3.1. Microstructural Analysis
Figure 2 shows the XRD patterns of pristine and irradiated In
2(Te
0.98Se
0.02)
3 films. The peak positions at 2θ = 40.69° corresponded to the (21
) plane of the In
2(Te Se)
3, agreeing with the standard JCPDS diffraction data (File number 76-1182). Comparing the pure In
2Se
3 and In
2Te
3 phase, a peak at 23.15° assigned to the pure In
2Te
3 phase of the film exhibited the preferential orientation of the (5 1 1) plane (JCPDS 16-0445). Further, the peaks at diffraction angles 2θ = 27.68° and 38.53° were assigned to the (0 0 6) and (1 2 0) planes, respectively, of γ-In
2Se
3 in pristine and irradiated films (JCPDS file number 71-0250). However, the formation of pure In
2Se
3 and the In
2Te
3 phase in the present work was compared with the available literature. Matheswaran et al. prepared InTe thin films and reported the existence of mixed phases in XRD patterns that include In
2Te
3 and In
2Te
5 phases [
26,
27]. Niranjan et al. prepared InSe thin films and showed the presence of InSe, In
4Se
3, and γ-In
2Se
3 phases. Comparing these results with the present work, the formation of pure γ-In
2Se
3 and In
2Te
3 phases along with preferential orientation also agreed with this literature. The reason for the formation of the In
2Se
3 and In
2Te
3 phase compounds can be simplified by considering the electronegativity difference among the choice of materials. The elements having high electronegativity differences may have high binding strength [
28], and the elements with a small difference in electronegativity may induce poor stability of a compound [
29]. For instance, the elements In, Te, and Se have 1.78, 2.10, and 2.54 Pauling, respectively. Among these elements, the electronegativity difference is higher for the In–Se system (0.76) compared to those of the In–Te (0.32) and Se–Te (0.44) systems. By considering these facts, we assume that there may be a possible chance to form a dominant In
2Se
3 phase primarily due to the high electronegative difference (0.76) and the rest of the compounds later (other possible phases).
The irradiation-induced structural modification in 1E13 slightly increased its peak intensities over those of the pristine, 1E11, and 1E12 samples. The phase formation was almost same for all samples. The only difference was the shift in diffraction angle and variation in the peak intensity. Notably, the lack of a peak that corresponded to the extra crystalline phase or any metallic peak (indium) in the XRD pattern revealed the stability of In2(Te0.98Se0.02)3 films under irradiation and also the lack of amorphization in the sample, even at 120 MeV Ni ion irradiation. Hence, the Se of 1110 eV/Å did not induce amorphization in the In2(Te0.98Se0.02)3 system.
The essential structural parameters, namely, crystallite size (D) (calculated using Debye–Scherrer [
30]), dislocation density (δ) [
31], and strain (ε) [
32], were estimated by the following equations:
where the constant k is the shape factor = 0.94, λ is the wavelength of X-rays (1.5406 nm for CuKα), θ is the Bragg angle, and β is the full width at half maximum of the diffraction peak measured in radians.
The crystallite size was determined, and the average crystallite size was about 23.5 nm for the pristine sample. The initial ion fluence produced a small increase in the crystallite size to 24.60 nm owing to the ion beam-induced effect below the threshold value of S
e, resulting in the crystallization of the materials. The decrease in the crystallize size may have been due to strain-induced fragmentation of crystallites by the influence of SHI irradiation. A similar grain growth mechanism was also reported by Kumar et al., namely, 120 MeV Au
9+ ion beam-induced modifications of SnO
2 and TiO
2 nanocomposite thin films with varying fluence from 5 × 10
11 ions cm
−2 increasing to 2 × 10
13 ions cm
−2 [
21]. Crystallite sizes were reduced to 19.36 nm and 17.15 nm for ion fluences of 1E12 and 1E13, respectively. This reduction in crystallite revealed the occurrence of grain fragmentation/recrystallization processes in the material. The prominent decrease in the crystallite size with the increase in ion fluence was due to the irradiation-induced lattice defects in the material. Mostly, the crystallite growth/grain fragmentation occurring in polycrystalline samples was due to the spread of energy loss by SHI irradiation. Additionally, this reduction in crystallite size could be attributed to the strain-induced grain fragmentation of crystallites as well. Based on the thermal spike model [
22] and the Coulomb explosion model [
33], the irradiation-induced defects/strain in the crystallites could be described.
In the case of the thermal spike [
22], SHI passed through the target and deposited large energy in the electronic sub-system of the material, creating defects. The highly excited electron quickly distributed its energy through electron–electron interaction until electrons were thermalized to dissipate their energy through electron–phonon coupling to the atoms in the target material. This energy was highly excited by electron–electron coupling and transferred to the lattice atoms. Thus, SHI irradiation through the system or target produced a large increase in lattice temperature that may have led to strain in the crystallite. The produced strain may have caused fragmentation in crystallites. The local temperature during the thermal spike phase increase up to ~10
4 K spread and quenched subsequently within ~10
−12 s. The resulting liquid-like non-equilibrium state induced various thermally activated processes, such as atom migration, evaporation of atoms, and atomic jumps across grain boundaries. This resulted in permanent structural and surface modifications that included defects or ion track phase transitions [
9,
10]. The coulomb explosion model explains that the ionized zone of the positively charged particle is enormously produced over the path of the incident ion by electrostatic repulsive forces, which ultimately induce strain in the system inside. Moreover, the existence of strain in the system by SHI irradiation may assist in fragmentation in the crystallites. The significant increase in dislocation density (δ) suggests notable damage on the surface as well and is consistent with the results obtained from the morphological analysis, as larger grains were fragmented to smaller size grains. The dislocation density in 1E11 was lower than that in the pristine sample but increased with the ion fluence, suggesting more grain fragmentation in material under a higher ion fluence. The widening of the peaks in the XRD patterns was attributable to the decrease in crystallite size, suggesting the presence of lattice defects/strain [
21]. This decrease in the crystallite size originated from the defect structure induced by the ion beam in the material. The observed results were similar to those reported by Panda et al., namely, 140 MeV Ni ion-irradiated AgInSe
2 and Ag
2Se composite thin films [
34].
3.2. Morphological Studies
The pristine thin film shown in
Figure 3a exhibits the presence of a smooth surface morphology with spherical grains, which is different from that of the 1E11 sample (
Figure 3b). The increase in ion fluence to 1E12 led to grain fragmentation, as larger spherical grains became smaller grains. The grains in 1E13 seemed to be smaller and denser, being significantly different to those in the pristine thin film. High-energy deposition on target materials reduced the larger grains into smaller grains, and this behavior was consistent with the structural analysis, as crystallite size decreased with ion fluence. Grains are composed of many crystallites. In the present case, it seems grains observed in SEM images were also composed of many crystallites with a size of about 20 nm. The observed behavior is similar to the result reported by Zara et al. on the influence of 100 MeV O
7+ and 100 MeV Si
7+ ion irradiation on indium thin films and explains irradiation-induced grain fragmentation in these materials [
23]. They found that heavy ion irradiation results in larger size grains becoming fragmented into smaller grains with an increase in the ion fluence for both O
7+ and Si
7+ ion species. Increasing the ion fluence reduces the crystallinity of the film due to the irradiation-induced grain fragmentation.
The elemental ratio for In:Te:Se is 40%:58%:2%. The elemental compositions of the films were analyzed by using the EDS technique. The actual elemental compositions of the films are displayed in
Table 2. A slight variation in the elemental composition of irradiated samples was observed compared to that of pristine film, which may have been because of the irradiation-induced high energy deposition in the materials by Ni ion beams. This deviation is clarified as follows: The pure crystalline/amorphousIn
2Se
3 phase was detected for all samples. From the calculated and measured elemental compositions, the Se and Te elemental ratio confirmed a smaller deficiency compared to that of In. Further, it also proved that because of the binding energy difference among these elements, the formation of the InSe phase was more comparable to those InTe phases. Moreover, the In ion evaporated significantly during the thermal processes due to the difference in atomic vapor pressure. The calculated and measured elemental ratios between In, Te, and Se are presented in
Table 2. Apart from In, Te, and Se peaks, a small amount of Si, C, and O peaks from the glass substrates were observed (i.e., we used the normal and distilled water to rinse the slides as well as agitate for cleaning purposes), confirming the nature of the prepared In
2(Te
1−xSe
x)
3 thin films.
Figure 4 presents a change in the AFM micrographs of In
2(Te
0.98Se
0.02)
3 as a result of ion irradiation. The micrograph of the pristine film revealed a smooth surface with spherical-shaped grains. The estimated average (R
a) surface roughness and root mean square (R
q) roughness of the pristine sample were about ~12.65 nm and ~16.23 nm, respectively. The observed R
a and R
q increased to ~13.54 nm and ~17.37 nm, respectively, for 1E11. However, R
a decreased to 10.18 nm and R
q to14.52 nm for 1E12 and 8.13 nm and 12.24 nm for 1E13. The grains were found to be uniformly distributed throughout the entire surface of the pristine sample, and their average size was ~30 nm. In 1E11, it slightly increased to ~32 nm. However, it decreased to ~27 nm and ~24 nm in 1E12 and 1E13, respectively. Thus, AFM studies proved surface smoothening as the ion fluence increased, possibly because of irradiation-induced viscous flow in the sample, as explained by Zhang et al., on Ti-based bulk metallic glass by heavy ion irradiation [
35]. Further, the mean surface roughness became reduced with an increasing 20 MeV Cl
4+ ion dose, which confirmed the smoothing of surfaces. It is believed that the process of surface smoothing and roughing in solids is rather complex, depending on the properties of the incident ion, incident angle, and the target materials. In the case of low-energy ion irradiation, the projectiles are implanted the near surface. At higher fluence, the key reason for surface roughening is likely surface erosion or deposition, whereas surface smoothing seems to be due to surface diffusion or viscous flow.
Therefore, ion beam-induced fragmentation or recrystallization reduces grain size under high energy irradiation, which causes melting followed by recrystallization. From the AFM image, the observed average grain size was about 30 nm for the pristine sample, i.e., the scanned image size was larger in AFM (5 µm). While AFM gave more information about these surfaces, the SEM image provided details of the grains. Grains were composed of many crystallites, and the estimated grain size in the SEM image was about 100 nm, as pointed out in
Figure 4. In the present case, it seems that grains observed in SEM images were also composed of many crystallites with a size of about 20 nm. Further, it is clear that both SEM and AFM showed very similar kinds of spherical shaped images with different magnifications, and also it seemed that larger grains were composed of many crystallites for the pristine sample.
3.3. Measurement of Seebeck Coefficient (S) and Electrical Resistivity
The Seebeck measurement is performed by creating a temperature difference using the differential method [
25]. The average temperature difference is measured by creating the temperature difference in both directions and taking the average of both. The resistivity is measured in a four-probe mode.
Figure 5 presents the measured S of In
2(Te
0.98Se
0.02)
3 at 300 K to 420 K temperature. The negative S value suggested the dominance of electron charge carriers in all samples. The observed S value for the pristine sample was ~221 µVK
−1. The S value was found to increases with ion fluence to about ~427 µVK
−1 for 1E13. This result indicated that S increased with increases in the ion fluence to a maximum (1E13), showing double the value of the pristine sample. Notably, S increased linearly with temperature for In–Se–Te, suggesting possible semiconducting behavior. The improved S value was evidence of an enhanced PF value in irradiated In
2(Te
0.98Se
0.02)
3 films. The observed S values consistent with the measured S of the n-type of In–Se-based chalcogenides reported by Dhama et al., were about −159 µVK
−1 to −568 µVK
−1 [
8]. However, not much work has been explored on the thermoelectric performance of In
2(Te
0.98Se
0.02)
3 alloys, especially under SHI irradiation.
Figure 6 displays the measured PF for pristine and irradiated In
2(Te
0.98Se
0.02)
3 thin films. The maximum power factor at 400 K was found to be ~2.37 µW/K
2m for 1E11, which displayed a higher PF value than the pristine sample (~1.23 µW/K
2m). The PF value for 1E12 was about ~3.72 µW/K
2m, better than that of the pristine sample. The PF value further increased to ~4.91 µW/K
2m for 1E13, which was four times higher than that of the pristine sample. The effect of heavy ion irradiation on In
2(Te
0.98Se
0.02)
3 samples demonstrated considerable enhancement of both S and PF, which is evidence of the presence of more SHI-induced defects in the irradiated samples than in the as-deposited films. The PF values were found to exponentially increase with the ion fluence, which showed considerable enhancement in the irradiated samples as compared to the pristine samples. The higher value of the S led to an increase in the PF values of the irradiated samples. The higher S value for the irradiated sample was possibly because of grain fragmentation from large nanograins into tiny nanograins, as evidenced from FESEM analysis. Further, irradiation created defects inside the material, and these defect centers helped in charge carrier filtering, increasing the Seebeck coefficient (S), while these defects hindered the motion of charge carriers in conductivity measurements, leading to decreases in conductivity with irradiation. The heavy ion irradiation in the material resulted in the formation of point defects or defect clusters, which increased with ion fluence, and consequently the mobility of charge carriers across these defects decreased, thereby causing enhancement in thermopower. Bala et al. also reported a similar result that enhanced the thermoelectric properties of CoSb
3 alloy by 100 MeV Ag ion irradiation [
10].
The existence of a high density of nanoscale grain boundaries might also lead to improvements in thermoelectric properties of In
2(Te
0.98Se
0.02)
3 thin films. The observed results also agree with earlier reports that suggest that phonon scattering through the nanoscale grain boundary leads to significant thermoelectric enhancement [
10,
36,
37]. Sanyal et al. studied the impact of grain boundary scattering in polycrystalline CuInSe
2 films, and their results suggest that electrical conductivity, Hall mobility, and carrier concentration are influenced by the dominant grain boundary scattering effects [
38]. Consequently, the effect of grain boundary scattering in the material could also lead to an impact on the electrical transport properties of the In
2(Te
0.98Se
0.02)
3 films. The presence of interface states along with thermionic emissions across the grain boundaries directly affects the charge transport mechanism in polycrystalline films. Wu et al. reported similar studies that prove that the formation of nanoscale grains can reduce the lattice thermal conductivity dramatically in nanocrystalline PbS materials, and further theoretical modelling also confirmed that high densities of nanoscale grain boundaries were more effective in reducing lattice thermal conductivity, thereby improving thermoelectric performance [
36]. Additionally, Poudel et al. also reported bismuth antimony telluride-based alloy compounds, which showed excellent thermoelectric properties due to the low thermal conductivity caused by the improved phonon scattering by nanograin boundaries and defects [
37]. By considering the above facts, it seems that the effect of grain boundary scattering in the present In
2(Te
0.98Se
0.02)
3 system could also be one of the leading factors in the enhancement of the thermoelectric properties of the materials.
In general, electrical resistivity (
ρ) and electrical conductivity are related to carrier concentration (n) through carrier mobility (µ):
Both the carrier concentration and carrier mobility contribute to the conductivity.
Further, the relation between thermoelectric power (S) and carrier concentration can be explained by the following Mott mathematical formula:
where kb is the Boltzmann constant, h is Planck’s constant,
m* is the effective mass of carriers, and
T is the absolute temperature. The above relation (5) proposes that the S value generally depends on the carrier concentration. Thus, increases in carrier concentration and ion fluence considerably reduce the S value, and S has been revealed to be inversely proportional to 2/3 power of carrier concentration from the above relation. However, an increase in ion fluence shows a significant increase in S value, owing to the SHI-induced defects in the material. The carrier concentration is not only the major reason for the variation in the S value. Addition factors such as defect level and charge scattering in grain boundaries are also defining properties of the materials. Hence, in the present case, ion beam-induced nanostructuring played a significant role in the improvement of S.
Figure 7 plots the measured electrical resistivity (
ρ) of In
2(Te
0.98Se
0.02)
3 thin films and confirms the semiconducting behavior of the materials [
39]. The
ρ curve seemed to be higher for irradiated samples than for pristine samples, revealing the influence of SHI irradiation, which modified the surface of the materials through the grain boundaries. This phenomenon may be responsible for the decrease in the carrier mobility of the In
2(Te
0.98Se
0.02)
3 system.
Table 3 presents the Hall measurements of pristine and all irradiated In
2(Te
0.98Se
0.02)
3 samples. The negative Hall coefficients indicated an n-type conduction of the films, as presented in
Figure 8b. Measured carrier concentrations were about 1.21 × 10
17 cm
−3 to 3.927 × 10
18 cm
−3, as shown in
Figure 8a.
Table 3 displays the resistivity, carrier concentration, and Hall mobility of pristine and irradiated samples. The carrier concentration for the pristine sample was found to be 1.21 × 10
18 cm
−3. The carrier concentration at different ion fluences of 1E11, 1E12 and 1E13 were found to be about 8.35 × 10
17, 17.24 × 10
17, and 39.27 × 10
17 cm
−3, respectively (shown in
Figure 8). The improvement in carrier concentration with an increase in the ion fluence may have been due to increases in defects such as vacancies or interstitial defects. The carrier concentrations were higher at room temperature for the irradiated films as compared to the pristine sample, which led to an increase in the electrical resistivity of the irradiated samples due to the decrease in the mobility of the charge carriers. Mostly, ion beam irradiation enhanced the resistivity due to the creation of defects. Hence, irradiated samples showed higher resistivity and revealed the presence of higher carrier concentrations and minimum carrier mobility that may have been a result of grain fragmentation. The higher carrier concentration in the irradiated samples also confirmed the presence of more defects.
However, the carrier mobility decreased as the ion fluence increased, and this effect may have been responsible for the higher
ρ of the irradiated samples, owing to grain fragmentation. Likewise, the
ρ curve increased, possibly because the ion irradiation created defects/impurities, reducing the mobility of carriers in the materials. Furthermore, the small grains favored electron scattering by grain boundaries, thereby enhancing the
ρ of the materials. The greater ratios of surface area to volume in small grains may have led to a greater ratio of grain boundary to dislocations being produced. Consequently, the
ρ increased with irradiation as grain size decreased, suggesting low electrical conductivity. Samples with small grains contain more grain boundaries and scatter electrons, thereby increasing the
ρ of the material. The observed result is similar to the observed case of n-type (Hf, Zr) CoSb thermoelectric material, demonstrating the grain size-dependent electrical properties that reveal the dominant grain boundary scattering mechanism [
40]. Further, some trapped states at the grain boundary may also contribute to the higher resistivity of the materials. The larger grain boundary region has an additional scattering center in In
2(Te
0.98Se
0.02)
3, which could be a reason for higher
ρ in irradiated samples than in the pristine sample. The presence of several scattering centers limits the
ρ of the materials, consistent with FESEM analysis. Then, the number of scattering centers leads to a rapid increase in electrical resistivity. Biswas et al. reported that the thermal conductivity of Al-doped ZnO quantum dots is reduced due to the selective phonon scattering by point defects and interfaces, and thereby an enhanced PF value [
41]. Further, the lattice thermal conductivity of this composite could be dominated by grain boundaries and hence phonon–phonon scatterings. Therefore, grain boundary scattering may have a strong influence on defining the Seebeck coefficient of the materials. Accordingly, the enhancement in thermopower for the irradiated In
2(Te
0.98Se
0.02)
3 films could also be attributed to charge scattering due to the grain boundary.
Additionally, point defects also could be one of the determining factors of impurity scattering results in the enhancement of thermopower. The high thermopower value for the irradiated sample is mostly because of the contrast in charge scattering due to the grain boundary. Ion irradiation creates defects and vacancies, which affect the transport properties of the carriers. The observed increase in S could be accounted for by the modification of these properties under irradiation. Moreover, an increase in ion fluence shows a significant increase in S value that may be due to the SHI-induced defects in the material.