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Polymers 2017, 9, 626 11 of 15 Polymers 2017, 9, 626 11 of 15 3.4. Urbach Energy and Materials Structure It was established that Urbach energy can be used to investigate the structure of polymeric materIitawlsathsreosutgabhltishheedetehcattioUnrobfatchhe denefeercgtylecvaenl wbeithuisnetdhetofoirnbvidesdteignabteantdhegasptru[3c6t]u.rTehoefUproblaycmhetaricl wmiadttehriwalassthesrtoiumgahtetdhethdroetuegchtiothneoffotlhloewdinefgecrtelaetvioenl w[5i4th,5i5n]:the forbidden band gap [36]. The Urbach tail width was estimated through the following relation [54,55]: α(ω) = αo exp(hυ/Et) (3) α(ω) = αo exp(hυ/Et) (3) where α is constant and E is the Urbach tail, which refers to the band tails width of the localized where αo is constant and Et is the Urbach tail, which refers to the band tails width of the localized states. One can determine E from the reciprocal of the slope of the straight lines obtained from the states. One can determine Et from the reciprocal of the slope of the straight lines obtained from the plots of ln(α) vs. photon energy hυ (see Figure 12). The determined value of E for the pure PMMA plots of ln(α) vs. photon energy hυ (see Figure 12). The determined value of Et for the pure PMMA 3.4. Urbach Energy and Materials Structure sample is found to be 157 meV, while it increased to 298 meV for the doped PMMA sample (GT 28). sample is found to be 157 meV, while it increased to 298 meV for the doped PMMA sample (GT 28). This increase of Urbach energy can be indirectly attributed to the increase of the amorphous nature This increase of Urbach energy can be indirectly attributed to the increase of the amorphous nature within the dye-doped PMMA samples. The larger energy tails indicate the creation of disorder and within the dye-doped PMMA samples. The larger energy tails indicate the creation of disorder and imperfection in the band structure of the host material [56]. Prasher et al. have also confirmed that the imperfection in the band structure of the host material [56]. Prasher et al. have also confirmed that increase of Urbach energy is an indication of the increase of the amorphous portion [57]. Figure 13 the increase of Urbach energy is an indication of the increase of the amorphous portion [57]. Figure 13 shows the XRD pattern of pure (GT 0) and dye-doped (GT 28) PMMA samples. It is evident from the shows the XRD pattern of pure (GT 0) and dye-doped (GT 28) PMMA samples. It is evident from the figure that the PMMA polymer exhibits two broad peaks. The broad peaks appearing around 2θ = 30◦ figure that the PMMA polymer exhibits two broad peaks. The broad peaks appearing around and 2θ = 43◦ reveals the amorphous structure of the pure PMMA polymer [58]. The disappearance of 2θ = 30° and 2θ = 43° reveals the amorphous structure of the pure PMMA polymer [58]. The the broad peak in the GT 28 sample reveals the amorphousness of the sample. From the Urbach energy disappearance of the broad peak in the GT 28 sample reveals the amorphousness of the sample. From study and XRD analysis, it is understood that the structure of the materials and the optical electronic the Urbach energy study and XRD analysis, it is understood that the structure of the materials and properties are strongly correlated. The XRD results confirmed the fact that the samples are transferred the optical electronic properties are strongly correlated. The XRD results confirmed the fact that the to complete amorphous phase material after the addition of the extracted GT solution. The achieved samples are transferred to complete amorphous phase material after the addition of the extracted GT Urbach energy values have strongly supported the XRD results. solution. The achieved Urbach energy values have strongly supported the XRD results. 3.3 2.8 2.3 1.8 1.3 0.8 4.94 4.99 5.04 5.09 5.14 5.19 y = 6.3455x - 29.846 R2 = 0.9943 GT0 hν (eV) 2.8 2.7 2.6 2.5 2.4 2.3 2.2 2.61 2.63 2.65 2.67 2.69 hν (eV) 2.71 2.73 y = 3.3503x - 6.4141 R2 = 0.9973 GT 28 Figure 12. Urbach plot for pure PMMA (GT 0) and PMMA doped (GT 28) samples. Figure 12. Urbach plot for pure PMMA (GT 0) and PMMA doped (GT 28) samples. Ln (α) Ln (α)PDF Image | Green Chemistry Fabricate Small Band Gap Polymers
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