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Polymers 2017, 9, 626 9 of 15 case, absorption or emission of phonon energy will always be associated to the electron transition from VB to CB with a right magnitude of crystal momentum [46]. To accurately estimate the energy band gap, from the plots of (αhυ)1/γ versus the photon energy hυ, it is necessary to extrapolate the linear portion of the curve to intersect the photon energy axis (x-axis) as shown in Figures 8–10. As a consequence, it is difficult to decide the dominant type of electronic transition in the samples. Earlier studies revealed that the value of γ can be achieved by using an analytical differentiation method, which was generally found to be an imprecise method [43,47]. For this purpose, d(ln(α))/d(hυ) versus Polymers 2017, 9, 626 9 of 15 photon energy (hυ) was plotted and a maximum peak was achieved. Furthermore, a perpendicular linefromthemaximumpeaktothephotonenergyaxisisdrawntoobtaintheE value.Thevalueof found to be an imprecise method [43,47]. For this purpose, d(ln(α))/d(hυ) versusgphoton energy (hυ) γ wwaassthpelontteesdtimanadteda fmroamximthuemsloppeeakofwthase lanc(hαiehvυe)dv.eFrsuurtshlenr(mhυor−e, Eag)pceurprvene.diTchuilsarprlionceedfruorme nteheds conmsiadxeimraubmle tpiemaek atondthies pnhoottaonprenceisrgeymaextihsoisdd[4ra3w,4n7]t.oInobthtaiisnwthoerkE,govpatliucea.lTdhielevcatlruiec olofsγs awnads Tthaeunc’s moedsetlimwaetreedufsreodmtothesstilmopaeteotfhteheoplnt(icαahlυb)avnedrsguasplna(nhdυt−hEege)lceucrtrvoen.iTchtirsapnrsoitcieodnutryepnese,erdesspcoenctsivdelrya.bTlehis is rteilmateeadntdoitshneoftaactptrheactistehme eotphtoicda[l4d3i,4e7le].ctInricthfiusnwctoirokn, ohpatridcalyl diepleecntrdicslonssmanadteTriaulsc’bsamnoddsetlrwucetruere. used to estimate the optical band gap and the electronic transition types, respectively. This is related At the same time, investigations of the optical dielectric function using UV–VIS spectroscopy are also to the fact that the optical dielectric function hardly depends on materials band structure. At the same found to be considerably useful in predicting the overall band structure of the materials [48]. Recent time, investigations of the optical dielectric function using UV–VIS spectroscopy are also found to be studies have confirmed that the imaginary part of the optical dielectric function, ε”, can mainly be considerably useful in predicting the overall band structure of the materials [48]. Recent studies have used to describe the electronic transition between occupied and unoccupied states [49–51]. The optical confirmed that the imaginary part of the optical dielectric function, ε′′, can mainly be used to describe dielectric loss spectra obtained for pure and doped PMMA samples are shown in Figure 11. It can the electronic transition between occupied and unoccupied states [49–51]. The optical dielectric loss be seen that all the samples exhibit a linear behavior at higher photon energies. The imaginary part spectra obtained for pure and doped PMMA samples are shown in Figure 11. It can be seen that all is seen to be related to the absorption coefficient [52]. It is clear that the optical band gap achieved the samples exhibit a linear behavior at higher photon energies. The imaginary part is seen to be from optical dielectric loss (see Figure 11) is almost equal to those estimated from Tauc’s model related to the absorption coefficient [52]. It is clear that the optical band gap achieved from optical (see Figure 10) for the doped samples. On the other hand, for the pure PMMA sample, the optical dielectric loss (see Figure 11) is almost equal to those estimated from Tauc’s model (see Figure 10) for band gap estimated from Tauc’s model (see Figure 8) is found to be approximately 5.04 eV, which is the doped samples. On the other hand, for the pure PMMA sample, the optical band gap estimated considerably close to that achieved (4.97 eV) from the optical dielectric loss plot (see Figure 11). Thus, from Tauc’s model (see Figure 8) is found to be approximately 5.04 eV, which is considerably close the type of electronic transition is the allowed direct transition for the pure PMMA sample and the to that achieved (4.97 eV) from the optical dielectric loss plot (see Figure 11). Thus, the type of forbidden direct transition for the doped samples. Consequently, it is understood from these results electronic transition is the allowed direct transition for the pure PMMA sample and the forbidden that the complex optical dielectric function can be successfully used for studying the band structure direct transition for the doped samples. Consequently, it is understood from these results that the and estimation of optical band gaps. Reducing the optical band gap from 5.04 eV for pure PMMA complex optical dielectric function can be successfully used for studying the band structure and samesptliemtaotio2n.6oefVopftoicratlhbeanddopgaepdsP. RMedMuAcin(gGtThe28o)ptsiacmalpblaendregvaepalfsrotmha5t.t0h4eeVexftorrapctuerde PGMTMsoAlustaimonplcean motdoif2y.6tehVe efolerctthreondiocpsetdruPcMtuMreAo(fGthTe2h8)osatmPMpleMrAevepaolslytmhaetrt;hienepxatraticctuedlaGr,Tthseoleuntieorngycasntamteosdbifeytwtheen theevleaclternonceicasntrductounrdeuocfttihoenhboasntdPsM.MHAerep,otlhyemaecrh;inevpeadrtbicaunladr,gtahpefeonrertghyesdtyatee-sdboeptewdeePnMthMeAva(lGenTce28) and conduction bands. Here, the achieved band gap for the dye-doped PMMA (GT 28) sample is sample is found to be smaller than the recently-reported band gap of Alq3 (2.83 eV) and has gained found to be smaller than the recently-reported band gap of Alq3 (2.83 eV) and has gained large large popularity among researchers due to its wide applications in photo-detectors, photovoltaic cells, popularity among researchers due to its wide applications in photo-detectors, photovoltaic cells, flat flat and flexible colour displays, and organic light-emitting diodes (OLEDs) [53]. and flexible colour displays, and organic light-emitting diodes (OLEDs) [53]. 70000 60000 50000 40000 30000 20000 10000 0 2 2.22.42.62.8 3 3.23.43.63.8 4 4.24.44.64.8 5 5.25.45.65.8 6 6.2 hν (eV) GT0 GT 14 GT 28 22 FigFuigruer8e.8T.hTehepplolotstsooff(α(αhhυυ)) vs. (hυ)foralllttheessaamppleles.s. (αhν)^2PDF Image | Green Chemistry Fabricate Small Band Gap Polymers
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