Materials Letters

Surface Oxidized Ti3C2 MXene: Lead-free Cs2AgBiBr6 Double Perovskite Solar Cell
Efficiency Enhanced by Interfacial Engineering
--Manuscript Draft--

Manuscript Number: MLBLUE-D-23-02380

Article Type: Short Communication

Keywords: Solar energy materials; Surface oxidized TiO2-Ti3C2; Interfaces; Cs2AgBiBr6

material; Interfacial engineering

Abstract: In this study, thermal oxidation method is followed to prepare surface oxidized titanium
carbide (TiO2-Ti3C2) nanomaterial. Here, the formation of anatase phase TiO2
nanoparticles over the surfaces of Ti3C2 MXene is confirmed by UV-Vis, FT-IR, XRD
and FE-SEM and HR-TEM studies. The TiO2-Ti3C2 MXene acts an interfacial layer in
double perovskite solar cell that exhibits high open circuit voltage (Voc of 1.01 V), short
circuit current density (Jsc of 2.64 mA/cm-2), fill factor (FF of 0.55) and power
conversion efficiency (PCE of 1.35%) under ambient conditions. Hence, we suggest
that this surface modified material will be useful for double perovskite photovoltaics
applications.

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Highlights (for review)

Highlights:
 A bi-phasic titanium carbide MXene fabricated by thermal oxidation process.
 TiO2-Ti3C2 MXene material shows excellent light harvesting behaviour.
 The MXene interfacial layer as improve the interfacial electron extraction.
 The surface oxidized interfacial layer is achieved high 1.06 Voc and 1.31% PCE.
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Surface Oxidized Ti3C2 MXene: Lead-free Cs2AgBiBr6 Double Perovskite Solar Cell

1 Efficiency Enhanced by Interfacial Engineering

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4 Nandhakumar Eswaramoorthya, Sathish Rajendranb, Vivek Elangovanc, Susanta Kumar Bhuniab,
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6 Selvakumar Pitchiyad* Kamatchi Rajarama*
7 a
School of Mechanical Engineering, Vellore Institute of Technology, Vellore 632 014, Tamil Nadu, India
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b
9 School of Advanced Sciences, Vellore Institute of Technology, Vellore 632 014, Tamil Nadu, India
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Department of Industrial Chemistry Engineering, Pukyong National University, Busan, South Korea.
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12 Faculty of Engineering and Science, Western Norway University of Applied Sciences, 5063 Bergen, Norway
13 *
Corresponding authors: rkkamatchi@gmail.com (Dr. Kamatchi Rajaram); sharewithselva@gmail.com
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15 (Dr. Selvakumar Pitchiya)
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20 Abstract
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22 In this study, thermal oxidation method is followed to prepare surface oxidized titanium carbide
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25 (TiO2-Ti3C2) nanomaterial. Here, the formation of anatase phase TiO2 nanoparticles over the
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27 surfaces of Ti3C2 MXene is confirmed by UV-Vis, FT-IR, XRD and FE-SEM and HR-TEM
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studies. The TiO2-Ti3C2 MXene acts an interfacial layer in double perovskite solar cell that
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32 exhibits high open circuit voltage (Voc of 1.01 V), short circuit current density (Jsc of 2.64
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34 mA/cm-2), fill factor (FF of 0.55) and power conversion efficiency (PCE of 1.35%) under
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37 ambient conditions. Hence, we suggest that this surface modified material will be useful for
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39 double perovskite photovoltaics applications.
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42 Keywords: Solar energy materials, Surface oxidized TiO2-Ti3C2, Interfaces, Cs2AgBiBr6
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44 material, Interfacial engineering.
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1. Introduction
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49 Two-dimensional (2D) transition metal carbides and nitride materials are used in energy
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51 conversion applications such as photovoltaic, photocatalytic, photodetector etc. owing to unique
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54 optical, chemical and electrical properties. In general, the formation of Ti3C2Tx (MXene) is
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56 obtained from the Ti3AlC2 (MAX) phase, where Tx indicates the insertion of ions such as
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59 fluorine (F2), hydroxide (OH)2 and oxygen (O2) [1]. The improved photovoltaic properties of
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61 Ti3C2Tx material motivates the researchers to use in lead-free perovskite photovoltaics in the
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 recent years. Also, MXene improves life time and reduces the surface defects of perovskite

1 photovoltaic devices [2]. However, Ti3C2 MXene has low light absorption behaviour. To
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overcome this issue, heat treatment, alkalinization and acid treatment are followed to modify the
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6 MXene surface. This surface modifications form M-O bond (metal oxide) that improves the light
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8 harvesting behaviour.
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11 In this work, TiO2-Ti3C2 MXene-the most representative 2D materials is obtained by thermal
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13 oxidation approach. The as-prepared pure and surface oxidized MXene interfacial layered
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16 Cs2AgBiBr6 perovskite solar cell is experimented under 1.5 AM solar irradiation. Results show
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18 that the surface oxidized MXene improves the light absorption behaviour and hence, this study
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21 will be useful for double perovskite (Cs2AgBiBr6) photovoltaic applications.
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24 2. Experimental section
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26 2.1 Synthesis of Ti3C2 MXene
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29 Typically, pure titanium carbide (Ti3C2) MXene was synthesized utilizing bulk titanium
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31 aluminum carbide (Ti3AlC2, size: 40 μm, 90% purity, Sigma-Aldrich) MAX phase through the
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34 acid etching process. Initially, 1g of Ti3AlC2 and 20 mL of hydrofluoric acid (HF, 48%, Sigma-
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36 Aldrich) was taken in a PTFE beaker. Further, the mixture was stirred for 12 h at room
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temperature (RT). The obtained sample was then washed several times with deionized water
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41 until the pH of the supernatant became neutral. The acquired sample was labelled as Ti3C2.
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2.2 Synthesis and paste preparation of surface oxidized TiO2-Ti3C2 MXene
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47 The surface oxidized Ti3C2 was synthesized using slightly modified method from the one
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49 described above. Subsequently, etched MXene was calcinated at 450 ˚C for 3 h in presence of
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52 ambient atmosphere. As a result, the MXene surface was oxidized and forms anatase TiO2. The
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54 obtained sample was labelled as TiO2-Ti3C2. Further, the MXene paste preparation process was
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57 schematically represented in Fig. S1 which was followed by our previous work [3].
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60 3. Device fabrication
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 Cesium bromide (CsBr, 99.99%, Alfa Aesar), silver bromide (AgBr, 98.95%, Alfa Aesar),

1 bismuth bromide (BiBr3, 99.92%) material was taken in the ratio of 2:1:1 and mixed with 10 mL
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hydrobromic acid (HBr, 48% in H2O, Sigma-Aldrich). The mixture was stirred continuously at
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6 120 ˚C for 90 min to attain a yellow colour product and then subsequently cooled at RT. The
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8 resultant mixture was then dried using rotary evaporation method to obtain as powder form.
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11 Then, the obtained powder was dissolved in dimethyl sulfoxide (DMSO, 99.9%, Sigma-Aldrich)
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13 to form a 0.5 mol L−1 concentration solution for carbon based double perovskite solar cell
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16 (DPSC) devices. Here, the photovoltaic device fabrication procedure was followed by our
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18 previous work [3]. The standard device ((DPSC-1 (FTO/c-TiO2/Cs2AgBiBr6/Carbon), pure
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21 Ti3C2 MXene (DPSC-2 (FTO/c-TiO2/Ti3C2/Cs2AgBiBr6/Carbon)) and surface oxidized MXene
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23 interfacial layered solar cell (DPSC-3 (FTO/c-TiO2/TiO2-Ti3C2/Cs2AgBiBr6/Carbon))
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25 fabrication processes are illustrated in Fig.S2.
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28 2.3 Characterization
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30 The prepared Titanium MXene material optical properties were analyzed through (JASCO (V-
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33 670 PC)) UV-Vis spectroscopy. Bruker, D8 Advance X-ray diffractometer was used to confirm
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35 the crystalline nature was confirmed. The morphological nature of the prepared sample were
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38 investigated using Thermo Fisher FEI-Quanta 250 FEG FE-SEM and HR-TEM analysis (FEI-
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40 Tecnai G2 20 Twin). The photovoltaics J-V characteristics for the fabricated devices were
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confirmed using an OREL solar simulator (AM 1.5 solar irradiation) through connected Keithley
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45 2450 source meter under ambient condition.
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47 3. Results and Discussion
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50 The UV-Vis DRS spectra is used to evaluate the optical behavior of TiO2 nanoparticles over the
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52 surface of the Ti3C2 nanolayers. Three absorption peaks are observed in the region at 260, 350
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55 and 550 nm. The two peaks at 260 nm and 550 nm corresponds to Ti3C2 and a additional peak at
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57 350 nm is attributed to the TiO2 nanoparticles as shown in Fig. S3(a) and Fig. 1(a). A Tauc’s
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plot is used to determine the bandgaps of Ti3C2 at 1.08 eV and TiO2-Ti3C2 at 3.17 eV
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 respectively, as illustrated in Fig. S3(b) and Fig. 1(b). The increased band gap will provide rapid

1 charge transfer between the host and guest energy positions.

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31 Fig.1 (a) UV-Vis spectra (b) Tauc plot (c) FT-IR and (d) XRD analysis of TiO2-Ti3C2 MXene
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35 Moreover, the functional groups of MXene before and after surface oxidation are assessed using
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37 the FTIR spectrum. Fig. S4 depicts the absorption peaks of pure Ti3C2 MXene at 3428, 2346,
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39 1626, 1374 and 1050 cm-1 which is attributed to surface hydroxyl groups and Ti-OH vibration.
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42 Besides, the peak at 500-700 cm-1 corresponds to Ti-O vibrations. The peak at 2923 cm-1
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44 indicates existence of alkyl groups. After oxidization, some of the peaks are shifted and
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47 disappeared. The peak at 3438, 2923, 1634, 1374 and 1122 cm-1 absorptions are significantly
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49 increased, additionally a new peak appears at 572 cm-1 which indicates pure TiO2 peak. These
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52 results clearly demonstrate the existence of surface oxidation in the formation of bi-phasic TiO2-
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54 Ti3C2 MXene material (Fig. 1(c)). In addition, Fig. S5 represents various crystalline peaks of
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Ti3AlC2, all the 2θ peaks (10.15˚, 19.65˚, 34.56˚, 36.53˚, 37.26˚, 39.47˚, 42.17˚, 45.36˚, 49.04˚,
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59 52.72˚, 56.90˚, 61.07˚, 65.73˚, 70.89˚, 72.85˚, 74.57˚, 76.53˚, 83.65˚ and 87.09˚) are well
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 matched with previously reported Mathis et al., 2021 and Shuck et al., 2019 works [SI-9,10].

1 After etching, the major peak of Al is disappeared at the peak position of 39.4˚, additionally, the
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peak at 10.1˚ got reduced and shifted to 8.6˚, which indicates the formation of Ti3C2 layers, as
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6 illustrated in Fig. S6. Compared to pure MXene peaks, the new TiO2 peaks are arrived for TiO2-
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8 Ti3C2 MXene which is shown in Fig. 1(d). These peaks are attained due to thermal oxidization
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11 and the respective JCPDS Card No is 98-000-5226. Also, titanium carbide (TiC) material
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13 (JCPDS Card No:98-009-3040) is associated with all samples due to synthesis of MAX phase.
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17 The surface morphologies of Ti3AlC2, Ti3C2 and TiO2-Ti3C2 are analyzed using FESEM
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19 analysis. The FESEM image of Ti3AlC2 MAX phase confirms formation of bulk size that are
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21 shown in Fig. S7(a, b). After etching, aluminium layers are removed resulting stacked layer
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24 formation as represented in Fig. S7(c, d). The thermal oxidation of Ti3C2 MXene lead to the
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26 formation of TiO2 as illustrated in Fig. 2(a). The corresponding reaction is represented in eqn.
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29 (1) and (2)
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31 Ti3AlC2+3HF→ Ti3C2+AlF3 (1)
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33 ∆
34 Ti3C2+O2→TiO2-Ti3C2 (2)
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37 Similarly, the HR-TEM image of TiO2-Ti3C2 represents sheet like structure, as illustrated in
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39 Fig. S8. Further, Fig. 2(b, c) displays the Ti3C2 MXene (d-spacing:0.49 nm) and TiO2 material
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(d-spacing:0.32 nm) lattice fringes because of the interplanar distance [4]. Fig. 2(d) shows
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44 selected area electron diffraction pattern (SAED) of TiO2-Ti3C2 MXene that corresponds to
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46 major h k l values (011, 111, 013 and 004) which is in agreement with the XRD results (Fig.
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49 1(d)). Generally, the pure Ti3C2 MXene materials have low band gap and hence, used in non-
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51 light absorbance applications. The prepared pure Ti3C2 MXene crystal structure has less
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54 response under sun lighting condition as represented the schematic diagram in Fig. 3(a) and (b).
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56 To overcome this issue, Ti3C2 MXene surface is oxidized through thermal treatment in mean
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59 time titanium and oxygen bonds are formed which is illustrated in Fig. 3(a) and (c).
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27 Fig.2 (a) FE-SEM image (b, c) Lattice fringes (d) SAED pattern of TiO2-Ti3C2 MXene
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31 This leads to formation of titanium-oxygen (Ti-O) bond that acts as n-type semiconductor in
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33 Ti3C2 MXene surface. These bi-phasic structure is responsive under lighting condition due to
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35 formation of TiO2 and schematically represented in Fig. 3(a). Further, the possible charge
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38 transfer mechanism of the fabricated TiO2-Ti3C2 MXene interfacial layered DPSC device is
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40 depicted in Fig. 3(d).
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43 Table 1 J-V characteristics of c-TiO2, pure Ti3C2 and TiO2-Ti3C2MXene layer
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45 Device structure Jmax (mA/cm-2) Vmax (V) Jsc (mA/cm-2) Voc (V) FF PCE (%)
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47 DPSC-1 0.44 1.04 1.158 0.71 0.56 0.46
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49 DPSC-2 0.57 1.33 2.32 0.94 0.34 0.76
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DPSC-3 0.76 1.78 2.64 1.01 0.50 1.35
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56 The device absorbs photons from the solar light causes rapid charge transfer. The double
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59 perovskite layer absorbs the photons and generates electrons and holes. The exited electrons
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 from the perovskite are captured by anatase phase of TiO2-Ti3C2 MXene and then transfers to

1 c-TiO2 layer/FTO while the holes are captured by carbon electrode.

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(a) Ti C O
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6

Ti3C2
7 TiO2-Ti3C2
8 hν
9 TiO2 CB
Without surface oxidation
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12 VB
TiO2-Ti3C2

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Anatase phase TiO2
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With surface oxidation
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less light absorbance in MXene surface Light absorbance induce in MXene surface
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hν
20 hν
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26 Ti3C2 MXene TiO2 -Ti3C2 MXene
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(d) (e) 3.5
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3.0
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Current Density (mA cm )

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-2

2.5
Cs2AgBiBr6

(c)
32 2.0
TO2 - Ti3C2

33 1.5
(b)
FTO

(a)
Carbon

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c-TiO2

1.0

35 0.5

36 0.0
37 -0.5
38 Electrons Holes
0.0 0.4 0.8 1.2

39 Voltage (V)

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42 Fig. 3(a) Schematic diagram of pure Ti3C2and Ti2C2-TiO2MXene material structure (b, c) light
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45 harvesting and (d) Charge transfer mechanism (e) The red (DPSC-1), brown (DPSC-2) and blue
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47 (DPSC-3) lines indicate the J-V characteristics of Cs2AgBiBr6 solar cells.
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50 This reaction continues until the light illuminations at the top surface of the device. The
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52 constructed TiO2-Ti3C2 MXene device induces two-step charge transfer as compared with pure
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55 Ti3C2 layer. Fig. 3(e) illustrates the current-voltage (J-V) curves of the fabricated DPSC-1,
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57 DPSC-2 and DPSC-3 device under AM1.5 solar irradiation. The corresponding J-V
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characteristics are listed in Table 1. As observed, the open circuit voltage (Voc) is in the order of
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 0.71, 0.94 and 1.01 V respectively. The short circuit current density (J sc) has a value of 1.15,

1 2.32 and 2.64 mA/cm-2 and power conversion efficiency (PCE) of 0.46, 0.76 and 1.35%
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respectively. The improved performance of the TiO2-Ti3C2 MXene device is mainly due to the
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6 reduced recombination losses in between c-TiO2/Cs2AgBiBr6 interface. Particularly, higher Voc
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8 is attained due to bi-phasic phase of MXene interfacial layer. Moreover, the fill factor (FF) of
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11 DPSC-2 is comparatively lower than DPSC-1 and DPSC-3 devices due to charge recombination
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13 phenomenon between the Ti3C2 layer over TiO2/Cs2AgBiBr6 perovskite interface. The DPSC
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16 device structure and performance is compared and summarized in Table ST1.
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18 4. Conclusion
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21 The J-V characteristics of pure Ti3C2 and oxidized MXene (TiO2-Ti3C2) interfacial layered
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23 Cs2AgBiBr6 photovoltaics are experimentally investigated and compared under solar irradiation.
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25 The oxidized MXene interfacial layer exhibits improved electron extraction and transportation
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28 behaviour than pure MXene. Also, oxidized MXene surface induces the anatase phase TiO2
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30 material which improves light absorbance, Voc and PCE respectively. Also, oxidized MXene
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33 prevents the surface defects, reduces electrical losses and enhances c-TiO2/Cs2AgBiBr6
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35 interfacial adhesion. In future, the oxidized 2D MXene material places a significant role in
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38 double perovskite photovoltaic fields.
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40 Data availability
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Data will be made available on request.
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45 References
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47 [1] X. Zhang, J. Shao, C. Yan, R. Qin, Z. Lu, H. Geng, T. Xu, L. Ju, Mat.& Des. 200(2021)109452.
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49 [2] W. Li, R. Li, D. Wang, G. Li, W. Pan, S. Wang, W. Sun, J. Wu, Z. Lan, ACS Appl. Ener. Mat. 5(10)
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51 (2022)12388-12395.
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53 [3] N. Eswaramoorthy, A. Arulraj, R. V. Mangalaraja, S. Pitchaiya, K. Rajaram, Int. J. Ener. Res.46 (14)
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56 (2022) 20194-20205.
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58 [4] G. Zhao, H. Lv, Y. Zhou, X. Zheng, C. Wu, C. Xu, ACS Ap. Mat.& Inte.10 (49) 2018. 42925-
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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: