A facile dedoping approach for effectively tuning thermoelectricity and acidity of PEDOT:PSS films

Tsai, Tsung Che; Chang, Hsiu Cheng; Chen, Chunhua; Huang, Yi; Whang, Wha Tzong

doi:10.1016/j.orgel.2013.12.023

Cited by 123 publications

(63 citation statements)

References 20 publications

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“…The doping level can also be reflected in the quinoid/ benzoid ratio of the PEDOT chain. 44 Raman spectra (Figure 4b) were used to analyze the aromatic structure of PEDOT (see the overall data and vibration modes in Supplementary Figure S2). To compare the difference in aromatic absorbances, the spectra were normalized by taking the peak at 990 cm − 1 , representing the oxyethylene ring deformation (including three peaks at 438, 573 and 990 cm − 1 ), 45 as the reference peak.…”

Section: Roles Of Anions W Shi Et Almentioning

confidence: 99%

“…44 In the present experiment, we used 0.1 M phenylhydrazine (PHZ), a mild and alcohol-soluble reducer, diluted with ethanol and acidified with different ratios of dodecylbenzenesulfonic acid to adjust the reducing ability of the reductant solution. According to the Nernst equation, the reducing potential increases with decreasing pH value, which is in turn determined by the acid/PHZ ratio.…”

Section: Roles Of Anions W Shi Et Almentioning

confidence: 99%

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Micron-thick highly conductive PEDOT films synthesized via self-inhibited polymerization: roles of anions

Shi

Qin

et al. 2017

NPG Asia Mater

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The inhibitor-dependent poly(3,4-ethylenedioxythiophene) (PEDOT) fabrication suffers major problems in the areas of controllability and film thickness. In this work, we found that anions play a key role in both the polymerization and the structure of PEDOT. As a precursor, anions greatly influence the reaction rate and oxidant solubility. In its role as a counter-ion, the anions also affect chain conductance and crystal growth. With these behaviors in mind, a self-inhibited polymerization approach using novel oxidants with appropriate anions was successfully developed to facilitate the fabrication of high quality in situ polymerized PEDOT films and solve the thickness limitation problem. Inhibitor-free heavy oxidative solutions with weakly basic anions enable the spin-coating of thick and homogeneous oxidant layers and also effectively inhibit both the crystallization of the oxidant and H + formation throughout the polymerization process. PEDOT: dodecylbenzenesulfonate (PEDOT:DBSA) exhibits the highest performance among all candidates due to its appropriate anion basicity and low steric effect. An extremely high doping level of 42.9% is achieved, and an electrical conductivity of~1100 S cm − 1 is successfully maintained for film thicknesses between 310 nm and 1.79 μm. In addition, the thermoelectric power factor (RT) for pristine films was improved to 77.2 μW mK − 2 from 69.6 μW mK − 2 by the dedoping treatment. This study provides a new approach for fabricating high performance PEDOT thick films using anion-based design. NPG Asia Materials (2017) 9, e405; doi:10.1038/am.2017.107; published online 14 July 2017 INTRODUCTION Thermoelectric (TE) materials realize direct conversion between heat and electricity, which can be used in refrigeration and power generation. The performance of TE materials is characterized by the ZT value (S 2 σT/κ) or power factor (S 2 σ), where S, σ, T and κ are the Seebeck coefficient, electrical conductivity, absolute temperature and thermal conductivity, respectively. Conducting polymer TE materials possess the advantages of low κ, good flexibility and low cost in comparison with inorganic materials. 1-4 Among them, commercially available PEDOT:polystyrenesulfonate (PEDOT:PSS) has received the most attention due to its excellent water processability and high σ ( refs 5-11 ) and is also widely used as an electrode or conductive adhesive material in applications including solar cells, 12,13 organic light-emitting diodes (OLEDs), 14,15 supercapacitors, 16,17 sensors 18,19 and so on. The PSS polyanion enables the formation of aqueous PEDOT:PSS solutions, which benefits both film printing and the synthesis of hybrid materials. However, such PSS-based processes also experience difficulties with performance optimization. For example, the insulating PSS lamellas remain in the polymer matrix, 20,21 resulting in an amorphous polymer 22 with limited σ and S. 5,9 Compared to PEDOT:PSS, PEDOT doped with smallsized anions (S-PEDOTs), such as tosylate (OTs) or triflate (OTf), have greater potential...

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Section: Roles Of Anions W Shi Et Almentioning

confidence: 99%

Section: Roles Of Anions W Shi Et Almentioning

confidence: 99%

Micron-thick highly conductive PEDOT films synthesized via self-inhibited polymerization: roles of anions

Shi

Qin

et al. 2017

NPG Asia Mater

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“…Among numerous conducting polymers candidates, many electrochromic devices based on poly(3,4-ethylenedioxythiophene) (PEDOT) and its composite have been developed due to innovative polymeric backbone possessing electron-rich nature and inhibiting α,β-and β,β-cross-links on polymerization, easy processability (PEDOT:PSS), reversible switching between two redox states, and high chemical stability [6][7][8][9]. For further improving electrochromic performance of PEDOT and its derivatives, researches therefore designed a series of strategies including modify the structure through introducing substituents, constructing network film through secondary polymerization, changing the polymeric solvent−electrolyte systems and something like that [10][11][12][13].…”

Section: Introductionmentioning

confidence: 99%

Aqueous electrosynthesis of an electrochromic material based water-soluble EDOT-MeNH2 hydrochloride

et al. 2016

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. (2016). Aqueous electrosynthesis of an electrochromic material based water-soluble EDOT-MeNH2 hydrochloride. Synthetic Metals, 211 147-154. Aqueous electrosynthesis of an electrochromic material based watersoluble EDOT-MeNH2 hydrochlorideAbstract 2'-Aminomethyl-3,4-ethylenedioxythiophene (EDOT-MeNH2) showed unsatisfactory results when its polymerization occurred in organic solvent in our previous report. Therefore, a water-soluble EDOT derivative was designed by using hydrochloric modified EDOT-MeNH2 (EDOT-MeNH2·HCl) and electropolymerized in aqueous solution to form the corresponding polymer with excellent electrochromic properties. Moreover, the polymer was systematically explored, including electrochemical, optical properties and structure characterization. Cyclic voltammetry showed low oxidation potential of EDOT-MeNH2·HCl (0.85 V) in aqueous solution, leading to the facile electrodeposition of uniform the polymer film with outstanding electroactivity. Compared with poly(2′-aminomethyl-3,4-ethylenedioxythiophene) (PEDOTMeNH2), poly(2′-aminomethyl-3,4-ethylenedioxythiophene salt) (PEDOT-MeNH3 +A-) revealed higher efficiencies (156 cm2 C-1), lower bandgap (1.68 eV), and faster response time (1.4 s). Satisfactory results implied that salinization can not only change the polymerization system, but also adjust the optical absorption, thereby increase the electrochromic properties.

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“…PSS − is a strong acid that can react with In 2 O 3 dissociating indium ions which can easily diffuse into active layer, deteriorating the stability of the devices [91]. A common way to neutralize acidic properties of PEDOT:PSS is to add strong bases such as NaOH [92], KOH [93] and guanidine [94]. However, the neutralization using strong base badly affects the conductivity of PEDOT:PSS, which results in low device performance [92].…”

Section: Enhancement In Stabilitymentioning

confidence: 99%

“…A common way to neutralize acidic properties of PEDOT:PSS is to add strong bases such as NaOH [92], KOH [93] and guanidine [94]. However, the neutralization using strong base badly affects the conductivity of PEDOT:PSS, which results in low device performance [92]. Wang et al used [95] mild base imidazole to improve the long-term stability of PSCs.…”

Section: Enhancement In Stabilitymentioning

confidence: 99%

A Review on Tailoring PEDOT:PSS Layer for Improved Performance of Perovskite Solar Cells

Reza¹,

Mabrouk²,

Qiao³

2018

Proc. Nat. Res. Soc.

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Poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS) is the most commonly used hole transport layer (HTL) in inverted (p-i-n) structured perovskite solar cells (PSCs) due to remarkable transparency and conductivity. Despite high transparency and conductivity, PEDOT:PSS has some concealed problems such as acidity, hygroscopic nature, lower work function than the ionization potential of perovskite, and poor electron blocking capability. All these properties hinder the efficient charge extraction and transport from perovskite absorber to ITO. In addition, acidic and hygroscopic nature of PEDOT:PSS can corrode the ITO electrode and degrade the moisture sensitive PSK layer, respectively. These can degrade the long-term stability and lower the performance of PSCs. Therefore, tailoring PEDOT:PSS HTL is essential for achieving highly efficient PSCs to mitigate these drawbacks. This review article gives an overview of approaches tailoring PEDOT:PSS that can minimize the limitations as HTL to improve the performance of PSCs. These include solvent treatment, composite structure, doping, and bi-layer structure PEDOT:PSS. In addition, the roles of tailored PEDOT:PSS HTL was understood in perovskite solar cells.

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A facile dedoping approach for effectively tuning thermoelectricity and acidity of PEDOT:PSS films

Cited by 123 publications

References 20 publications

Micron-thick highly conductive PEDOT films synthesized via self-inhibited polymerization: roles of anions

Micron-thick highly conductive PEDOT films synthesized via self-inhibited polymerization: roles of anions

Aqueous electrosynthesis of an electrochromic material based water-soluble EDOT-MeNH2 hydrochloride

A Review on Tailoring PEDOT:PSS Layer for Improved Performance of Perovskite Solar Cells

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