Tethered tertiary amines as solid-state n-type dopants for solution-processable organic semiconductors

Abstract

Tertiary amines covalently tethered to electron-deficient aromatic molecules by alkyl spacers enable solid-state n-doping.

Anion-induced N-doping of naphthalenediimide polymer semiconductor in organic thin-film transistors

“…The doping effect of TBAF is a somewhat unusual one, and given recent reports on the use of tertiary amines as n-type dopants, 23 we were interested if the presence of tributylamine (TBA) may have caused the doping effect. TBA may either have been present as an impurity in the commercial TBAF, or may arise from Hofmann type eliminations occurring during thermal annealing.…”

“…TBA may either have been present as an impurity in the commercial TBAF, or may arise from Hofmann type eliminations occurring during thermal annealing. 23 Therefore we investigated the device performance of films formed from solutions with 0.025 eq. of TBA ( Figure S6).…”

“…11,12 Nevertheless a few stable n-type dopants have been reported via mechanisms other than integer charge transfer. [13][14][15][16][17][18][19][20][21][22][23][24][25] For example the addition of 1H-benzimidazole or benzimidazolium salts has succeeded in tuning of the work function of graphene and the conductivity of fullerene derivatives. 13,26 Mechanistic studies in the solution phase found that the dopant reacted with the fullerene derivative through hydride or hydrogen atom transfer to afford host radical anions, which were responsible for the doping effect.…”

Air‐Stable n‐Type Thermoelectric Materials Enabled by Organic Diradicaloids

“…[2] n-Type OTE materials are prepared by chemical doping of n-type organic semiconductors such as fullerene derivatives [3] and P-(NDIOD-T 2 ). [4] Although af ew strategies such as selfdoping [5] and side-chain and backbone [6] engineering have been proposed recently to address the issue in controlling doping efficiency and microstructure,air stability,the biggest challenge in n-doped systems,has still not been solved. [7] We envision that neutral single-component organic conductors (NSOCs) [8] may provide an important alternative way to meet this challenge.…”

“…[18] Thet wo diradicaloids,2 DQQT-S and 2DQQT-Se,s how very low electrochemical band gaps (E g CV )o f0 .67 and 0.65 eV and extremely low LUMO energy levels of À4.74 and À4.73 eV,r espectively.W ithout external n-type doping, pristine thin films of 2DQQT-S and 2DQQT-Se exhibit electrical conductivities as high as 0.0080 and 0.29 Scm À1 ,r espectively.C onductive 2DQQT-Se is further applied for thermoelectric application, delivering ap ower factor of 1.4 mWm À1 K À2 ,w hich is excellent among n-type OTEm aterials. [5,6] Most strikingly,t hese n-type diradicaloid thermoelectric materials show excellent air stability and the initial electrical conductivity can be maintained for over 260 hours under ambient conditions.…”