Combination of Counterion Size and Doping Concentration Determines the Electronic and Thermoelectric Properties of Semiconducting Polymers

被引:10
作者
Baustert, Kyle N. [1 ]
Bombile, Joel H. [2 ,3 ]
Rahman, Md Tawabur [1 ]
Yusuf, Augustine O. [1 ]
Li, Ruipeng [4 ]
Huckaba, Aron J. [1 ]
Risko, Chad [2 ,3 ]
Graham, Kenneth R. [1 ]
机构
[1] Univ Kentucky, Dept Chem, Lexington, KY 40506 USA
[2] Univ Kentucky, Dept Chem, Lexington, KY 40506 USA
[3] Univ Kentucky, Ctr Appl Energy Res, Lexington, KY 40506 USA
[4] Brookhaven Natl Lab, Upton, NY 11937 USA
基金
美国国家科学基金会;
关键词
conjugated polymers; counterion size; electrochemical doping; organic semiconductors; thermoelectrics; CHARGE-TRANSFER; ORGANIC SEMICONDUCTORS; POLY(3-HEXYLTHIOPHENE); TRANSPORT; DISORDER; POWER;
D O I
10.1002/adma.202313863
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
In both chemical and electrochemical doping of organic semiconductors (OSCs), a counterion, either from the electrolyte or ionized dopant, balances the charge introduced to the OSC. Despite the large influence of this counterion on OSC optical and electronic response, there remains substantial debate on how a fundamental parameter, ion size, impacts these properties. This work resolves much of this debate by accounting for two doping regimes. In the low-doping regime, the Coulomb binding energies between charge carriers on the OSC and the counterions are significant, and larger counterions lead to decreased Coulomb interactions, more delocalized charge carriers, and higher electrical conductivities. In the high-doping regime, the Coulomb binding energies become negligible due to the increased dielectric constant of the films and a smoothing of the energy landscape; thereby, the electrical conductivities depend primarily on the extent of morphological disorder in the OSC. Moreover, in regioregular poly(3-hexylthiophene), rr-P3HT, smaller counterions lead to greater bipolaron concentrations in the low-doping regime due to the increased Coulomb interactions. Emphasizing the impact of the counterion size, it is shown that larger counterions can lead to increased thermoelectric power factors for rr-P3HT. Electrochemically doped organic semiconductors display higher electrical conductivities with larger counterions at low doping concentrations due to decreased Coulomb interactions between counterions and charge carriers. In the high doping regime, the higher dielectric constant allows all charge carriers to be "free" regardless of counterion size and morphological disorder dominates the observed electrical conductivity. image
引用
收藏
页数:10
相关论文
共 74 条
[1]   Designing π-conjugated polymer blends with improved thermoelectric power factors [J].
Abtahi, Ashkan ;
Johnson, Stephen ;
Park, So Min ;
Luo, Xuyi ;
Liang, Zhiming ;
Mei, Jianguo ;
Graham, Kenneth R. .
JOURNAL OF MATERIALS CHEMISTRY A, 2019, 7 (34) :19774-19785
[2]   Effect of doping on the density-of-states distribution and carrier hopping in disordered organic semiconductors -: art. no. 045214 [J].
Arkhipov, VI ;
Heremans, P ;
Emelianova, EV ;
Bässler, H .
PHYSICAL REVIEW B, 2005, 71 (04)
[3]   Tunable Dopants with Intrinsic Counterion Separation Reveal the Effects of Electron Affinity on Dopant Intercalation and Free Carrier Production in Sequentially Doped Conjugated Polymer Films [J].
Aubry, Taylor J. ;
Winchell, K. J. ;
Salamat, Charlene Z. ;
Basile, Victoria M. ;
Lindemuth, Jeffrey R. ;
Stauber, Julia M. ;
Axtell, Jonathan C. ;
Kubena, Rebecca M. ;
Phan, Minh D. ;
Bird, Matthew J. ;
Spokoyny, Alexander M. ;
Tolbert, Sarah H. ;
Schwartz, Benjamin J. .
ADVANCED FUNCTIONAL MATERIALS, 2020, 30 (28)
[4]   Effects of dopants on the biomechanical properties of conducting polymer films on platinum electrodes [J].
Baek, Sungchul ;
Green, Rylie A. ;
Poole-Warren, Laura A. .
JOURNAL OF BIOMEDICAL MATERIALS RESEARCH PART A, 2014, 102 (08) :2743-2754
[5]   Charge-Transfer Intermediates in the Electrochemical Doping Mechanism of Conjugated Polymers [J].
Bargigia, Ilaria ;
Savagian, Lisa R. ;
Osterholm, Anna M. ;
Reynolds, John R. ;
Silva, Carlos .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2021, 143 (01) :294-308
[6]   Impact of the anion on electrochemically doped regioregular and regiorandom poly(3-hexylthiophene) [J].
Baustert, Kyle N. ;
Abtahi, Ashkan ;
Ayyash, Ahmed N. ;
Graham, Kenneth R. .
JOURNAL OF POLYMER SCIENCE, 2022, 60 (03) :602-609
[7]  
Bubnova O, 2014, NAT MATER, V13, P190, DOI [10.1038/NMAT3824, 10.1038/nmat3824]
[8]   Tuning the Thermoelectric Properties of Conducting Polymers in an Electrochemical Transistor [J].
Bubnova, Olga ;
Berggren, Magnus ;
Crispin, Xavier .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2012, 134 (40) :16456-16459
[9]   Electrochemical Doping in Ordered and Disordered Domains of Organic Mixed Ionic-Electronic Conductors [J].
Cavassin, Priscila ;
Holzer, Isabelle ;
Tsokkou, Demetra ;
Bardagot, Olivier ;
Rehault, Julien ;
Banerji, Natalie .
ADVANCED MATERIALS, 2023, 35 (35)
[10]   Role of the Anion on the Transport and Structure of Organic Mixed Conductors [J].
Cendra, Camila ;
Giovannitti, Alexander ;
Savva, Achilleas ;
Venkatraman, Vishak ;
McCulloch, Iain ;
Salleo, Alberto ;
Inal, Sahika ;
Rivnay, Jonathan .
ADVANCED FUNCTIONAL MATERIALS, 2019, 29 (05)