4.1. Vacuum Filtration Method

Uniform and well-controlled MXene thin films are required for different applications, including energy storage, conversion, and optoelectronic applications. The simplest method to achieve uniform MXene thin films is Vacuum-assisted filtration (VAF). In this method, a stable dispersion of MXene was prepared, and a suction filtration device was used to filter it. MXene sticks on the porous membrane’s surface after filtration and forms a thick layer (Figure 3A) [56]. The thickness of the film depends on the concentration of MXene, and as filtration is a self-limiting phenomenon, so uniformity of the film on the filter membrane is self-leveling [57] van der wall forces are also involved in bringing the MXenes closer to each other on the surface of the filter membrane. After that thick MXene layer need to be peeled off from the filter membranes and can be used in different applications. Filter membrane, suction speed, solvent, and MXene concentration are the factors that affect film formation. Although the VAF method is easy to use, it takes much time and energy to prepare a film. To make this process fast, a different approach is used by adding a small amount of alkali in Ti₃C₂ MXene before filtration to narrow down the time of filtration to about dozens of seconds rather than hours [58]. Another critical aspect of the MXene thin films fabricated by the VAF method is the peeling of complete film for patterning it to obtain advanced applications. Obtaining a thick layer from VAF could lead to ease in peeling from the filter membrane, and then patterned cutting of this film through laser enhanced its applicability in tattoo-based sensors and electromagnetic interference shielding [59,60].

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Figure 3

(A) VAF method for MXene thin films (reproduced with permission [56]. Copyright 2021, Elsevier); (B) SEM image of a multilayered thin film of Ti₃C₂ sheets (reproduced with permission [68]. Copyright 2018, American Chemical Society); (C) Application in supercapacitors, (reproduced with permission [62]. Copyright 2020, American Chemical Society); (D) Adjusting the properties of MXenes with different polymers (reproduced with permission [67]. Copyright 2014, National Academy of Sciences).

Hu et al. fabricated a thick film of few-layered Ti₃C₂ MXene nanosheets using the vacuum deposition method on Millipore filters [61]. The uniformity of the MXenes thin films fabricated by using the VAF method has been confirmed by utilizing electron microscopy (Figure 3B). Plenty of MXene composites-based thin films were prepared by using the VAF method. To provide unique properties to MXenes thin films, polymers were functionalized on the surface by chemical and physical means. For instance, conductive polymer polyvinyl alcohol (PVA) mixed with Ti₃C₂ to form flexible thin films by exploiting the VAF method for high-capacity charge storage applications (Figure 3C) [62]. MXene composite materials in thin films have been used in various applications, including solar cells, batteries, supercapacitors, adsorbents, and energy conversion systems [63]. The mandatory requirement to utilize the properties of MXenes in solar cells, batteries, supercapacitors, and adsorbents is to obtain its uniform thin film. In this regard, Huang et al. designed a highly stable, flexible, and higher specific capacity (221 Fg⁻¹) containing MXene@carbon nanotubes and MnO₂-based hybrid thin film via the VAF method to use it as a supercapacitor [64]. Further, to obtain insight into the advanced level studies of MXene-based thin films for supercapacitors, the VAF method was utilized to fabricate MXene@Holey-Graphene films. Holey graphene was used to avoid self-restacking of Ti₃C₂, and a very unique, highly porous connectivity network was established there for the immense acceleration of ion transport, and it also shortened the transport pathway for ions and electrons [65]. VAF method has been used to fabricate micro-supercapacitors of Ti₃C₂ MXene. Well-dispersed MXene solution was vacuum filtered on an interdigital patterned mask and obtained a thin, highly conductive film used as a supercapacitor [66]. Other composites also cause a significant impact on the physical properties of MXenes. The nature of the dopant or polymer decides the final product’s flexibility, conductivity, and chemical properties. To tune the mechanical properties of MXenes, Ling et al. tried poly(diallyldimethylammonium chloride) and PVA polymers with MXene, and the resulting thin films have shown different properties in terms of conductivity and flexibility (Figure 3D) [67].

Tuning of the thickness of MXene film is required to use it in different electronic applications. Lightweight and ultrathin MXene films are needed for integrated electronics. Composite of MXene sheets with conductive polymers are not always favorable for energy storage and electronic applications. A controlled amount of dopant is required to obtain an advantage from the MXene composite films. For instance, to avoid electromagnetic waves, Liu et al. designed a Ti₃C₂/PEDOT: PSS-based biomimetic thin films shield by using VAF [68]. VFM has also been utilized to form mixed metal-containing MXene materials. In this regard, Halim et al. fabricated free-standing Mo₂TiC₂T_x MXene thin films by simply using the VAF method [69]. Similarly, doping into MXene leads to improvement in the mechanical properties of the MXene films. Dopamine doping in Ti₃C₂ MXene thin films provided seven times enhanced tensile strength with a tremendous increase in elongation fabricated by VAF [70].

4.2. Electrodynamic Atomization and Electrophoretic Deposition

The electrohydrodynamic atomization technique (EHAT) has been utilized to form thin films of different materials. EHAT can be performed in two ways, (i) electrospraying and (ii) electrospinning [71]. In a typical EHAT process, the formation of droplets occurs when a well-dispersed liquid is poured into the nozzle. On applying a strong electric field, these droplets get charged, and the droplet at the end of the nozzle forms a cone shape spraying mode. A charged jet of liquid fall on the collector, which has an opposite charge to droplet or grounded. By changing the voltage, and distance between collector and droplet spray, this technique causes the formation of nanoparticles or fibers [72]. Different atomization modes can be applied to form particles and fibers, including micro-dripping, spindle, cone-jet, and multi-jet. Droplet size depends on the applied voltage, flow rate, and physical properties of the liquid. In the case of MXenes, Ali et al. utilized the EHAT technique for the hole-free and uniform growth of Ti₃C₂Tx (100–400 nm) MXene thin film [73]. Similarly, Fang et al. applied the electrostatic and electrospray deposition method to fabric MXene/polymer-based composite thin films and have been utilized for strain sensors (Figure 4A) [74].

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Figure 4

(A) Electrospray; (B) Electrophoretic method for the fabrication of Ti₃C₂T_x films; and (C) SEM images of the Ti₃C₂T_x formed under different voltage conditions for 600 sec each in water and polypropylene carbonate suspension. (reproduced with permission [74]. Copyright 2021, MDPI) (reproduced with permission [75]. Copyright 2017, IOP Science).

While in the case of electrophoretic deposition (EPD), an electric field is applied to the stable colloidal suspension present between two electrodes, and it causes the deposition of charged MXenes on the respective electrode (electrophoresis). In the second case, after applying an electric field to the colloidal solution containing MXenes, deposit coagulation is formed at the interface of suspension and electrode (deposition) (Figure 4B) [75]. On varying the voltage, the film formation process, thickness, morphology, and flake orientation may change. To test this, Collini et al. fabricated Ti₃C₂ MXene thin films by EPD process at 5 V, 10 V, 15 V, and 20 V for 600 s each, and it was observed that initially, the conductivity of Ti₃C₂ MXene thin films was decreased, but later for 10 V, it increased to a specific value (Figure 4C).

4.3. Spin Coating Method (SCM)

Spin coating is a standard method for fabricating thin films of different materials [76,77]. In this technique, a substrate is spun at high speed with a liquid solution on its surf. The involvement of centripetal force and surface tension of the liquid cause even distribution of the liquid on the surface of the substrate. After evaporating any solvent from the surface of the substrate, a few nanometers to micrometers of thin films can be obtained. MXene thin films were also fabricated by using the spin coating method (SCM). The nature of the substrate is dependent on the application of the MXene materials. For instance, for solar cell fabrication ITO, FTO, and other flexible substrates were used for spin coating of MXenes. The spin coating can be performed by casting a solution on a spinning substrate or pouring a solution onto a stationary substrate and rotating it to the required rotation to obtain thin films. A substrate with a 10 cm diameter can be used commercially in spin coater. Two significant factors that affect the formation of MXene films in SCM involved rotation speed and the concentration of MXene in a respective solvent. Higher the rotation per minute, less area will be covered by the film on the substrate surface. Similarly, a high concentration of the MXene solution will cover the larger area on the substrate, and a uniform film will obtain. In contrast, a gradual increase in speed will cause a decrease in the thickness of the MXene film. To obtain a uniform thin layer, it is mandatory to reach the ramping speed in SCM. The multilayered thin films can also be obtained with SCM. By changing the parameters mentioned above, it is possible to change the thickness of the MXene films in SCM. In this regard, Zhang et al. fabricated Ti₃C₂ MXene thin films on silica substrate by using SCM for a memristive device (Figure 5A) [78]. The film’s characterization was performed using different microscopic techniques, including SEM, TEM, and AFM, and the thickness of the Ti₃C₂ film was about 2.2 µm. It is possible to design intelligent thin films by using SCM. SCM has also been used in fabricating MXene thin films on patterned substrates. For instance, Huang et al. fabricated Kapton masked hydrophilic silica substrate to obtain suitable adhesion of Ti₃C₂ MXene thin films (Figure 5B) [79]. The treatment of silica substrate with hydrophilic groups causes uniformity and integrity in the thin film Ti₃C_2, while the thickness of the film was about 142 nm. Ti₃C₂T_x MXenes synthesized by SCM have shown excellent physical, electronic, and chemical properties as it is easy to tune the thickness. Dillon et al. fabricated highly conductive Ti₃C₂ MXene films with a roughness of 3 to 9 nm and tunable thickness ranging from 2 to 81 nm (Figure 5C) [80]. Different titanium carbide films synthesized using SCM have shown the highest conductivity value of about 5000 S cm⁻¹. The transparency of these films was about 80% [30,81]. SCM is not only limited to Ti₃C₂ and Ti₂C MXenes but has been used for the fabrication of other MXenes. Ying et al. have used SCM to fabricate transparent V₂CT_x films in tetrabutylammonium hydroxide (TBAOH) dispersant. The conductivity value for thicker and thinner V₂CT_x films was about 3300 ± 100 S/cm [82]. Because of the improved electrochemical performances of the MXene thin films fabricated by using SCM, this method has been explored to fabricate MXene-based composite films. MXene-based composite thin films have also been used in different applications, including energy storage and sensors, which require foldability, flexibility, and scalability. In this regard, Gund et al. fabricated Ti₃C₂@PEDOT: PSS-based flexible and foldable thin films to be used as supercapacitors. The thickness of the film obtained was about <1 µm, and it has a faster charge and ion transportation (Figure 5F) [83].

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Figure 5

(A) Schematic drawing of SCM (reproduced with permission [78]. Copyright 2019, Elsevier); (B) Schematics of Ti₃C₂T_x MXene film formation on patterned silicon substrate using SCM method, (reproduced with permission [79]. Copyright 2020, Elsevier); (C) SEM images of Ti₃C₂T_x MXene film formed by SCM. The scale bar is 5 µm (reproduced with permission [80]. Copyright 2019, Wiley-VCH); (D) Fabrication of Ti₃C₂T_x MXene film on a flexible substrate with SCM (reproduced with permission [85]. Copyright 2020, American Chemical Society); (E) Photolithography was performed for patterning, and SCM was utilized for the fabrication of MXene film on the designed surface (reproduced with permission [86]. Copyright 2019, Wiley-VCH); (F) Schematic of MXene@PEDOT: PSS thin films fabricated using SCM and symmetric capacitors, photographic images of composite MXene thin films their scalability, foldability, and rollability (reproduced with permission [83]. Copyright 2018, Elsevier).

The number of layers of MXene sheets could also be tuned by repeating the spin cycles. By increasing the speed of the rotator and diluting the solution to a more considerable extent, it is possible to attain single-layered MXene thin films for a variety of applications. For instance, Zou et al. fabricated the thin films of Ti₃C₂ at a lower rotation speed of about 200 rpm, and the thickness of the film was about 25 µm [84]. Another important aspect of SCM is the fabrication of thin films on different substrates, including glass, ITO, FTO, and polymeric flexible substrates. To obtain free-standing and flexible substrate-based MXene nanosheets, Li et al. have utilized SCM to fabricate Ti₃C₂ and poly(vinylidene fluoride) trifluoroethylene composite MXene thin film on a glass substrate. After getting a uniform thin film on a glass substrate, it was heated to about 80 °C and then immersed in water to obtain free-standing flexible MXene thin films for wearable electronics (Figure 5D) [85]. Patterned MXene thin films on different substrates were obtained by using complicated techniques involving laser cutting and printing techniques. SCM has also been utilized to fabricate patterned thin films of MXene, but it involves the masking of the substrate. In this regard, Montazeri et al. masked the gallium arsenide (GaAs) substrate for the fabrication of guided and patterned Ti₃C₂ thin film (19.2 nm) to be used in photodetector (Figure 5E) [86]. Hence, by utilizing SCM, it is possible to coat different MXene materials on various surfaces, either solid or flexible, for useful applications. MXene thin films fabricated by SCM are homogeneous in nature because of the involvement of different forces, including electrostatic, centrifugal, air shear, and viscous forces. These forces cause the adsorption and rearrangement of the MXene thin films along with dehydration of the films on the substrate [87]. In summary, SCM is a widely used method for fabricating single-layered or multilayered uniform, homogeneous and thin MXene films.

4.4. Spray and Dipping Method

Defect-free films are essential for higher conductivity values. The Chemical Vapor deposition method has been used to form various films on different substrates. The higher fabrication cost and limitations in size cause commercialization problems. Further, spin coating and electrodeposition methods have shown higher R_s values because of inter-flake distance and defects. The spray-coating method emerged as a new solution-based method for fabricating defect-free MXene films to overcome these obstacles. The spray-coating method is the fastest method for the fabrication of thin films, and in comparison to SCM, it is helpful on an industrial scale. Consecutive washing and spraying MXene solution on the substrate can cause the fabrication of thin and uniform layers. It is beneficial to control the thickness and transparency of MXene thin films. Spray flow, spray speed, nature of substrate, and cycles of spray affect the viscosity of MXene thin films. For instance, Gogotsi et al. fabricated Ti₃C₂ MXene thin film with thickness varying from 5 to 70 nm by utilizing the spray-coating method (Figure 6A) [88].

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Figure 6

(A) Spray coating of Ti₃C₂ MXene; (B) AFM image of the MXene thin film synthesized by using the spray-coating method, (reproduced with permission [88], Copyright 2016 Wiley-VCH); (C–E) I-V curves, resistance vs. temperature plot, and SEM image of the Ti₃C₂T_x thin film fabricated by using the spray-coating method, (reproduced with permission [89]. Copyright 2018 Wiley-VCH); (F–H) Cross-sectional SEM image, high-resolution TEM image, and photographic picture of the MXene@rGO thin films (reproduced with permission [90]. Copyright 2019 Wiley-VCH).

The spray-coating method is considered the best option for large area processing techniques, including inkjet printing and roll-to-roll processing. In the case of device fabrication, researchers always require a suitable method to obtain excellent electronic and chemical properties from the fabricated MXene thin films on a large scale. The spray-coating method has also been explored to fabricate large-scale MXene thin films without causing any damage to their physical or chemical properties. Wang et al. synthesized large area Ti₃C₂ MXene thin films for the n-type and p-type transistors with a thickness in the range of 3.69 nm and excellent electronic properties of MXene thin films obtained by using the spray-coating method (Figure 6B–E) [89]. MXene composite materials played an essential role in the enhancement of conductivity and improvement in the MXene electrochemical properties. The fabrication of large-scale uniform MXene thin films is a time-consuming process. The spray-coating method has been efficiently used to fabricate large-scale MXene film in a short time. Zhao et al. fabricated MXene/reduced graphene (r-GO) paper-based thin films by spray-coating method to prepare binder-free electrodes directly used in Na-ion batteries as an anode material [90]. Layer-by-layer assembly of Ti₃C₂ MXene and graphene films obtained by this method can be seen clearly from high-resolution transmission electron microscopy (TEM) (Figure 6F–H). In summary, the spray-coating method is widely used to fabricate uniform, ultrathin and flexible monolayer and multilayers films of MXene materials. In the spray-coating method, MXene layers are well organized and distinct from each other.

Different methods are required to tune the thickness of MXene thin films. It is always a requirement to improve the mechanical, chemical, physical, and electrical properties of MXene thin films. Although vacuum filtration, spray, and SCM proved efficient for fabricating transparent, highly conductive, and flexible thin films of MXenes. Still, due to ease in use and fabrication of ultrathin films with lower solution concentration, the dip-coating approach gained much attention. The dip-coating method (DCM) is another way to produce MXene thin films with tunable thickness and lower roughness. In this method, the substrate is manually immersed in the MXene solution to obtain thin films with different thicknesses. Different factors that affect the film fabrication process in DCM involve substrate nature, surface modification of substrate, dipping time, and concentration of MXene solution. For sufficient layer deposition, it is always required to dip the substrate in MXene solution for almost 5 min. Consecutive cycles of dipping and washing the substrate are required to obtain uniform and defect-free films. Due to less contact with open air, DCM provides a coating shield to MXene. MXene thin films prepared from DCM have been used in different applications, including electromagnetic interference shielding, micro-supercapacitors, flame retardancy, and a suitable absorber [91,92,93,94]. In the DCM, a substrate with or without functionalization is dipped into the solution containing MXene. After plenty of dipping cycles in and out, a very uniform thin layer formed on different substrates. Salles et al. fabricated Ti₃C₂ MXene thin film by utilizing the dip-coating method with extraordinary optoelectronic properties. The dip-coating method was employed to obtain the different thicknesses of Ti₃C₂ MXene thin films ranging from 20 to 150 nm (Figure 7A,B) [93]. Salles et al. fabricated another Ti₃C₂T_x MXene thin film with 30 nm thickness, different film surface roughness, and T550 nm = 65% transmittance to obtain a variety of applications [95]. Multiple factors are involved in getting a homogeneous and uniform layer of MXene in the case of DCM, such as dipping speed, MXene composition, substrate, surface chemistry of MXenes, and environmental factors. Higher the thickness of the films better the absorption in the UV region. It is always interesting to obtain a uniform assembly of MXene nanosheets on different sizes and shapes of the substrate. DCM proved to be an efficient method to obtain films of MXene on any kind of substrate, whether it is flat or randomly designed surfaces. In this regard, Shui et al. fabricated uniform Ti₃C₂ coatings on the sponge by simply dipping a sponge in Ti₃C₂ solution for about 5 min and acted as a suitable terahertz absorber (Figure 7C,D) [91]. Such versatility of DCM proved beneficial not only for energy storage devices but also for sensing devices. Such coatings are beneficial for different sensors because of the network-based structure of the sponge or coating material [96]. Similarly, Yue et al. utilized the 3D network of sponge material and coated it with Ti₃C₂ to obtain a piezoresistive sensor (Figure 7E) [96]. MXene-coated sponge material has shown excellent mechanical stability, porosity, and electrical properties. Controlling the number of layers of MXene thin films is another challenging task to improve the mechanical and chemical properties of MXene. The DCM proved to be an efficient method for controlling the number of layers of MXene sheets.

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Figure 7

(A) Schematic illustration of the preparation of Ti₃C₂ MXene thin film by using the dip-coating method, DLS measurements including size and zeta potential value of as obtained MXene flakes; and (B) SEM images of Ti₃C₂T_x thin films with different thickness (reproduced with permission [93]. Copyright 2018 Wiley-VCH); (C,D) Schematic of coating MXene on sponge and SEM images of MXene sponge foam (1–3) showing the different Ti₃C₂ flakes, (reproduced with permission [91] Copyright 2020 Wiley-VCH); (E) Schematic process for the fabrication of MXene-based sponge, (reproduced with permission [96] Copyright 2018 Elsevier).

Bilayer Ti₃C₂@montmorillonite MXene sheets were fabricated by dipping the substrate into piranha solution for one hour and then in poly(vinylpyrrolidone) solution for 15 min. Lastly, dipping this substrate into Ti₃C₂@montmorillonite solution caused the formation of bilayer sheets. After repeating these dipping cycles, it is possible to obtain the desired number of bilayers of sheets [97]. Due to ease of use and inherent scalability, a drop-casting method is an excellent option for synthesizing large-scale MXene films. The drop-casting process has not been studied extensively because of planar and hydrophilic substrates. Despite such limitations, Lipton et al. fabricated large-scale (125 cm²) Ti₃C₂ MXene film with 23.2 µm thickness and 14 nm roughness [98]. Except for Ti₃C₂, other MXene materials, owing to their higher conductivity and excellent stability, were utilized to fabricate thin films to obtain advanced applications, including supercapacitors, sensors, and batteries. In this regard, Lee et al. fabricated vanadium carbide (V₂C) thin films by using the drop-casting method for the gas-sensing application [99].

Surface modification of substrate plays an essential role in the uniform fabrication of MXene thin films. Plenty of substrates are treated with ozone prior to MXene film formation, but in some cases, to obtain uniform and strong binding of MXene with the substrate, its modification with hydrophilic or hydrophobic groups is considered to be an important step. In this regard, park et al. used flexible poly (ethylene terephthalate) (PET) substrate, modified its surface with amine groups, and then dipped it in the solution of MXene [100]. Uniform and well distribution of MXene thin films over all the surface of PET fibers were obtained only because of substrate modification.

6.1. MXene Thin Films for Electromagnetic Interference Shielding

All electronic devices that use electrical energy generate electromagnetic interference (EMI). Electromagnetic interference affects the performance of electronic devices. An increase in EMI in devices could cause substantial damage not only to devices but also it can affect human health. A shielding material with strong, defect-free, highly conductive, and electromagnetic radiation absorption properties are always required to stop this EMI effect [142]. Plenty of 2-D materials, including metals, polymer matrices, and composite materials, have been explored to prevent EMI, but their limitations inhibit their direct use in electronic devices [143]. MXene thin films played a vital role in EMI shielding because of their excellent conductivity, flexibility, and ease of binding with different polymers [144]. To obtain a higher EMI shielding effect, controlling the concentration of MXene, thickness of thin films, and conductivities is mandatory.

Firstly, Shehzad et al. fabricated 45 μm highly flexible sodium alginate-based Ti₃C₂ MXene thick films with excellent EMI shielding effectiveness of about 92 decibels [145]. Ti₃C₂ thick film architecture and conductivity played a vital role in providing a higher shielding effect. EM waves are reflected from the surface of the first layer of MXene because electrons and the remaining waves pass through the films. The passed waves interact with MXene electrons and induce current there, which causes ohmic losses, reducing the energy of EM waves. Finally, back and forth, a reflection of these EM waves in between the layers of MXene causes their complete absorption in layers (Figure 10A).

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Figure 10

(A) EMI shielding mechanism uses Ti₃C₂ MXene thin films (reproduced with permission [68]. Copyright 2018, American Chemical Society); (B) Specific EMI shielding dependence on the thickness of Ti₃C₂ MXene thin films (reproduced with permission [146]. Copyright 2020, Elsevier); (C) Natural polymer doped MXene thin films for higher specific EMI shielding (reproduced with permission [147]. Copyright 2020, Elsevier); (D) Comparison of total EM radiation absorption and reflection for free-standing and flat MXene thin films (reproduced with permission [98]. Copyright 2018, Wiley-VCH).

After pure MXene, different MXene composites have been explored for EMI shielding applications. A composite material can provide beneficial aspects over the pure MXene material. For instance, Weng et al. have used spin-spray coating layer-by-layer method to develop semitransparent MXene and carbon nanotubes-based EMI shielding material. The composite thin films have higher conductivity (130 Scm⁻¹) and a higher specific shielding capacity of about 58 187 dB cm² g⁻¹ [107]. Similarly, polymer films utilized for the EMI shielding effect and different fillers in the polymer matrix enhanced the EMI shielding effect. In this regard, Jin et al. fabricated 27 μm thick poly (vinyl alcohol) mixed MXene films using multilayered drop-casting. These films provided higher conductivity (716 S/m) along with suitable specific EMI shielding effectiveness (9343 dB cm² g⁻¹) (Figure 10B) [146]. Mechanical stability and higher conductivity are required to obtain a higher EMI shielding effect. Doping of another material does improve not only the conductivity but also the mechanical properties of MXene. Multivalent aluminum ions doped MXene thin films have shown exceptional mechanical strength and blocked almost 99.99% of EM radiations. Aluminum ions provided extra stability to MXene thin films that could also resist oxidation in water [60]. Compared to synthetic polymers, naturally available polymeric materials are easy to use, and they are biodegradable with significantly lower toxicity that can be used for EMI shielding. In this regard, Liu et al. fabricated chitosan-doped Ti₃C₂ MXene thin films (30 µm) by using VFM to obtain an enhanced EMI shielding effect with specific EMI shielding effectiveness of about 15,153.9 ± 153 dB cm⁻¹. These films were helpful in the EMI shielding effect and applied in monitoring the humidity in the air because of the exceptional conductivity of MXene thin films (Figure 10C) [147].

The primary purpose of utilizing different methods to fabricate MXene thin films for EMI shielding is to obtain a clear insight into which method is most suitable and reliable to work at an industrial scale. VAF has also been utilized to fabricate thin films of Hydroxyethylcellulose mixed with Ti₃C₂ MXene to obtain flexible and green EMI shielding material. The integrated electron migration in Ti₃C₂ MXene thin films causes the dissipation of EM waves in the form of heat [148]. The drop-casting method has also been explored to fabricate free-standing films of Ti₃C₂ MXene on a large scale to obtain the EMI shielding effect. About 38% increased EMI shielding was obtained with such free-standing films compared to the regular flat films. This increase was due to the 3D pattern of MXene films because various incident angles were observed after the scattering of EM waves on 3D films. Hence the higher absorption was measured for the free-standing MXene thin films (Figure 10D) [98].

Almost 30 different MXene materials have been explored for the EMI shielding effect. Han et al. published an excellent systematic and comparative study of 16 other MXene materials for the EMI shielding effect to study the impact of the layer structure, metal element arrangements, and elemental composition [149]. Monometal MXenes ordered double-metal MXenes, and random solid solution MXenes were synthesized in the lab. Their thin films were fabricated using spin-casting, spray coating, and VAF with thicknesses ranging from nanometers to micrometers for the EMI shielding effect (Figure 11A). A study of electricity dependence and thickness of all the films on the EMI shielding effect revealed that higher conductivity and the higher thickness could provide specific EMI shielding exceeding 20 dB. The average EM radiation absorption and reflection of all the MXene thin films were monitored. Results have shown that mono-X MXene thin films have a better EMI shielding effect than other double-X MXenes (Figure 11B). The MXene synthesis procedure, film formation method, and MXene type strongly affect the EMI shielding effect. Therefore, it is always important to control the concentration of MXene and thickness of MXene thin films for composite materials fabrication to obtain an excellent EMI shielding effect. Along with MXene, a suitable dopant also affects the electrical, mechanical, and EMI shielding properties of MXene thin films.

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Figure 11

(A) Digital images of mono-transition metal MXenes (1M), double-transition metal MXenes (2M), Solid solution on M sites (SS-M), Solid solution on X sites (SS-X) by utilizing VFM, and (B) The average EMI shielding reflection, absorbance, and transmittance (SE_R, SE_A, and SE_T) of variety of MXene thin films with thickness range from 5 ± 0.3 μm in the 8.2–12.4 GHz range (reproduced with permission [149], Copyright 2020, American Chemical Society).

6.2. MXene Thin Films in Batteries

MXene with excellent electrical conductivity (6500 S cm⁻¹) can behave like a semiconductor or metallically conductive material. Electronic properties of the MXene materials can be tuned by doping with a suitable organic or inorganic nanomaterial. Owing to exceptional conductivity and capacitance (300 F cm⁻³), even in the presence of bigger cations that can be inserted and extracted into the MXene layers and have shown excellent power for the storage of multivalent cations such as Mg²⁺, Al³⁺, Ca²⁺, MXene has been widely explored for battery materials. MXene materials have been utilized as electrode materials and separators (Table 1. MXene nanosheets owing to large interlayer spacing can accommodate Li ions and can feasibly be used in Li-ion batteries. The lithium storage of MXenes depends on plenty of factors, including the synthetic approach of MXenes, M element, their surface chemistry, entire porous structure, and doped atoms. If there are F and OH groups on the surface of MXenes, it will hinder the storage of Li⁺ by blocking the transportation of Li⁺. Hence, by changing the surface chemistry of MXenes, it is possible to tune the Li⁺ storage. MXenes thin films are also used as a current collector material in batteries. In this regard, Wang et al. designed 5 µm thick films of Ti₃C₂ MXene as an anode material and LiFePO₄ as a cathode material (Figure 12A) [150]. MXene thin film-based electrodes cause poor ions transport, which usually leads to loss of surface reactivity and conductivity. Ma et al. designed 3D porous Ti₃C₂/r-GO-based films using the VAF method to avoid such problems. These films showed excellent rate capability of 98.9 mAh g⁻¹ at 4 A g⁻¹ and outclass performance of 212.5 mAh g⁻¹ for lithium-ion batteries without any degradation (Figure 12B,C) [52]. Meanwhile, V₂C, in comparison with Nb₂C and Ti₂C, presented developed capacity, i.e., 280 mAh g⁻¹. The most favorable method to tune the band gap and surface functionality of MXenes involved the introduction of heteroatoms. Inserting different heteroatoms, including Mo atoms and Co²⁺, into Mo₂TiC₂T_x and V₂C MXenes to obtain thin films by using the VAF method guaranteed the increase in Li²⁺ storage capacity.

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Figure 12

(A) Comparison of MXene thin film with Cu and Al foil and their densities (reproduced with permission [150]. Copyright 2018, American Chemical Society); (B,C) Cycle performance and capacity retention ratio of rGO, Ti₃C₂, and different composites of rGO@ Ti₃C₂ at 1 A g⁻¹ current density after 1000 cycles (reproduced with permission [52]. Copyright 2018, American Chemical Society); (D) Rate performance of spray-coated Ti₃C₂T_x/NiCo₂O₄ films (reproduced with permission [151]. Copyright 2016, Elsevier); (E) Schematic diagram showing the use of MXene-coated polypropylene separator; (F) MXene@polypropylene-based separator based improved cycling performance of the Li-S batteries at 0.5 C and 1 C rates (reproduced with permission [131]. Copyright 2016, American Chemical Society); (G) Comparison of rate performances of MX-NF/polypropylene cells with polypropylene, Nafion@polypropylene, MXene@polypropylene, MX@Nafion/polypropylene (reproduced with permission [152]. Copyright 2019, Elsevier).

The fabrication method for thin films of MXene could affect the performance of Li ions storage in Li-ion batteries. For instance, Zhao et al. hybridized transition metal oxides such as Co₃O₄ and NiCo₂O₄ with Ti₃C₂ MXene using three different approaches, including repeated filtration, spray coating, and wet chemical method. As prepared, flexible metal oxide and MXene-based films were utilized in Li-ion batteries without any binder. The free-standing hybrid films synthesized using spray coating have shown excellent electrochemical performance with a high reversible capacity of about 1330 mAh g⁻¹ at 0.1 C (Figure 12D) [151].

In Li-S batteries, MXene has played an essential role as a separator [153]. Plenty of materials, including carbon nanotubes, graphene/graphene oxide, TiO₂, and other 2-D nanomaterials, have been used as a separator to suppress the migration of polysulfides [136,154,155]. MXene coatings by using VFM have also been used on polypropylene membranes as a separator in Li-S batteries, and it causes a significant improvement in cycling stability and rate capability of Li-S cells (Figure 12E,F) [131]. Similarly, Wang et al. modified the polypropylene separator with Ti₃C₂ MXene and Nafion composite to inhibit the shuttle effect. VFM has been utilized to obtain a layer-by-layer modification of Nafion with MXene material. This composite material provides excellent conductivity and suitable cycling stability and causes effective transport of Li ions with highly enhanced initial capacity and rate performance compared to other materials (Figure 12G) [152]. Suitable charge capacity and excellent stability are crucial requirements for a suitable battery. MXene-derived derivatives also played an essential role as a separator in batteries. TiN@C sheets derived from MXene acted as a separator in Li-S batteries, and an excellent initial discharge capacity at 0.1 C (1490.2 mAh g⁻¹) was obtained by VFM [156]. MXene materials proved efficient in preparing stable, long life, and higher charge capacity batteries because their exceptional electrical, physical, and chemical properties and surface modification could bring more to the battery world.

6.3. MXene Thin Films in Sensors

Sensing devices will be a great need in the near future in industries, homes, hospitals, and most places. Plenty of materials, including graphene, metal nanoparticles, carbon nanotubes, and black phosphorous, have been explored for gas sensing, body motion sensing, heavy metal ion detection, and organic moieties sensing. Materials owing high conductivity, ease in functionalization, flexibility, and long-term stability are essential for next-generation self-powered sensors. MXene thin films with all the aforementioned properties have been explored for various sensors. Zhang et al. used layer-by-layer self-assembly process to fabric MXene/black phosphorus thin films applied in pressure sensors with o 77.61 kPa⁻¹ pressure sensitivity at 0.45 MPa elastic modulus. Furthermore, this flexible sensor has shown a fast response time and monitors human heart motion [157].

MXene thin films, because of their 2-D layer structure and ease in surface modification, have played an important role in gas sensing. Ti₃C₂T_x owing to ease in surface termination, has been tested for NH₃ sensing. To check the changes happening in MXene thin films during the sensing mechanism, Koh et al. have performed an in situ X-ray study of Ti₃C₂ MXene thin films fabricated using VAF upon CO₂ and ethanol sensing. An X-ray study revealed that MXene thin films displayed dynamic and selective swelling upon interaction with ethanol over CO₂ in the presence of NaOH (Figure 13A) [158]. Similarly, the insertion of Na ions in Ti₃C₂ MXene thin films prepared by the dip-coating method improved the humidity and gas-sensing properties of thin film by increasing the oxygen-fluorine groups on the surface [159]. To obtain a clear insight into the mechanism of gas sensing, Lee et al. fabricated Ti₃C₂T_x thin films by drop-casting method and tested for sensing of ammonia, ethanol, methanol, and acetone gas (100 ppm) at room temperature by tuning the electrical properties of MXene thin films. Due to the lack of F group on the surface, Ti₃C₂T_x MXene thin films have shown higher affinity toward ammonia gas molecule and lowest toward acetone gas in a chemiresistive sensor (Figure 13B) [160]. The basic requirements for the highly sensitive sensor are low electrical noise and strong signal production, and development in MXene thin film-based sensors fulfill these requirements. Basically, gas adsorption on MXene thin film effect charge carrier transport, resulting in the change in resistance usually measured. In this regard, Kim et al. fabricated pure Ti₃C₂T_x MXene thin films by VFM for acetone, ammonia, ethanol, propanol, NO₂, SO_2, and CO₂ gas sensing [161]. The MXene-based sensor has shown a change in resistance under exposure to 100 ppm of all the mentioned gases, which is a suitable agreement that on gas adsorption, the charge carrier transportation gets disturbed. The Ti₃C₂T_x-based sensor has shown a suitable response to ethanol with a limit of detection of 50 ppb to 1000 ppm because of hydrogen bonding. It has demonstrated the most negligible response to NO₂, SO_2, and CO₂ gases (Figure 13C,D). The thickness of the MXene films also affected the gas-sensing mechanism because of the available active sites. MXene 3D porous structures based on the thin film by using the electrospinning method have also been used as a gas sensor for acetone, ethanol, methanol, ammonia, toluene, water vapor, and NO₂ sensing. Polar gases obtained an extraordinary response because of the polar surface of MXene thin films, while the non-polar gases did not show any significant change in resistance on interaction with MXene thin films [162].

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Figure 13

(A) Schematics of in situ XRD analysis of Ti₃C₂ thin films sensing mechanism, (reproduced with permission [158]. Copyright 2019, American Chemical Society); (B) Gas-sensing results of thin Ti₃C₂ films-based gas sensors in response to 100 ppm ethanol, methanol, ammonia, and acetone at room temperature (reproduced with permission [160]. Copyright 2017, American Chemical Society); (C) Schematic of chemiresistive Ti₃C₂ thin films-based gas sensor; (D) Resistance change and maximal resistance variation in Ti₃C₂ MXene thin film gas sensor upon exposure to 100 ppm of acetone, ethanol, ammonia, propanol, NO₂, SO₂, and 10,000 ppm of CO₂ at room temperature, (reproduced with permission [161]. Copyright 2018, American Chemical Society); (E) Schematic showing gas-sensing mechanism of V₂CTx MXene thin film, (reproduced with permission [99]. Copyright 2019, American Chemical Society); (F) Ti₃C₂ and TiO₂/Ti₃C₂ thin film gas-sensing mechanism toward NO₂ gas and comparison of enhancement factor of gas response for Ti₃C₂ and TiO₂/Ti₃C₂ film at five ppm gas concentration (reproduced with permission [163]. Copyright 2020, Wiley-VCH).

Regardless of the higher conductivity and exceptional sensing properties of Ti₃C_2, other MXene materials have also shown suitable sensing abilities because of their non-polar nature. For instance, Lee et al. prepared single/few layers of vanadium carbide MXene thin films (V₂CT_x) on polyimide film by VFM and used them as a chemiresistive sensor for polar (hydrogen) and non-polar (methane) gas sensing with 2 and 25 ppm limit of detection (Figure 13E) [99]. Similarly, molybdenum carbide (Mo₂C) thin film fabricated by VFM has also been used for NH₃ and NO₂ gas sensing with gases concentration ranging from 0.125 to 5 ppm [164]. Furthermore, except for pure MXene, mild reduction in MXene also proved efficient for gas-sensing applications. As in the case of Ti₃C₂, control reduction in Ti₃C₂ can produce TiO_2, which can be further used as a composite TiO₂/Ti₃C₂ material for chemiresistive gas sensors. VFM produced TiO₂/Ti₃C₂ MXene film treated with an alkaline solution and used for selective sensing of NO₂ gas with a 125 ppb limit of detection (Figure 13F) [163]. In conclusion, although all the MXene thin film fabrication seems great for gas sensing as compared to drop-casting, vacuum-filtration, and dip-coating methods, the electrospinning method can fabricate thinner MXene films that could lead to higher active surface area and efficient gas sensing. Alkali treatment of all the MXene films before gas sensing contributes to the gas sensing mechanism. It is possible to functionalize MXene thin films surface with different chelating agents and polymers to obtain selective gas sensing that can be further used in industries.

6.4. Mxene Thin Films in Solar Cells

To overcome future energy crises and global warming, researchers are inclined to progress with renewable energy sources. Among various sources, the solar energy source is considered a competitive candidate to deal with future clean energy demands. For this purpose, multiple efforts have been made to develop efficient and stable solar cells by introducing novel materials. Two-dimensional Mxenes have recently attracted increasing attention in solar cells application due to their high metallic conductivity, superior carrier mobility, high transparency, and tunable work function [50]. In this review, we have highlighted the use of MXenes thin films prepared by different methods for solar cell application.

Mxenes have been considered a promising electron transport layer (ETL) or a dopant in ETL for efficient and stable perovskite solar cells. Yang et al., spin-coated Ti₃C₂ Mxene doped SnO₂ as an ETL in n-i-p perovskite solar cell (PSC) [111]. The resulting ETL provides superior charge transfer paths, boosts electron extraction, and minimizes the electron transfer resistance at the perovskite and ETL interface. The SnO₂-Ti₃C₂ spin-coated ETL enhanced the power conversion efficiency (PCE) from 17.23% to 18.34%. Wang et al. modified the SnO₂ with Ti₃C₂ Mxene spin coated over the FTO, promoting superior mobility, higher charge transfer ability of SnO_2, and strong interface interaction [165]. Further, the modification of SnO₂ with Mxene enabled the preferable growth platform for the perovskite film with reduced trap densities. As a result, an enhanced PCE of 20.65% was achieved with negligible hysteresis. Lin Yang et al. treated the spin-coated Ti₃C₂ Mxene with UV-ozone, improved electron transfer at the ETL/perovskite interface, and suppressed the recombination as well [115]. The devices fabricated based on UVO-treated Ti₃C₂ result in 17.17% champion PCE compared to UVO untreated devices with only 5%. PCE. Saranin et al., spin-coated Mxene doped PC₆₁BM ETL in p-i-n PSCs to modify the work function and band alignment of PC₆₁BM relative to the perovskite layer [118]. The Mxene-modified device achieved 19% PCE with improved stabilized power output compared to the reference device. Agresti et al. tuned the perovskite film work function from 4.72 to 4.37 eV by spin coating Mxene doped MAPbI₃. As a result, 26.5% improvement in PCE was achieved after simultaneously spin coating Ti₃C₂ as an ETL with Mxene doped MAPbI₃ [114].

Furthermore, the Nb₂C-SnO₂ ETL spin coated over the ITO enables a larger SnO₂ grain size and provides higher quality and superior crystalline perovskite film [124]. The detailed Nb₂C-SnO₂ ETL process is demonstrated in (Figure 14A). The high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) confirmed that the doping of the Nb₂C MXene increased the lattice spacing facets of SnO₂, which improves the surface energy, roughness, and defects in SnO₂-Nb₂C-based ETL. The lattice fringes correspond to (101) (110) SnO₂ with the spacing of 0.320 (B₁) and 0.240 nm (B₂). Similarly, the incorporation of Nb₂C in SnO₂ changes the lattice spacing to 0.253 (C₁) and 0.330 (C₂) nm corresponding to (101) and (110) SnO₂. Moreover, the Nb₂C introduction enhances the grain size of SnO₂ from 179 nm to 256 nm. The Nb₂C-SnO₂ ETL results in PCE of 22.86% compared to the control device with 18.96%.

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Figure 14

(A) The preparation process of SnO₂-Nb₂C MXene solution; (B) Photoluminescence spectra of SnO₂ and SnO₂-Nb₂C MXene; (C) J-V curves, and photoconversion efficiency of SnO₂ and SnO₂-Nb₂C MXene thin films fabricated by an SCM, reproduced with permission [124]. Copyright 2020, American Chemical Society); (D) Schematic representation of the automated spraying apparatus of large-scale deposition of Ti₃C₂T_x flakes as the back electrode for SHJ solar cells, Insets: (Bottom-left) Corresponding layer-by-layer structure of an SHJ solar cell. (Bottom-right) Tilted top-view SEM micrograph of the Ti₃C₂T_x flakes covering the ITO-coated pyramidal textured surface of SHJ solar cells; (E) JV curves of ITO, ITO/Ag, and ITO/MXene thin films; (F) JV curves after 609 days of a device fabricated (reproduced with permission [166]. Copyright 2020, American Chemical Society).

Furthermore, the PL spectra indicate that the addition of Nb₂C in SnO₂ had a lower PL emission that confirms the reduced recombination and enhanced photogenerated carrier generation (Figure 14B). Subsequently, the devices fabricated on SnO₂ and Nb₂C SnO₂ had a PCE of 18.96% and 22.86%, respectively (Figure 14C). The device stability was tested under 40–60% humidity. The Nb₂C-SnO₂ ETL retained 98% of the initial PCE, while the SnO₂ ETL retained only 85%. This indicates the effectiveness of Nb₂C doping in SnO₂ for stable PSCs.

Besides ETL, MXenes are also a suitable material as a dopant in HTL. Hou et al., spin-coated MXene doped PEDOT: PSS results in more charge transfer channels between PEDOT nanocrystals in organic solar cells [167]. The addition of MXene transformed the PEDOT from coil structure to linear coil structure, leading to enhanced electrical conductivity. The MXene doped PEDOT: PSS spin-coated film achieved 11.02% PCE compared to 9.72% for the controlled device.

Spray coating has been considered a well-known method for fabricating dense, homogeneous, and uniform MXene thin films. Cao et al. spray-coated MXene paste over the MXene photoanode as a back electrode [119]. The sprayed MXene electrode was hot-pressed to create a seamless contact between perovskite and Ti₃C₂. The device was prepared based on the MXenes electrode and had a PCE of 13.83%, 27% higher than the device designed on a carbon-based electrode. Recently, spray-coated MXenes electrodes were fabricated to replace Ag for SHJSC at an Industrial-scale [166]. The fabricated MXene contacts had a high uniform coverage over the typical micron-scale pyramidal textured backside of SHJSC. The MXene spray-coated electrode results in more than 20% PCE over medium (4.2 cm²) and large (243 cm²) cell areas with 99% PCE retention for over 600 days in an ambient environment. The schematic of the spray-coating process of the MXene electrode is demonstrated in (Figure 14D). Although spray-coating enables uniform and fast coating over a large area, this becomes challenging in the case of complex geometries such as random-pyramidal textured SHJSC. Therefore, the uniformity of the surface coverage has been determined by scanning electron microscopy. The cross-section SEM graphs indicate the complete range of MXene over the facts of backside pyramids. To analyze the optimum MXene rear contact thickness on SHJ cells, an array of devices was fabricated with a cell area of 4.2 cm² by spraying MXene dispersion in DI water (Figure 14D). The MXene spray-coating cycles varied from 40 to 260. The fabricated devices based on different thicknesses showed 140 cycles as an optimum value with the highest PCE of 19.8%. Upon increasing the spraying cycles to 160, the PCE dropped to 19.3%. Moreover, the further increase in spraying cycles to 260 causes a further reduction in PCE to 18.9%. J–V curves of devices with different rear electrode stacks (Figure 14E). The presence of metallic contact to the rear ITO has a higher PCE and FF than without contacted cells. The reason is that Ag-connected cells provide better back reflection than MXene-contacted cells due to the high absorption cross-section of Ti₃C₂ films. Thus, the NIR response of the MXene-based device is slightly less than the Ag-based device revealed by EQE measurements. The stability of the MXene-based devices was tested after keeping them in an ambient environment for more than 20 months (Figure 14F). The PCE of the device dropped to 19.5% after such a long time duration. Ag-based devices remained unchanged for a long time, but such stability for MXene-contacted devices is notable considering the oxidation sensitivity of MXenes.

During the past few years, spin-coated MXene thin films have been developing progress in solar cell research. However, spray-coating can be a viable option to fabricate MXenes films on an industrial scale. Further, other methods, such as dip coating, doctor blade coating, and inkjet printer films, can scale up the MXene thin film preparation for solar cell application.