In situ and ex situ spectroscopic study of poly(3-hexylthiophene) electrochemically synthesized

Cervantes, Thiago Nogueira Marques; Bento, Danielly Cristina; Maia, Elaine Cristina Rodrigues; Zaia, Dimas Augusto Morozin; Laureto, Édson; Silva, M.A.T. da; Moore, Gregory J.; Santana, Henrique de

doi:10.1007/s10854-012-0880-9

Cited by 11 publications

(5 citation statements)

References 31 publications

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“…In the P3OT deconvoluted in situ Raman spectra, Fig. 6c, when applying 1.90 V, two defined bands were seen at frequencies of 1,448 and 1,469 cm -1 , dication and radical cation characteristics, respectively, [6,[26][27][28][29], and that band referring to dication was more intense compared to the band attributed to the radical cation.…”

Section: Resultsmentioning

confidence: 99%

“…For better viewing of the results, the spectral region between 1,400 and 1,580 cm -1 of the Raman spectra was deconvoluted, because this region refers to the characteristic frequencies of symmetric C=C stretching of the thiophenic ring, sensitive to the changes that it sustained in the thiophenic ring of the homopolymers [6,[26][27][28]. Figure 2 shows the homo and copolymer deconvoluted ex situ Raman spectra generated on ITO in 0.100 mol L -1 of LiClO 4 /ACN.…”

Section: Resultsmentioning

confidence: 99%

“…In the ex situ spectra, Fig. 2, bands were seen at 1,428-1,438, 1,443-1,461 and 1,460-1,483 cm -1 attributed to the aromatic, c species, respectively [6,[26][27][28] with variation in the relative intensity for different samples.…”

Section: Resultsmentioning

confidence: 99%

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Complementary study on the electrical and structural properties of poly(3-alkylthiophene) and its copolymers synthesized on ITO by electrochemical impedance and Raman spectroscopy

Bento

Maia

Cervantes

et al. 2014

J Mater Sci: Mater Electron

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Targeting the use of organic conjugated polymers in organic solar cells, this study looks at the electrochemical properties of poly(3-alkylthiophene) films: poly(3-methylthiophene), poly(3-hexylthiophene), poly(3-octylthiophene) and its copolymers electrochemically synthesized on a tin-doped indium oxide (ITO) substrate. Electrochemical impedance spectroscopy (EIS) was used to monitor the change in the electrochemical behavior of these films on the ITO and the charge transfer resistance (R CT ) values were determined in open circuit potential (OCP) and at different overpotentials. Together with the EIS, the ex situ and in situ Raman spectroscopy was used to characterize the influence of aromatic radical cation and dication species, present in the polymer matrix of homo and copolymers, in the management processes seen in the Nyquist and Bode-phase diagrams for different systems obtained on ITO. The EIS results in OCP showed an decrease in resistance demonstrating increased conductivity with the copolymerization, and through the Bode-phase diagram and the ex situ Raman spectra, these changes were related to the oscillation of the radical cation and dication along the polymer matrix. By studying Nyquist and Bodephase diagrams in the overpotentials, an increase in R CT values in higher potentials was seen that could be related to the bipolaronic process, which after the deconvolution of the in situ Raman spectra, was possible to relate these results to the stabilization of the dication species in the homo and copolymers matrix when subjected to high potential.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Complementary study on the electrical and structural properties of poly(3-alkylthiophene) and its copolymers synthesized on ITO by electrochemical impedance and Raman spectroscopy

Bento

Maia

Cervantes

et al. 2014

J Mater Sci: Mater Electron

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“…These bands are characteristic of stretching vibrations of bonds between sp 2 -hybridized carbons typical for aromatic polymers, graphene, and carbon nanotubes. 30–34 The in-plane bending vibrations of the methine C–H bonds are recognized as responsible for the shoulder peaks appearing at 1234 cm −1 31–32 . These peaks were absent in the Cu(II)CaMMT, thus indicating the presence of PPP phase in the clay composite PPP-Cu(II)CaMMT.…”

Section: 0 Results and Discussionmentioning

confidence: 99%

Model system study of environmentally persistent free radicals formation in a semiconducting polymer modified copper clay system at ambient temperature

et al. 2016

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This paper systematically investigates how environmentally persistent free radicals (EPFRs) are formed in a phenol contaminated model soil. Poly-p-phenylene (PPP) modified and copper-loaded montmorillonite (MMT) clays were developed and used as models of soil organic matter and the clay mineral component, respectively, with phenol being employed as a precursor pollutant. The polymer modification of the clays was carried out via surface-confined Kumada catalyst-transfer chain-growth polymerization. The presence and location of the polymer were confirmed by a combination of thermogravimetric analysis (TGA), Raman spectroscopy, and X-ray diffraction data. EPFRs were formed by the Cu(II)-clay (Cu(II)CaMMT) and poly-p-phenylene-Cu(II)clay (PPP-Cu(II)CaMMT) composite systems under environmentally relevant conditions. The g-factor and concentration of EPFRs formed by the Cu(II)CaMMT and PPP-Cu(II)CaMMT systems were found to be 2.0034 and 1.22 × 1017 spins/g and 2.0033 and 1.58 × 1017spins/g, respectively. These g-factors are consistent with the formation of phenoxyl radicals. Extended X-Ray absorption fine structure (EXAFS) analysis shows that there are distinct differences in the local stuctures of the phenoxyl radicals associated with only the Cu(II) redox centers and those formed in the presences of the PPP polymer. X-ray absorption near edge spectroscopy (XANES) results provided evidence for the reduction of Cu(II) to Cu(I) in the EPFR forming process. The 1/e lifetimes of the formed EPFRs revealed a decay time of ~20 h for the Cu(II)CaMMT system and a two-step decay pattern for the PPP-Cu(II)CaMMT system with decay times of ~13.5 h and ~55.6 h. Finally, the generation of reactive oxygen species (hydroxyl radical; •OH) by these clay systems was also investigated, with higher concentrations of •OH detected for the phenol-dosed Cu(II)CaMMT and PPP-Cu(II)CaMMT systems, compared to the non-EPFR containing undosed PPP-Cu(II)CaMMT system.

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“…The P3ATs chemically synthesized presented an energy gap of around 1.93 eV (640 nm) [5,6,[8][9][10][11][12]. Interestingly, this energy gap independent of the size of the alkyl lateral chain because it is not conjugated.…”

Section: Introductionmentioning

confidence: 99%

Electrochemical Deposition of P3AT Films Used as a Probe of Optical Properties in Polymeric System

Sá¹,

Basílio²,

Santana³

et al. 2017

Modern Technologies for Creating the Thin-Film Systems and Coatings

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Poly(3-alkylthiophene) (P3ATs) have been extensively used in photovoltaic devices such as a p-type organic Semiconductors. However, several electronic properties of P3ATs present energy transfer inter-and intra-chains that have direct consequences on the performance of optoelectronic devices. Traditionally electrochemical techniques, such as cyclic voltammetry, chronoamperometry and chronocoulometry, have been applied to process polymer thin ilms and unconventional spectroscopy techniques are used to characterize the electronic properties. In the present work, we used an innovative technique called ellipsometry emission to investigate the optical properties of P3AT ilms. We propose a new approach to study the electrochemical synthesize and unintentional doping processes of polymeric systems. We showed a strong correlation between the electrochemical synthesis and the optical properties controlling the ilm growth conditions for P3ATs. The results obtained in the present study can be potentially utilized for applications in organic devices, mainly in photovoltaic cells when the ilm deposition and the optical properties control are relevant.

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In situ and ex situ spectroscopic study of poly(3-hexylthiophene) electrochemically synthesized

Cited by 11 publications

References 31 publications

Complementary study on the electrical and structural properties of poly(3-alkylthiophene) and its copolymers synthesized on ITO by electrochemical impedance and Raman spectroscopy

Complementary study on the electrical and structural properties of poly(3-alkylthiophene) and its copolymers synthesized on ITO by electrochemical impedance and Raman spectroscopy

Model system study of environmentally persistent free radicals formation in a semiconducting polymer modified copper clay system at ambient temperature

Electrochemical Deposition of P3AT Films Used as a Probe of Optical Properties in Polymeric System

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