
e-
3
Macao Institute of Materials Science and Engineering (MIMSE), MUST-SUDA Joint
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Research Center for Advanced Functional Materials, Macau University of Science and

Technology, Taipa 999078, Macao, China.

al
rn

4
Department of Energy Science and Engineering, Nanjing Tech University, Nanjing
u

210009, China
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#
These authors contributed equally to this work.

*
Corresponding author.

**
Corresponding author.

Email addresses: ljzhang@wzu.edu.cn (L. Zhang), Peijian Wang

(pjwang@wzu.edu.cn) (P. Wang).

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ro
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 Thinner 2D α-MoO3 makes setting up memristors

easier
Yukun Hong,#,1 Shangui Lan,#,2 Baojun Pan,3 Zhixiang Zhang,2 Bingbing Chen4, Lijie Zhang,*,1

Peijian Wang*1
1
Key Laboratory of Carbon Materials of Zhejiang Province, College of Chemistry and Materials

of
Engineering, Wenzhou University, Wenzhou 325035, Zhejiang, China

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2
ZJU-Hangzhou Global Scientific and Technological Innovation Center, Zhejiang University,

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Hangzhou 311215, China re
3
Macao Institute of Materials Science and Engineering (MIMSE), MUST-SUDA Joint Research
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Center for Advanced Functional Materials, Macau University of Science and Technology, Taipa

999078, Macao, China.

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4
Department of Energy Science and Engineering, Nanjing Tech University, Nanjing 210009,
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China
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Keywords: Ultrathin molybdenum trioxide, thickness controlling, high transferability, memristor,

low power consumption

ABSTRACT:

Two-dimensional (2D) metal oxide α-MoO3 shows great potentials because of its very high

dielectric constant, air stability and anisotropic phonon polaritons. However, a method to produce

ultrathin single crystalline α-MoO3 with high transferability for functional device architecture is

1
lacking. Herein, we report on the controllable synthesis of ultrathin α-MoO3 single crystals via

chemical vapor deposition (CVD) assisted by plasma pretreatment. We also carried out systematic

computational work to explicate the mechanism for the slantly-oriented growth of thin nanosheets

on plasma-pretreated substrate. The method possesses certain universality to synthesize other

ultrathin oxide materials, such as Bi2O3 and Sb2O3 nanosheets. As-grown α-MoO3 presents a high

dielectric constant (≈ 40), ultrathin thickness (≈ 3nm) and high transferability. Memristors with

α-MoO3 as the functional layers show excellent performance featuring high on/off ratio of

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approximately 104, much lower set voltage around 0.5 V, and highly repetitive voltage sweep

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endurance. The power consumption of MoO3 memristors is significantly reduced, resulted from

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reduced thickness of the MoO3 nanosheets. Single crystal ultrathin α-MoO3 shows great potentials
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in post-Moore memristor and the synthesis of CVD assisted by plasma pretreatment approach
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points to a new route for materials growth.

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1. Introduction
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Memristor is a type of device promising for integrating computational and memory devices
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together in the post-Moore era, beneficial for tackling the problem of “Memory wall” and “Heat

wall” in the conventional von Neumann architecture, showing great potentials for memory device

and neuromorphic electronics.[1,2] In the electrochemical metallization (ECM) memristor, an

electrochemical deposition and dissolution of a metallic conductive bridge is exploited to perform

the resistive switching operation. One possible way of designing the memristor structure is

depositing an insulating thin film layer with a high "κ" dielectric sandwiched between two

conducting layers in a metal-insulator-metal (MIM) structure. Thus, the thickness is important in

building memristors mediated by 2D materials, involving with several reasons. Firstly, in

memristors, the thickness of functional layers determines the length of filament formed by metallic

2
atoms or oxygen vacancies driven by the voltage. Shorter the length of filament is, the lower the

power consumption its formation takes. Moreover, the thinner thickness is beneficial for the device

dimension shrinking and scalable integration. Besides, transferability is also a significant issue

because in the MIM structure, the fabrication of the contact between the bottom electrode and the

materials normally needs a transferring procedure for integration. But in the epitaxial growth, the

interaction between the materials and the substrates are relatively strong, resulting in difficulties

in the separation between the epitaxial materials and substrates and also flexible choices of contact

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interfaces. [3]

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Compared with the extremely hot area of graphene and transition metal dichalcogenides

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(TMDs), [4–6] two-dimensional metal oxides (2D MOs) consisting of at least one metal cation and
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an oxygen anion, are relatively less dived into. Recently, 2D MOs induce researchers’ interests for
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their superior air stability, high dielectric constants, and excellent electronic, optoelectronic,
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magnetoelectronic properties.[7,8] For example, high-κ 2D Sb2O3 appeared as an excellent van der
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Waals dielectric layer for building high performance 2D field effect transistors (FETs),
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highlighting a low subthreshold slope (SS) of 64 mV/dec and high on/off ratio of 108.[9] Among

MOs, layered molybdenum oxide (MoO3) possesses high dielectric constant, wide gap band (>3

eV) and large electron affinity,[10] promising an excellent candidate functional block in building

high performance memristors. Although the high-κ constant and air-stability of 2D MoO3 crystals

enable them to have great potentials in memristors, the crystal quality, thickness controllability

and easy-transferability is of critical importance. The best quality 2D MoO3 crystals are usually

obtained by mechanical exfoliation of bulk single crystals, but limited to low efficiency, small size

and randomness.[11] Gao Xuan P. A. et al. grew thick (5–15 um) MoO3s by physical vapor

deposition (PVD) in tube furnace and integrated it as a high-κ gate dielectric in WSe2 FET.[12] Li

3
Xuesong et al. used PVD to grow high crystalline 2D α-MoO3 (thickness ≈ 2.18 μm) for 405 nm

photodetection.[13] Gwan-Hyong Lee et al. used reaction of Mo and oxygen to deposit MoO3 on

multilayer graphene epitaxially to reach the thickness of 1.4 nm for stable MoO3.[14] However, the

size is extremely limited, hard for device fabrication. The separation between the substrate and

material is not so easy as well. Thickness thinning is a significant topic in 2D materials.

Researchers have proposed many ways, such as plasma bombardment, [15] chemical etching, [16]

metallic exfoliation[17] and laser irradiation[18]. However, these methods have shortcomings such

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as non-uniformity, material damage, defects, and much labor/time/economy costs. Up to now,

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scalable synthesis of pure, ultrathin, 2D MoO3s with high quality and transferability, desired for

post-Moore memristors, is still a challenge.

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In this work, a facile plasma pretreatment assisted synthesis technique of 2D MoO3 crystals
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which changes the electrostatic environment of substrates is developed. We used the unique
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reverse chemical reaction of the synthesis of MoS2, namely to use the reaction of MoS2 and O2 to
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synthesize MoO3. MoO3 itself has a high vapor pressure (4,045 × 10−7 atm. at 958 K) and is prone
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to grow thick flakes, as demonstrated by DFT results (Fig. S1)[19]. By oxidizing MoS2, the

evaporation of MoO3 can be controlled by the flow rate of oxygen, resulting in materials with

smaller thickness. This approach is highly stable and reproducible. Ultrathin MoO3 nanosheets

(down to 3 nm, around two layers) were synthesized, close to two orders of magnitude thinner than

those grown without plasma pretreatment. [20] The plasma pretreatment time can be a variable to

clearly influence the tendency of the thickness of the products. We also conducted systematic

computational work to elucidate the mechanism for nanosheets to become slantly-oriented and

thinner in the growth with plasma pretreatment. Due to the unique growth mode, the MoO3

nanosheets standing on the substrates highlight easiness to be transferred to arbitrary substrates by

4
dry method for electronic device fabrication. Meanwhile, the method possesses universality and

can be expanded to synthesize other thin oxide materials, e.g. thinner Bi2O3 and Sb2O3 nanosheets.

We systematically studied the structural, chemical, optical and electrical properties of the few-

layer MoO3 nanosheets. In addition, 2D MoO3 based memristors with the MIM structure were

fabricated using various metal contacts, showing the nonvolatile resistive switching behavior. The

set voltage of memristors based on the MoO3 nanosheets obtained by plasma pretreatment assisted

method is about 0.5 V, merely one-fourth of those based on normal MoO3 nanosheets grown

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without plasma pretreatment approach, in favor of much lower power consumption. The ohmic

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contact between the MoO3 and graphene further decreases the dynamic power consumption.

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Furthermore, the memristors displayed a high ON/OFF ratio (>104) and long retention time (>104
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s). Therefore, the as-grown 2D MoO3 with ultrathin thickness offers a promising material platform
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for the post-Moore memristor.

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2. Experimental section
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Plasma pretreatment of SiO2/Si substrates: Firstly, ultrasonication of the SiO2/Si substrate (with
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a SiO2 oxide layer thickness of 285 nm) was used in acetone and isopropanol for 10 minutes each

to remove impurities adsorbed on the surface; The remaining organic solvents (acetone and

isopropanol) were rinsed with deionized water to obtain the clean SiO2/Si substrates. The cleaned

SiO2/Si substrate were placed into a plasma treatment setup with a coil wrapping the quartz

chamber for air or argon plasma treatment. The pressure was pumped down to 10 Pa. Argon or air

gas flow in the flow rate of 8 sccm was introduced into the plasma chamber. Then the power was

increased to 50 W for 10 minutes treatment to obtain the plasma treated SiO2/Si substrate.

5
Synthesis of MoO3 nanosheets: The silicon wafer was put into the plasma treatment device, with 8

standard cubic centimeters (sccm) Ar flow. The power was set at 50 W, and pretreatment time was

set at 10 minutes. After the pretreatment was completed, the substrates were placed into a 30 mm

tube furnace on the downstream side, with a distance of 18 cm from the furnace center. 10 mg of

molybdenum disulfide powder was placed in the ceramic boat in center zone of furnace. The

furnace was heated to 770 °C within 24 minutes and maintained at this temperature for 7 minutes

under 60 sccm Ar and 5 sccm O2 carrier gas flow. The heating procedure was then halted and the

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furnace was naturally cooled down to room temperature.

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Synthesis of Bi2O3 nanosheets: The silicon wafer was put into the plasma treatment device, with 8

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standard cubic centimeters (sccm) Ar flow. The power was set at 50 W, and pretreatment time was
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set at 5 minutes. After the pretreatment completed, the substrates were placed into a 30 mm tube
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furnace on the downstream side, with a distance of 18 cm from the furnace center. 10mg of BiI3
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powder was placed in the ceramic boat in center zone of furnace. The furnace was heated to 400
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°C within 12 minutes and maintained at this temperature for 7 minutes under 60 sccm Ar and 5
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sccm O2 carrier gas flow. The reaction could be expressed by follow equation:

2BiI3 + 3O2 = 2Bi2 O3 + 3I2 (1)

The heating procedure was then halted and the furnace was naturally cooled down to room

temperature.

Synthesis of Sb2O3 nanosheets: The silicon wafer was put into the plasma treatment device, with 8

standard cubic centimeters (sccm) Ar flow. The power was set at 50 W, and pretreatment time was

set at 15 minutes. After the pretreatment completed, the substrates were placed into a 30 mm tube

furnace on the downstream side, with a distance of 18 cm from the furnace center. 10 mg of Sb2O3

6
powder was placed in the ceramic boat in center zone of furnace. The furnace was heated to 670

°C within 16 minutes and maintained at this temperature for 7 minutes under 60 sccm Ar carrier

gas flow. The heating procedure was then halted and the furnace was naturally cooled down to

room temperature.

Device fabrication: Cr/Au or Cr/Ag bottom electrodes (5/45 nm) were deposited on a 285 nm thick

SiO2 oxide/Si wafer through direct-write laser (DWL, HEIDELBERG DWL66+) lithography and

thermal evaporation of metals. The fabrication of top electrodes of memristors with different

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electrodes is a litho-free process. The electrode/MoO3/electrode structure was stacked by standard

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Polydimethylsiloxane (PDMS) dry transfer method: A MoO3 nanosheet was transferred onto the

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bottom electrode by PDMS (Shanghai Onway Technology Co., Ltd). The top electrode was then
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transferred on to the MoO3 nanosheet.
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Characterizations: The Raman spectroscopy was performed in a Horiba LabRAM Odyssey system
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under 532 nm laser excitation. The PL spectrum measurement was carried out under 266 nm laser
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excitation. The SHG spectrum measurement was done under 1,064 nm laser excitation. The AFM
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measurement was conducted on a DimensionXR system (Bruker). The STEM measurement was

carried out with an acceleration voltage of 200 kV on FEI Titan G2 80-200 ChemiSTEM. HRTEM

imaging was done on a FEI Tecnai G2 F20 S-TWIN TEM. Current-voltage sweeping curves and

resistance of the memristors were measured on a Keithley 2450 sourcemeter.

Density functional theory (DFT) calculation of the additive free energy of MoO3 and MoS2: The

geometrical optimizations were conducted by DFT with Perdew-Burke-Ernzerhof generalized

gradient approximation (PBE-GGA) functional with projector augmented wave (PAW) potentials,

realized in Vienna Ab-initio Simulation Package (VASP). The kinetic cutoff energy was selected

7
as 450 eV for planewave basis set. The valence electron configurations for Mo (4p65s14d5), S

(3s23p4) and O (2s22p4) were utilized. The first Brillouin zone was characterized by a Γ-point-

centered Monkhorst-Pack 6×6×4 grid k-mesh. The tolerance for energy convergence was set at

1.0×10–4 eV for structural optimizations. The criteria for force components convergence was set

at –0.02 eV/Å with symmetrization of the charge density used. For the additive free energy per

E[(n+1) layer]−E[n layer]

atom, it is defined as , E is the free energy. The rest ones can be done in the
addtive atom number

same manner.

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Density functional theory (DFT) calculation of the adsorption energy, migration energy barrier of

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MoO3: The Vienna Ab Initio Package (VASP)[41,42] was employed to perform all the spin-polarized
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density functional theory (DFT) calculations within the generalized gradient approximation
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(GGA) in the PBE[43] formulation. The projected augmented wave (PAW) potentials [44,45] were

chosen to describe the ionic cores and take valence electrons into account using a plane wave basis
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set with a kinetic energy cutoff of 450 eV. Partial occupancies of the Kohn−Sham orbitals were
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allowed using the Methfessel-Paxton smearing method and a width of 0.10 eV. The electronic
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energy was considered self-consistent when the energy change was smaller than 10–5 eV. A

geometry optimization was considered convergent when the residual forces were smaller than 0.05

eV/Å. During structural optimizations, a 1×1×1 k-point grid in the Brillouin zone was used for k-

point sampling, and the bottom two atomic layers were fixed while the top two were allowed to

relax. The transition state of an elementary reaction step was located by the nudged elastic band

(NEB) method[46]. In the NEB method, the path between the reactant(s) and product(s) was

discretized into a series of structural images. The intermediate images were relaxed until the

perpendicular forces were smaller than 0.05 eV/Å. Finally, the adsorption energies (Eads) were

calculated as Eads= Ead/sub–Ead–Esub, where Ead/sub, Ead, and Esub are the total energies of the

8
optimized adsorbate/substrate system, the adsorbate in the structure, and the clean substrate,

respectively.

3. Results and discussion

Fig. S1 shows the density functional theory (DFT) calculation of layer dependence of additive

free energy normalized to per atom for MoO3 and typical transition metal dichalcogenides MoS2.

The additive free energy per atom of MoO3 in the additional layer is much more negative than that

of MoS2, implying the MoO3 nanosheet would prefer to be relatively thicker than the MoS2

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nanosheet. This, to some extent, explains why the existent works about 2D MoO3 are more on

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mechanically exfoliated samples and the CVD grown materials are almost thick ones. [20] In the

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following study, we conducted experiments of growth of MoO3 with the substrates pretreated by
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plasma as our protocols (described in the experimental section). We carried out experiments of
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growth of MoO3 without any substrate pretreatment as the control group. We found the growth
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assisted by the plasma pretreatment of the substrates aids us to synthesize thinner 2D MoO3
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nanosheets.
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Fig. 1a illustrates the approach of plasma pretreatment of the substrates and CVD

configurations for materials synthesis. We used reverse reaction of the common-seen reaction to

produce 2D MoS2 in which MoO3 powder reacts with sulfur, i.e. reaction of MoS2 and O2 to

generate 2D MoO3 (see experimental section), expressed by follow equation:

2MoS2 + 7O2 = 2MoO3 + 4SO2 (2)

The substrates were pretreated by argon plasma to synthesize thin MoO3. Fig. 1b

demonstrates the optical microscope (OM) image of the MoO3 crystals which were synthesized by

our growth method. Fig. S2 demonstrates the images which could distinguish standing MoO3

9
nanosheets and lying flat MoO3 nanosheets after being pressed by another substrate. We could

control the thickness of the MoO3 by tuning the power and time of plasma pretreatment. The OM

of different thickness of MoO3 are exhibited in supporting information (Fig. S3). Fig. 1c shows

the scanning electron microscopy (SEM) image of the as-grown MoO3 nanosheets. Noticeably,

the MoO3 nanosheets are slantly-oriented with respect to the substrate. Fig. 1d illustrates the

average thickness of the as-grown MoO3 nanosheets with plasma pretreatment and without plasma

pretreatment. The average thickness of MoO3 nanosheets synthesized by plasma pretreatment

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decrease by two orders of magnitude. The Raman spectra taken from the central region of the

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trapezoid flake clearly shows distinct features. The Raman spectra (orange curve in Fig. 1e) from

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the central region in the flake exhibits four prominent peaks at 282, 336, 818 cm–1 and 994 cm–1
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corresponding to the B1g and Ag resonance modes of α-MoO3. The Photoluminescence (PL) studies
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also show prominent PL peak at 400 nm on the central region of the flake (Fig. 1f), indicating a
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band gap around 3.1 eV.

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Fig. 1g shows the AFM image and the thickness line-scan of the as-synthesized material. The
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thickness profile revealed the as-grown material is ~3 nm thick, about two layers of MoO3

nanosheets (The lattice constant of c in MoO3 is 13.856 Å ≈ 1.4 nm).[21] We compare the thickness

of MoO3 nanosheets between this work and previous works in Table 1. The thickness of MoO3

synthesized on SiO2/Si by this approach is much thinner than other literature reports. To identify

the composition and morphology of the as-synthesized MoO3, transmission electron microscopy

(TEM) and relative measurements was conducted. Fig. 1h–i show the selected area electron

diffraction (SAED) and high angle annular dark field scanning transmission electron microscopy

(HAADF-STEM) of as-grown layered α-MoO3 and reveal its single-crystalline nature with a

lattice spacing of 0.4 nm. [22] Fig. 1h shows a single set of orthorhombic-arranged diffraction spots

10
with equivalent orientations of [100] and [010]. The STEM image of MoO3 displays the

orthorhombic symmetry and the great single crystalline quality. High resolution transition electron

microscopy (HRTEM) and energy dispersive spectroscopy (EDS) characterizations were carried

out as well. Fig. S4 illustrates that the EDS mapping of the MoO3 nanosheet. The elements of Mo

and O distribute uniformly. Fig. S4 shows the absorption edge of the electron energy loss

spectroscopy (EELS) of the as-grown MoO3 nanosheet, which displays the band gap of MoO3 (3.3

eV), consistent with the PL emission position.

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Table 1. Comparison of the thickness of MoO3 nanosheets between this work and previous works.

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References Thickness Substrate Method
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Ref. 12 50 nm–1 μm / PVD and Mechanical exfoliation

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Ref. 23 4 nm Mica Van der Waals Epitaxy

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Ref. 24 25 nm SiO2/Si CVD

Ref. 25 Bulk SiO2/Si PVD

Ref. 26 70 nm SiO2/Si Hydrothermal synthesis

This work 3 nm SiO2/Si CVD

Fig. 2a shows the lattice structure of α-MoO3. It presents an orthorhombic lattice with a Pbnm

space group (a = 3.696 Å, b = 3.961 Å, c = 13.853 Å), composed of atomically thin sheets layered

11
in the c direction. Each sheet consists of linked and distorted MoO6 octahedra and is stacked by

van der Waals (vdW) force with strong in-plane covalent bonding. We further measured the

second-harmonic generation (SHG) spectra from MoO3 nanosheets. Fig. 2b shows the azimuthal

dependence of the SHG intensity, as signaled by four lobes vertical to each other, revealing the

intrinsic orthorhombic symmetry essence in the alpha phase. The reason for the appearance of

observed SHG signal is attributed to the spatial inversion symmetry breaking in the crystal

structure, as shown in the Fig. 2a. The anisotropy of 2D MoO3 is further confirmed by the polarized

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Raman spectrum of as-grown MoO3 nanosheets in Fig. S5: the peak of B1g (282 cm–1) would

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appear when the angles of the polarizer and the analyzer are anti-parallel; on the other hand, the

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peak of Ag (818 cm–1) would appear when the angles of the polarizer and the analyzer are parallel.
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Moreover, we did C (capacitance)-f (frequency) measurements to probe the relative dielectric
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constant of MoO3. Fig. 2c shows the correlation between the relative dielectric constant and the
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frequency of the stimulating signal, exhibiting a damped oscillator resonance. The relative
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dielectric constant of MoO3 is about 40, highlighting a high-κ material. We also adopted another
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method of measuring dielectric constant by conductive atomic force microscopy (c-AFM). [27] The

details can be seen in Note S1 in the Supporting Information. Fig. 2d shows the curve of lnI vs √𝑉.

The slope in the fitting indicates that the relative dielectric constant of MoO3 is 44, consistent with

the C–f result. Note the scattered data shows non-linearity which deviates from the theoretical

linearity, due to that the accumulation of oxygen vacancy under the electric field results in the

decrease of effective oxide thickness d which can lead to the increase of the slope.

Fig. 2e depicts the XPS diagram of O 1s orbit of MoO3 nanosheet which is on pure Si

substrate. After decomposing the spectra, it shows three O 1s subpeaks located at 529.4, 532.2 eV

12
and 532.9 eV, which are associated with lattice oxygen, oxygen vacancy and adsorpted oxygen,

respectively. [23] Therefore, the as-grown MoO3 nanosheets possess oxygen vacancies.

We did statistical height measurements by profiler under different substrate plasma

pretreatment conditions, such as different argon plasma pretreatment time, air plasma

pretreatment, unprocessed substrate or plasma-processed substrate placed in the ambient

environment for one week. Fig. 3a shows the statistical distribution histogram of layer thickness

of the above-mentioned four cases, comparing the thickness of 2D MoO3. It reveals that the growth

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condition to achieve thinnest nanosheets is with argon plasma pretreatment of ten minutes. In the

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situation without plasma pretreatment, the thickness of 2D MoO3 nanosheets varied widely. The

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thickest of 2D MoO3 nanosheets synthesized on unprocessed substrate is thicker than 200 nm,
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while the thinnest of MoO3 nanosheets is about 50 nm. In comparison, the MoO3 nanosheets
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synthesized with substrate plasma pretreatment all became thinner than those on the unprocessed
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substrate. In particular, when the argon plasma treatment is in ten minutes, the thinnest MoO3
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nanosheet is only around 3 nm, accompanied by an average thickness of 10 nm. Therefore, the
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plasma pretreatment time can be a knob to tune the product thickness. Interestingly, we observed

that the MoO3 nanosheets synthesized on the substrate which was pretreated by air plasma would

also be thinner than those the unprocessed substrate. The average thickness of MoO3 nanosheets

synthesized on the substrate treated by air plasma treatment is about 20 nm, also validating air

plasma pretreatment in synthesizing thinner MoO3. Moreover, the charge the substrate carries in

the ambient environment would be neutralized by air gradually, resulting in expiry of the

pretreatment. Thus, we did experiments on the substrate pretreated by argon plasma for 10 min but

placed in the ambient environment for a week. After one week, we used these substrates for

growth. The average thickness is comparable to the totally unprocessed substrate, corroborating

13
that it is the electrostatic charges that take the major effect in the growth rather than the surface

roughness, resulting in the thinning of the MoO3 flakes. We carried out kelvin probe force

microscopy (KPFM) measurements on the substrates with/without plasma pretreatment. Fig. 3b

shows that the surface potential of Si/SiO2 pretreated by argon plasma is higher than that of

unprocessed Si/SiO2, meaning that the Si/SiO2 carried negative charges after pretreatment (surface

root mean square (RMS) roughness data are in Table S1). Moreover, the surface potential of

Si/SiO2 treated by air plasma is lower than that of unprocessed Si/SiO2, indicating that Si/SiO2

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carried positive charges after air plasma pretreatment. However, whichever sign of the charges the

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Si/SiO2 substrate carries, thin few-layer MoO3 nanosheets could both be synthesized. Besides, we

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also did experiments on the mica. Fig. S6 shows the MoO3 on the van der Waals material mica
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which was treated by argon plasma. The MoO3 on mica which was not pretreated by plasma (Fig.
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S6) were in in-plane epitaxy growth mode. The electrostatic charges after plasma pretreatment
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give rise to many slant pieces as well (Fig. S6), similar to the case on the silicon wafer. These facts

would further prove the growth approach with plasma pretreatment to be effective.
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Raman spectra of different layer number MoO3 is shown in Fig. 3c–d. Fig. S7 shows the

corresponding AFM images. The intensity of Raman spectra reasonably decreases as the number

of layers diminishes and the peaks of 900–1000 cm–1 is the peak of Si which reasonably increase

as the thinning of the MoO3. When the layer decreases to two layers (3 nm), B1g 282 cm–1, one of

the major peaks of MoO3’s Raman spectra, disappeared. The 303 cm–1 peak originates from

Si/SiO2 substrate as the laser penetrates through the thin MoO3 nanosheet to reach the substrate

and the Raman peak of the substrate became prominent.

To figure out the mechanism why the MoO3 nanosheets would grow slantly-oriented and the

thickness of the MoO3 nanosheets decrease, we carried out systematic DFT study. Fig. 4a shows

14
the adsorption energy of MoO3 clusters on regular SiO2/Si substrate and SiO2/Si substrate with

charges and higher surface roughness by plasma pretreatment in reality. The adsorption energy of

MoO3 cluster on regular SiO2/Si substrate is –0.559 eV, smaller than that on charged SiO2/Si

substrate (–0.372 eV), revealing the adsorption onto the surface becoming harder with regard to

the plasma pretreated substrate. Meanwhile, the adsorption energy of MoO3 cluster on 2D-MoO3

surface (Fig. S8a–b) is much lower than that on regular SiO2/Si substrate, implying stronger

adsorption of MoO3 cluster on the surface of lying 2D MoO3 and inducing the lying 2D MoO3 on

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regular substrate thick. Besides, the adsoption energy of the MoO3 cluster onto the slant 2D MoO3

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edge (–2.351 eV, Fig. 4b) is much lower than that upon the lying 2D MoO3(Fig. S8c, –1.224 eV),

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both on the charged substrate, indicating stronger adsorption of the MoO3 cluster onto the slant
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MoO3 nanosheet and inducing the tendency of the growth of slant MoO3 nanosheets. Moreover,
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The adsorption energy of the MoO3 cluster on the edge of the slant MoO3 nanosheet (–2.351 eV)
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is significantly lower than that on the top in the slant-oriented MoO3 nanosheet (–1.961 eV, Fig.

4b), showing that the additive MoO3 clusters prefer to grow laterally rather than vertically,
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resulting in the formation of thin 2D-MoO3 nanosheets. Fig. 4c displays the schematic illustration
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of MoO3 cluster migration on charged SiO2/Si substrate. Fig. 4d shows that the migration barriers

of the MoO3 cluster on the charged SiO2/Si substrate is 1.47 eV, significantly higher than that on

the regular SiO2/Si substrate (0.93 eV). This higher energy barrier of migration for the MoO3

clusters on the charged substrate surface, together with their low adsorption energy, are one aspect

of the causes for the slant-oriented growth of the MoO3 nanosheets on plasma pretreated SiO2/Si.

Once the thermal fluctuations make the adsorbed atomic clusters oriented with some degrees to

the substrates, the continuous lateral extension becomes easy due to the low adsorption energy on

the edge of the slant-oriented 2D MoO3 nanosheet. Thus, the nucleation and slant-oriented growth

15
occurs. Furthermore, Fig. 4e and Fig. S9 show the schematic illustration of MoO3 cluster migration

on slant MoO3 nanosheet and lying 2D-MoO3 nanosheet, respectively. Inferred from the

corresponding computational results in Fig. 4f, the migration barriers of the MoO3 cluster to the

edge of the slant MoO3 nanosheet (0.49 eV) is significantly smaller than that on the lying 2D-

MoO3 nanosheet (0.82 eV), indicating that it is easier for the slant MoO3 nanosheet to grow thinner

and bigger. The result from the DFT interrogation is in good agreement with the experimental

results.

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To show that the plasma pretreatment assisted approach to produce thin 2D MOs possesses

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certain universality, we also synthesized non-layered 2D Bi2O3 nanosheets by this approach using

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the reaction of BiI3 with O2. Fig. S10, S11, S14 show the OM, Raman, SEM, and AFM images of
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the products grown with or without plasma pretreatment, also validating this method on growing
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thin and slant non-layered 2D Bi2O3 with thickness down to 6 nm. The lower intensity of Raman
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and AFM image could both testify that the as-grown Bi2O3 is very thin. Plasma pretreatment
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assisted approach could also be applied on Sb2O3 nanosheets. Fig. S12–14 show the OM, Raman,
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SEM and AFM of Sb2O3 nanosheets of the products grown with or without plasma pretreatment,

and the thickness of Sb2O3 reduces from micrometer level to nanometer level. These results all

corroborate that our approach with the electrostatic charge growth possesses certain universality.

The reduced thickness enables the 2D MoO3 promising for the post-Moore memristor

applications. Accordingly, we fabricated multiple MIM structural memristors with different

electrodes. The different electrode metal would cause distinct filaments forming mechanism of

metallic atoms or oxygen vacancies. The active metal such as silver would undergo

electrochemical reaction to be oxidized on one side, and reduced and deposited on the other side

to form metallic filament in the functional layer, forming a connection between two electrodes. [27]

16
On the other hand, the memristors with inert metal electrodes do not undergo oxidation-reduction

process and have distinct filament forming mechanism. Under the electric field, the oxygen defects

(vacancies) would migrate and aggregate to form conductive channels between the electrodes on

both sides of the functional layer.[27]

Fig. 5a illustrates of the convenient transferring process, unlike other CVD grown materials

with high stickiness to the substrates.[28] Because the as-synthesized ultrathin MoO3 flakes were

standing and not in close contact with substrates, its advantage is augmented with easiness for

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transferring MoO3 by dry method with Polydimethylsiloxane (PDMS) stamp with significantly

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fewer organic residues than the wet chemical transferring (Fig. S15 shows the OM images of the

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thin flakes on the transfer stamp). Fig. 5b illustrates the device MIM structure of the as-fabricated
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memristor. The top electrode was the metallic one such as transferred silver or gold. Fig. 5c
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exhibits the single electrical sweep hysteresis of the memristor with top Ag electrode and bottom
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Au electrode. The set voltage is 0.5 V, as well as the on/off ratio reaching 104. Both of the dash
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circled areas (labeled as 1 and 3) display Ohmic charge transport behavior. The inset of Fig. 5c
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shows the linear fitting of I vs V. The I–V relationship can be expressed as follows:

𝑉𝑆
𝐼= (3)
𝜌𝑡

where ρ is the resistivity, t is the length of current flow passage, and S is the cross-section area of

the current flow passage.

Fig. 5d depicts the band alignment of the interface between silver and MoO3, indicating the

reason of the ohmic charge transport behavior of the device in the high resistive state (HRS) stage

(labeled 1). The work function of silver (~4.3 eV) is lower than that of MoO3 (4.7 eV, literature

value, also confirmed by KPFM measurement, Fig. S16).[14, 29] The potential barrier seen by the

17
electrons in the silver in the interface is very low, resulting in an ohmic contact. The charge

transport mechanism in low resistive state (LRS) (labeled as 3) is also ohmic due to that the

conductive sliver filament has connected the both-side electrodes throughout the functional layer.

Fig. S17 demonstrates sixteen cycles of I–V curves of the memristor with the transferred silver

electrode. Although the memristor with the silver electrode shows a great on/off ratio, the

endurance and stability of the memristor with the silver electrode is not ideal. Because the

memristors were fabricated by transferred electrodes which were etched by buffered oxide etch

of
(BOE), the interface quality between material and top electrodes might be not good, also likely to

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lead to the nonvolatility.[30]

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Furthermore, Fig. 5e shows the curve of memristor with gold electrodes on both sides. As the
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curves of memristor with both Au electrodes, the current would suddenly rise by several orders of
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magnitude when the voltage rises to above 1 V. But the current has not reached the limited current
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(Icc) immediately, indicating that the resistance of oxygen filament is a little higher than above-
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mentioned silver filament. It is noteworthy that the set voltage of the memristor with the gold top
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electrode is higher than that with the silver top electrode (1 V vs. 0.5 V), meaning that the oxygen

vacancies need more energy than silver cations to migrate. Fig. 5f reveals the charge transport

mechanism with the gold top electrode. A line fits well in the lnI vs √𝑉 in the HRS section,

indicating that the charge transport mechanism is the Schottky emission. The formula for the

Schottky emission is as followed:

−𝑞(ᶲb −√𝑞𝑉/π𝜀r 𝜀0 𝑑
𝐼 = 𝐴𝑇 2 exp( ) (4)
𝑘b 𝑇

where A is a pre-exponential factor given by the Richardson constant A0 times a material specific

factor λr (between 0 and 1, typically 0.5), T is temperature, kb is Boltzmann’s constant, q is the

18
fundamental charge, ᶲb is the field-free barrier height, V is the voltage, d is the thickness, and εr

and ε0 are the relative permittivity and permittivity of vacuum, respectively.

Then we transform into the relationship between ln I and √𝑉

−𝑞(ᶲb −√𝑞𝑉/π𝜀r 𝜀0 𝑑)
lnI = +Constant (5)
𝑘b 𝑇

and thus in the Schottky emission, lnI is proportional to √𝑉.

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The work function of gold (5.1 eV) is higher than the work function of MoO3 nanosheet (4.7

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eV)[29], resulting in the formation of the Schottky barrier between the electrode and MoO3.

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However, the linearity of I–V curve in the LRS section as shown in Fig. 5g indicates good ohmic
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contact in LRS, because the oxygen vacancies filament mediates as a conductor.
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Notably, the repeatability of the voltage cyclic sweeping of memristors with silver electrodes
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or gold electrodes on both sides is not very good (See Fig. S17–18), highly likely due to the
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interfacial effect between the functional layer and the electrodes. The gold electrode is not a van
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der Waals materials, with dangling bonds on the surface, which also probably causes the instability

of the MoO3 memristors. Therefore, we thought of using a van der Waals material with dangling-

bond free surface to be the electrode of MoO3 memristors.

Graphene features an ideal electrode with inert surface and highly conductive

(2,700 S/cm).[31] Fig. 6a displays the 150 repetitive switching cycles of MoO3 memristor with Ag

in the bottom and multi-layer graphene on the top side. Obviously, the repeatability is significantly

enhanced than the memristor with Ag or Au electrodes (two sides), which corroborates our

conjecture. The van der Waals interface contact between MoO3 and graphene would become

significantly better than the transferred etched metallic electrode and MoO3. The on/off ratio keeps

19
at 104, and the set voltage keeps at around 0.5 V. Fig. 6b shows the histogram of resistance in the

HRS and LRS section of memristor with Ag/graphene electrode, extracted by automated fitting.

No overlap of the resistances in HRS and LRS can be observed, indicating that these two states

can be reliably distinguished. Fig. 6c demonstrates that the cumulative probability of set voltage

and reset voltage. The curve of cumulative probability of set voltage is almost a straight line

perpendicular to the horizontal axis, exhibiting the excellent stability of set voltage. The curve of

cumulative probability of reset voltage shows slightly larger variation compared to the set voltage.

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Fig. 6d shows that the fitting curves of charge transport mechanism of HRS and LRS states of the

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memristor with Ag/graphene electrodes. The linear fitting shows that the charge transport

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mechanism of HRS is ohmic, due to that the work function of graphene (4.7 eV)[32] is close to that
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of MoO3 (4.7 eV).[29] The ohmic contact can also decrease the power consumption. In the Schottky
lP

contact, a capacitance exists, expressed by the follow equation:

na

𝑒𝜀𝜀0 𝜌0
𝐶 = 𝐴√ (6)
2(𝑉 bi −𝑉)
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Jo

where A is the contact area, e is the fundamental charge, 𝜀 is the relative permittivity and, 𝜀0 is the

permittivity of vacuum, 𝜌0 is the doping density of the semiconductor, 𝑉bi is the built-in potential,

and 𝑉 is the voltage bias.

The additional dynamic power consumption resulted from this capacitance is:

𝑃 = 𝐶𝑉 2 𝑓 (7)

where P is the dynamic power consumption, C is the capacitance, V is the voltage, and 𝑓 is the

read frequency of HRS.

20
 Furthermore, the charge transport mechanism of LRS state of the memristor with

Ag/graphene electrodes is also ohmic transport, as seen from the linear fitting (Fig. 6d inset), due

to the formed silver filament. Fig. 6e shows the retention of the resistive state with respect to time.

The device could keep the stability of HRS and LRS over 10,000 seconds without issues.

Fig. 6f compares the set voltage mean value of memristors with MoO3 nanosheets grown

with/without plasma pretreatment which show different thickness level, including 10 nm level

(nanosheets grown with plasma pretreatment) and 100 nm level (nanosheets grown without plasma

of
pretreatment). The set voltage mean value of memristor with thinner functional layer grown with

ro
pretreatment is about 0.5 V, while the set voltage mean value of thicker functional layer grown

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without pretreatment is about four times higher (The typical I–V sweep curves from different
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devices and AFM images are in Fig. S19–21).[29] This can be rationalized that the set voltage is
lP

the driving force of the metallic atom to ionize and transit through the blockage layer; thus, the
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thinner thickness lowers the set voltage. The significantly lower setting voltage will lead to much
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lower power consumption.

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For evaluation of the device performance of 2D MoO3 memristor by our approach, the Table

2 shows the comparison of the device characteristics between this work and previous works with

2D materials. Obviously, the device of this work exhibits great on/off ratio, low set voltage (i.e.

lower power consumption) and excellent endurance, exhibiting the superiority of our 2D MoO3.

Table 2. Comparison of the device characteristics between this work and previous works.

21
 References Materials On/Off ratio Set Voltage Sweep Scan Cycles

This work MoO3 104 0.5 V 150

Ref. 26 MoO3 105 0.75 V 20

nanobelt (Ag

electrode)

Ref. 33 TiS3 102-103 1V 100

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Ref. 34 BiO2Se2 102 1.5V /

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Ref. 35 WS2/MoS2 104
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>1 V <50
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Ref. 36 H-BN 104 1V 200
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Ref. 37 MoSe2 103 3V /

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Ref. 37 WSe2 103 2V /

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Jo

Ref. 38 MoO3 102–103 1V 100

Ref. 39 MoO3 <10 1V 3

Ref. 40 Ag doped <100 0.8 V /

MoO3

4. Conclusions

22
 In conclusion, we have synthesized ultrathin MoO3 nanosheets with control on the thickness

and high transferability by plasma substrate pretreatment. The weak adsorption and high surface

diffusion barrier of MoO3 clusters on the plasma-pretreated substrates lead to slant growth of the

2D MoO3 nanosheets. In addition, low diffusion barrier of the clusters on the surface of the slant

MoO3 nanosheets and their strong adsorption on the nanosheet edge leads to extended 2D growth

of the nanosheets. This approach possesses certain universality and we corroborate its feasibility

in other 2D metal oxide material systems. We further fabricate memristors with the ultrathin 2D

of
MoO3 with different electrodes and explicated the charge transport mechanisms. Among them, the

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memristor with Ag/graphene electrode exhibits high on/off ratio (≈ 104), low set voltage (≈ 0.5

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eV), long retention time (>104 s) and excellent repeatability in voltage sweeping cycles (>150).
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Particularly, the power consumption of setting MoO3 memristors is reduced by four times, as an
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efficacy of the reduced thickness of MoO3 nanosheets. These results point to the exciting prospect
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of thinning down thickness of 2D metal oxides and the promise of the ultrathin MoO3 as a

functional block for the memristive device applications in the post-Moore era.
ur
Jo

Author Contributions

The manuscript was written through contributions of all authors. All authors have given approval

to the final version of the manuscript. # These authors contributed equally to this work.

Declaration of competing interest

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.

Acknowledgment

23
The authors acknowledge the support from National Natural Science Foundation of China (Grant

Nos. 51902061, 52072272, 62090031 and U22A2076). The authors also thank the computational

support from Nanjing Yinzhi Technology Co., Ltd.

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Figure
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Fig. 1 Plasma assisted CVD growth and OM images of as-grown MoO3 nanosheets. (a) Schematic

illustration of the setups for the growth of MoO3 nanosheets, (i) Schematic illustration of plasma

pretreatment to the substrates, (ii) Schematic illustration of the CVD growth. (b) OM image of the

as-grown MoO3 nanosheets on the SiO2/Si substrate. The slant MoO3 nanosheets are highlighted

by yellow arrows. For clarity, the sample is pressed by another silicon substrate to make some

originally slant flakes appear to lie flat. (c) SEM image of as-grown MoO3 nanosheet on the plasma

pretreated substrate. (d) Average thickness of the as-grown MoO3 nanosheets with plasma

pretreatment or without plasma pretreatment. W: with, W/O: without. (e) Raman spectra of the as-

29
grown MoO3 nanosheet. (f) PL spectra of the as-grown MoO3 nanosheet. (g) AFM image and the

cross-sectional thickness profile of the as-grown thinnest MoO3 nanosheet. (h) SAED image of the

as-grown MoO3 nanosheet. (i) HAADF-STEM image of the as-grown MoO3 nanosheet, showing

lattice spacing of 0.4 nm.

Fig. 2 (a) Lattice structure of α-MoO3 crystal under different orientations. (b) Azimuthal mapping

of the SHG intensity from the as-grown MoO3 nanosheet. (c) Capacitance-frequency device test

of the as-grown MoO3. (d) lnI vs. square root of voltage in the voltage sweeping by the c-AFM.

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Inset: conductive AFM mapping image of MoO3. (e) XPS spectrum of O 1s orbit of the as-grown

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MoO3 nanosheet.

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Fig. 3 (a) Statistics of the thickness of MoO3 nanosheets synthesized with various substrate
lP

pretreatment (“Ar 5 min” means in Ar plasma for 5 min; “Ar 10 min & a week later” means that

the substrates are used a week after the 10 min Ar plasma pretreatment; “Air 10 min” means 10
na

min pretreatment in air plasma). (b) Histogram of surface potential by KPFM of the substrates
ur

under different plasma treatment. (c, d) Raman spectra of different layer thickness of the as-grown
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MoO3 nanosheet. Inset: magnification of Raman spectra of MoO3 nanosheets of the Raman shift

zone between 900–1,000 cm–1.

Fig. 4 (a) Adsorption energy calculations of MoO3 cluster on regular SiO2/Si substrate and charged

SiO2/Si substrate with higher surface roughness. (b) Adsorption energy calculations of MoO3

cluster on top of the slant MoO3 nanosheet and the edge of the slant MoO3 nanosheet. (c) Three

states (initial state (IS), transition state (TS) and final state (FS), from left to right) of migration of

MoO3 cluster on charged SiO2/Si substrate. (d) Relative energy of MoO3 cluster on regular SiO2/Si

substrate and charged SiO2/Si substrate with higher surface roughness, revealing the migration

30
energy barrier. (e) Three states (from left to right) of migration of MoO3 cluster on the slant MoO3

nanosheet. (f) Relative energy of MoO3 cluster on top of the slant MoO3 nanosheet and lying 2D

MoO3. The arrows and the numbers show the migration energy barrier.

Fig. 5 (a) Schematic illustration of the transferring process. (b) Schematic illustration of the device

structure of the memristor. The top electrode can be graphene or gold, and the bottom electrode

can be silver or gold. (c) Typical current-voltage cycle of memristor with Ag/MoO3/Au structure.

Inset, current fitting results for HRS of memristor with Ag/MoO3/Au structure. (d) Schematic

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illustration of the band alignment on the interface between silver and MoO3. (e) Representative

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current-voltage curve of memristor with Au/MoO3/Au structure. (f) Fitting curve of HRS of the

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memristor with Au/MoO3/Au structure. (g) Fitting curve of LRS of memristor with Au/MoO3/Au
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structure.
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Fig. 6 (a) Repetitive voltage sweeping cycles of current-voltage of memristor with

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Ag/MoO3/graphene structure. (b) Histogram of resistances of HRS and LRS of memristor with
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Ag/MoO3/graphene structure. Inset: Schematic illustration of Ag/MoO3/graphene structure. (c)

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Cumulative probability curve of set voltages and reset voltages of memristors with

Ag/MoO3/graphene structure. (d) Linear fitting of I vs. V of the LRS of the memristor with

Ag/MoO3/graphene structure. Inset: the linear fitting of HRS of the memristor with

Ag/MoO3/graphene structure. (e) Retention of the resistive state with respect to time. (f)

Comparison of set voltage mean value of memristor with MoO3 grown by the approach with or

without plasma pretreatment. W: with, W/O: without.

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Lijie Zhang
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Yukun Hong
 Shangui Lan

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Highlights:
1. A facile chemical vapor deposition for standing ultrathin MoO3 nanosheets assisted
by substrate pretreatment is developed.

2. Thickness of MoO3 nanosheets decreases dramatically, compared with counterparts

by growth without this approach.

3. Memristors based on the thickness-reduced 2D MoO3 show significantly lower set

voltage and other superior properties.

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4. This facile method assisted by surface charges shows universality in thickness-
controlled growth of other 2D metal oxides.
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5. 2D thin MoO3 by this approach is easy to transfer, beneficial for device fabrication.
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Peijian Wang received his B.Sc., M.Sc., and Ph.D. degrees from Peking University, the
University of Pennsylvania, and the University of Massachusetts, Amherst, respectively. He then
became a postdoctoral Research Fellow at the State University of New York, Buffalo. In the
following, he became a Researcher at the ZJU-Hangzhou Global Scientific and Technological
Innovation Center, Zhejiang University. Currently, he is an Associate Professor in College of
Chemistry and Material Science in Wenzhou University. His research interests focus on the growth
and electronic, optical, and magnetic properties of 2D materials, corresponding heterostructures and
interfaces, and applications in future electronic and optoelectronic devices.

Lijie Zhang graduated from Changchun University of Science and Technology with a bachelor's
and master's degrees, and his Ph.D. from the University of Chinese Academy of Sciences. He is now
a Research Professor in College of Chemistry and Material Science in Wenzhou University. His

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main research areas are low-dimensional semiconductor growth and optoelectronic devices.

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Yukun Hong is currently a master student in the College of Chemistry and Material Science in
Wenzhou University. His recent research focuses on the growth and characterization of low-
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dimensional functional materials.
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Shangui Lan received his Ph.D degree in Huazhong University of Science and Technology, China,
in 2021. He joined Zhejiang University in 2021, and is now a postdoc at the College of Integrated
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Circuits, Zhejiang University, China. His current research interests concern mainly the growth,
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electronic and optical properties of 2D materials and perovskites.

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