Materials Letters
Effect of Intercalant Type on the Exfoliation of Sb2Se3 for Preparation of Thin Layers
--Manuscript Draft--
Manuscript Number: MLBLUE-D-24-02478
Article Type: Short Communication
Keywords: Thin layer sheets, semiconductors, Raman, exfoliation, intercalation, oxidation
Abstract: The atomically thin sheets of Sb2Se3 hold a great potential in semiconductor
applications. The present work reports intercalation-assisted exfoliation methods using
various types of intercalants for the preparation of Sb2Se3 thin layers. The efficacy of
the intercalants to penetrate the layers and thereby exfoliate the intercalated layers is
structurally and electrochemically investigated. The structural characterization
demonstrated successful exfoliation of bulk Sb2Se3. The bulk and exfoliated samples
when exposed electrochemically to H+ and K+ ions exhibited unique redox activity,
which was correlated to the thickness of the exfoliated layers. The intercalating ability
of intercalants was compared to the degree of exfoliation.
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Graphical Abstract
Graphical abstract
Highlights (for review)
Highlights
An intercalation-assisted exfoliation strategy was used to exfoliate Sb2Se3 layers.
Different intercalants (H2O, PVP, Na+ and Li+) showed varying intercalation ability and
thereby exfoliation efficiency.
Cyclic voltammetry studies in H2SO4 and KOH electrolytes demonstrated redox
behaviour indicating re-insertion/deinsertion of small cations.
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Effect of Intercalant Type on the Exfoliation of Sb2Se3 for Preparation of
1 Thin Layers
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4 Samidha S. Narvekar, Anisha Naik, Anjani P. Nagvenkar*
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7 School of Chemical Sciences, Goa University, Goa 403206, India
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9 *Corresponding author. Email address: [email protected], Tel no. +919049244139
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12 Abstract
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15 The atomically thin sheets of Sb2Se3 hold a great potential in semiconductor applications. The
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18 present work reports intercalation-assisted exfoliation methods using various types of
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20 intercalants for the preparation of Sb2Se3 thin layers. The efficacy of the intercalants to
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23 penetrate the layers and thereby exfoliate the intercalated layers is structurally and
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25 electrochemically investigated. The structural characterization demonstrated successful
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exfoliation of bulk Sb2Se3. The bulk and exfoliated samples when exposed electrochemically
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30 to H+ and K+ ions exhibited unique redox activity, which was correlated to the thickness of
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32 the exfoliated layers. The intercalating ability of intercalants was compared to the degree of
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35 exfoliation.
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38 Keywords:
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41 Thin layer sheets, semiconductors, Raman, exfoliation, intercalation, oxidation
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44 1. Introduction
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48 Among metal selenides, antimony triselenide (Sb2Se3) owing to its layered crystal structure
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50 has gained increased attention as a promising narrow band gap 2D semiconductor for energy
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53 applications mainly in photovoltaics[1], thermoelectrics[2], and electrochemical storage
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55 devices [3]. The intriguing properties offered by atomically thin layers of Sb2Se3 such as high
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surface area, electronic/thermal conductivity, numerous active sites, make them superior for
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60 application over its bulk counterparts[4]. In order to fabricate atomically thin sheets (mono-to
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few-layer thick), intercalation-based exfoliation strategy has proven to be a potential strategy
in terms of mass production, scalability, cost effectiveness, and high yield of thin layers [5].
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3 So far, cryo-assisted liquid exfoliation [6], water assisted intercalation-based exfoliation [7]
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5 and the generic method of Li+ intercalation-based exfoliation strategies have been
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8 successfully reported as methods to exfoliate bulk Sb2Se3 for obtaining thin layers [8].
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10 However, there has been a dearth in the studies on various methods of intercalation-assisted
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13 exfoliation of bulk Sb2Se3. In this regard, a comparative study on types of intercalation
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15 strategies for efficient exfoliation of Sb2Se3 can be very significant.
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18 Herein, we report four different intercalant-assisted exfoliation approaches for bulk Sb2Se3
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21 exfoliation. The different intercalants were classified into inorganic cations (Na+, Li+),
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23 organic polymeric molecules (polyvinylpyrrolidone, PVP) and H2O. The efficacy of the
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intercalants to penetrate the layers of bulk Sb2Se3 and weaken the van der Waals interactions
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28 is determined by characterizing the exfoliated samples by XRD, Raman and cyclic
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30 voltammetry.
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34 2. Experimental
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37 The bulk Sb2Se3 was hydrothermally synthesized, wherein, 5 mmol NaOH in 20 mL distilled
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water and 1 mmol Se powder in 8 mL hydrazine hydrate were separately dissolved. The two
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42 solutions were mixed and stirred for 20 min. To this, 0.8 mmol of antimony potassium tartrate
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44 dissolved in 8 mL hydrazine hydrate was added dropwise with constant stirring. The solution
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47 mixture was transferred to a 100 ml Teflon-lined stainless-steel autoclave and heated at 210
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49 °C for 8 hrs. The black precipitate was washed with ethanol and distilled water and dried
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52 under vacuum at 220 °C for 2 hrs.
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55 The Sb2Se3 powder was subjected to following intercalation-assisted exfoliation procedures:
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57 (i) Water freezing-thawing-assisted intercalation: 0.2 g of Sb2Se3 dispersed in 10 mL distilled
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60 water and stirred for 24 hrs. The solution was frozen at -26 °C for 96 hrs and thawed at RT.
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(ii) Salt and water co-assisted intercalation: 0.2 g of Sb2Se3 dispersed in 10 mL 0.5 M Na2SO4
solution and stirred for 24 hrs. The solution was frozen at -26 °C for 96 hrs and thawed at RT.
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3 (iii) Organic polymer assisted intercalation: 0.2 g of Sb2Se3 dispersed in solution of 0.2 g PVP
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5 dissolved in 40 mL N-methylpyrrolidone. The solution was stirred for 24 hrs. The precipitate
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8 was washed with ethanol. (iv) Lithium-ion intercalation: 0.2 g of Sb2Se3 dispersed in 2.5 mL
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10 n-butyllithium (1.6 M in hexane) and 10 mL hexane and stirred at RT under N2 atmosphere
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13 for 48 hrs. The precipitate was washed several times with hexane and ethanol. All the
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15 intercalated samples were exfoliated in water by ultrasonicating for 5-6 hrs. The exfoliated
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precipitate was centrifuged, dried under vacuum at 220 °C for 1 hr.
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21 The crystallographic data was recorded on Rigaku SmartLab X-ray diffractometer using
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23 CuKα as X-ray source. Raman vibrational modes were recorded using Horiba’s LABRAM-
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HR Evolution Raman microscope. Cyclic voltammetry (CV) measurements were performed
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28 on electrochemical workstation (CHI 6107, CH instruments) in a three-electrode system. The
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30 working electrode was glassy carbon electrode (GCE) coated with a paste of Sb2Se3 and
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33 nafion binder (5 wt%), dried in vacuum oven at 80 °C for 2 hrs. The Ag/AgCl and Pt wire
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35 were used as reference and counter electrodes, respectively. The CV measurements were
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38 recorded in 2M H2SO4 and 2M KOH in the potential range of +1 V to -1 V at 100 mV/s scan
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40 rate.
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3. Results and discussion
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47 The chemical intercalation-assisted exfoliation strategy was employed for the exfoliation of
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49 bulk Sb2Se3. The different intercalants that were used (H2O, PVP, Na+ and Li+) functioned as
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52 guest species that could penetrate into the interlayer spacing of Sb2Se3 host and weaken the
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54 van der Waals interactions for easy exfoliation. The bulk Sb2Se3 samples treated with H2O,
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57 salt (Na2SO4), organic polymer (PVP) and n-BuLi were mechanically exfoliated by
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59 ultrasonication. The efficacy of different intercalants in intercalation-assisted exfoliation
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procedures is shown in Fig.1. The exfoliated powders were structurally analysed using XRD
(Fig. 2a). The peaks of bulk Sb2Se3 correspond to the standard orthorhombic phase matching
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3 the JCPDS No. 15-0861. When compared with the exfoliated powders, the XRD patterns
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5 revealed significant decline in the number of peaks. This strongly indicates the absence of
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8 constructive interference from the missing planes, further evidencing that the exfoliation must
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10 have occurred along these planes causing a reduction in number of layers [9,10]. Also, the
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13 peaks corresponding to (230), (301) planes shifted to smaller angles, indicating the expansion
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15 of layers along that direction [11]. The Raman spectrum of bulk Sb2Se3 (Fig. 2b) showed two
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distinct peaks corresponding to the Raman shifts at 185 cm-1and 250 cm-1 which are
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20 characteristics of Sb2Se3 phase [7]. The Raman band centered at 185 cm-1 represents Ag mode
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22 of Se-Sb-Se bending vibrations, while the one at 250 cm-1 represents nonpolar Sb-Se
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25 stretching B1g mode [12]. For the exfoliated samples, the Raman bands showed increased
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27 intensity in the following order of intercalants used: Li+> Na+ > PVP > H2O. The increased
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30 intensity of the peaks could be a function of decreased thickness of Sb2Se3 sheets [13]. In
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32 addition, the gradual red shift of the peaks in the case of exfoliated samples can be ascribed to
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the softening of lattice vibrational modes caused by weakened long-range coulombic
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37 interactions in few layered Sb2Se3 [7]. Thus, the observed variation in the structural and
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39 molecular vibrational properties of bulk and exfoliated samples revealed successful
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42 intercalation-assisted exfoliation of bulk Sb2Se3. The electrochemical behaviour of bulk and
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44 exfoliated layers of Sb2Se3 was determined by cyclic voltammetry in a three-electrode system
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47 dipped in 2M H2SO4 and 2M KOH aqueous electrolyte solution. In a control experiment, a
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49 blank cyclic voltammogram (CV) with uncoated GCE showed a straight line indicating
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52 electrolyte stability and no redox activity within the potential window [14]. The CVs in acidic
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54 medium (Fig. 3a) exhibited a typical redox behaviour with characteristic peaks around -3.5 V
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for anodic scan and around +3.0 V for cathodic scan. This may indicate reversible
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59 insertion/deinsertion of H+ ions into/out of the Sb2Se3 layers [15]. For n-BuLi exfoliated
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Sb2Se3 sample, there is an absence of anodic peak. The results further indicated a gradual
decrease in peak current density in the following order of intercalant treated samples: H2O >
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3 PVP > Na2SO4 > n-BuLi which may be associated with the exfoliation efficiency. The
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5 prerequisite for intercalation in two-dimensional materials is the presence of at least two
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8 layers to accommodate a foreign species within the van der Waals spaces. For the exfoliated
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10 Sb2Se3 samples, the electrochemical re-intercalation ability (of H+ ions) is lowered with the
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13 decreased thickness of Sb2Se3 layers, subsequently decreasing the peak current density. A
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15 similar trend for the exfoliated Sb2Se3 samples is also observed in KOH electrolyte solution.
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The cathodic and anodic peaks originating from reversible intercalation and deintercalation of
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20 K+ ions in the potential range -1 to -0.6 V are displayed in Fig. 3b, demonstrating a redox
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22 character of the voltammogram. As observed in previous voltammograms, there is a similar
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25 systematic decrease of the peak current density in the order: bulk Sb2Se3 > H2O > PVP >
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27 Na2SO4 and absence of redox behaviour in Na2SO4 and n-BuLi treated samples. Moreover, a
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30 broad peak appeared at -0.11 V, -0.17 V, -0.21 V, -0.31 V and -0.4 V for bulk Sb2Se3, H2O,
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32 PVP, Na2SO4 and n-BuLi treated samples, respectively, which is associated with formation of
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KSb2Se4 [16,17]. From the results, it can be inferred that owing to their small size, inorganic
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37 cations (Li+, Na+) can serve as potential intercalants which can penetrate deeply in the layers
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39 of 2D materials causing excessive weakening of van der Waals interlayer interactions and
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42 efficient exfoliation. The hindrance caused by dipolar nature of H2O molecule makes it a
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44 weak intercalant as compared to bulkier organic/polymeric molecules.
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48 4. Conclusion
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51 The bulk Sb2Se3 was exposed to three types of intercalants, namely, H2O, organic polymer
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53 molecule (PVP) and inorganic cations (Na+, Li+). Although XRD and Raman analysis
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56 partially indicated magnitude of exfoliation, the results of electrochemical studies can be
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58 closely linked to the efficiency of intercalants and thus to the extent of exfoliation achieved in
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the samples. The inorganic cations showed superior intercalation ability which is evident from
the high exfoliation achieved upon sonication of the intercalated samples.
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21 Fig. 1. Intercalation-assisted exfoliation of Sb2Se3. Intercalation was achieved using H2O,
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23 PVP, Na+ and Li+ as intercalants.
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44 Fig. 2. (a) XRD patterns and (b) Raman spectra of bulk and exfoliated Sb2Se3 samples.
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Fig. 3. Cyclic voltammograms of bulk and exfoliated Sb2Se3 samples in (a) 2M H2SO4 and
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20 (b) 2M KOH solutions.
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23 Acknowledgements
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26 This work was supported by Start-up Research Grant (SRG/2022/002191) provided by
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29 Science and Engineering Research Board of Department of Science and Technology (DST-
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31 SEB), India.
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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.
☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests:
