Effect of Donor Molecular Structure and Gate Dielectric on Charge‐Transporting Characteristics for Isoindigo‐Based Donor–Acceptor Conjugated Polymers

This study investigates the effect of the molecular structure of three different donor units, naphthalene (Np), bithiophene (BT), and thiophene–vinylene–thiophene (TVT), in isoindigo (IIG)‐based donor –acceptor conjugated polymers (PIIG‐Np, PIIG‐BT and PIIG‐TVT) on the charge carrier mobility of organic field‐effect transistors (OFETs). The charge transport properties of three different IIG‐based polymers strongly depend on donor units. PIIG–BT OFETs showed 50 times higher hole mobility (0.63 cm² V^?1 s^?1) than PIIG–TVT and PIIG–Np ones of ≈ 0.01 cm² V^?1 s^?1 with CYTOP dielectric though the BT units have less planarity than the TVT and Np units. The reasons for the different mobility in IIG‐based polymers are studied by analyzing the energy structure by absorption spectra, calculating transport levels by density functional theory, investigating the in‐ and out‐of‐plane crystallinity of thin film by grazing‐incidence wide‐angle X‐ray scattering, and extracting key transport parameters via low‐temperature measurements. By combining theoretical, optical, electrical, and structural analyses, this study finds that the large difference in OFET mobility mainly originates from the transport disorders determined by the different microcrystal structure, rather than the intrinsic transport properties in isolated chains for different polymers.     

A Timely Synthetic Tailoring of Biaxially Extended Thienylenevinylene‐Like Polymers for Systematic Investigation on Field‐Effect Transistors

Considering there is growing interest in the superior charge transport in the (E)‐2‐(2‐(thiophen‐2‐yl)‐vinyl)thiophene (TVT)‐based polymer family, an essential step forward is to provide a deep and comprehensive understanding of the structure–property relationships with their polymer analogs. Herein, a carefully chosen set of DPP‐TVT‐n polymers are reported here, involving TVT and diketopyrrolopyrrole (DPP) units that are constructed in combination with varying thiophene content in the repeat units, where n is the number of thiophene spacer units. Their OFET characteristics demonstrate ambipolar behavior; in particular, with DPP‐TVT‐0 a nearly balanced hole and electron transport are observed. Interestingly, the majority of the charge‐transport properties changed from ambipolar to p‐type dominant, together with the enhanced hole mobilities, as the electron‐donating thiophene spacers are introduced. Although both the lamellar d‐spacings and π‐stacking distances of DPP‐TVT‐n decreased with as the number of thiophene spacers increased, DPP‐TVT‐1 clearly shows the highest hole mobility (up to 2.96 cm² V^?1 s^?1) owing to the unique structural conformations derived from its smaller paracrystalline distortion parameter and narrower plane distribution relative to the others. These in‐depth studies should uncover the underlying structure–property relationships in a relevant class of TVT‐like semiconductors, shedding light on the future design of top‐performing semiconducting polymers.     

Layer‐by‐Layer Conjugated Extension of a Semiconducting Polymer for High‐Performance Organic Field‐Effect Transistor

A donor–acceptor (D–A) semiconducting copolymer, PDPP‐TVT‐29, comprising a diketopyrrolopyrrole (DPP) derivative with long, linear, space‐separated alkyl side‐chains and thiophene vinylene thiophene (TVT) for organic field‐effect transistors (OFETs) can form highly π‐conjugated structures with an edge‐on molecular orientation in an as‐spun film. In particular, the layer‐like conjugated film morphologies can be developed via short‐term thermal annealing above 150 °C for 10 min. The strong intermolecular interaction, originating from the fused DPP and D–A interaction, leads to the spontaneous self‐assembly of polymer chains within close proximity (with π‐overlap distance of 3.55 Å) and forms unexpectedly long‐range π‐conjugation, which is favorable for both intra‐ and intermolecular charge transport. Unlike intergranular nanorods in the as‐spun film, well‐conjugated layers in the 200 °C‐annealed film can yield more efficient charge‐transport pathways. The granular morphology of the as‐spun PDPP‐TVT‐29 film produces a field‐effect mobility (μ _FET) of 1.39 cm² V^?1 s^?1 in an OFET based on a polymer‐treated SiO₂ dielectric, while the 27‐Å‐step layered morphology in the 200 °C‐annealed films shows high μ _FET values of up to 3.7 cm² V^?1 s^?1.     

Visible‐Near Infrared Absorbing Polymers Containing Thienoisoindigo and Electron‐Rich Units for Organic Transistors with Tunable Polarity

Systematic creation of polymeric semiconductors from novel building blocks is critical for improving charge transport properties in organic field‐effect transistors (OFETs). A series of ultralow‐bandgap polymers containing thienoisoindigo (TIIG) as a thiophene analogue of isoindigo (IIG) is synthesized. The UV‐Vis absorptions of the TIIG‐based polymers ( PTIIG‐T , PTIIG‐Se , and PTIIG‐DT ) exhibit broad bands covering the visible to near‐infrared range of up to 1600 nm. All the polymers exhibit unipolar p‐channel operations with regard to gold contacts. PTIIG‐DT with centrosymmetric donor exhibits a maximum mobility of 0.20 cm² V^?1 s^?1 under gold contacts, which is higher than those of the other polymers containing axisymmetric donors. Intriguingly, OFETs fabricated with aluminum electrodes show ambipolar charge transport with hole and electron mobilities of up to 0.28 ( PTIIG‐DT ) and 0.03 ( PTIIG‐T ) cm² V^?1 s^?1, respectively. This is a record value for the hitherto reported TIIG‐based OFETs. The finding demonstrates that TIIG‐based polymers can potentially function as either unipolar or ambipolar semiconductors without reliance on the degree of electron affinity of the co‐monomers.     

Functionalized Asymmetric Linear Acenes for High‐Performance Organic Semiconductors

A series of compounds from the tetraceno[2,3‐b]thiophene and the anthra[2,3‐b]thiophene family of semiconducting molecules has been made. Specifically, synthetic routes to functionalize the parent molecules with bromo and then hexyl groups are shown. The bromo‐ and hexyl‐functionalized tetraceno[2,3‐b]thiophene and anthra[2,3‐b]thiophene were characterized in the top‐contact thin‐film transistor (TFT) geometry. They give high mobilities, ranging from 0.12 cm² V^?1 s^?1 for α‐n‐hexylanthra[2,3‐ b]thiophene to as high as 0.85 cm² V^?1 s^?1 for α‐bromotetraceno[2,3‐b]thiophene. Notably, grain size increases, going from the shorter anthra[2,3‐b]thiophene core to the longer tetraceno[2,3‐b]thiophene core, with a corresponding increase in mobility. The transition from undesirable 3D to desirable 2D thin‐film growth is explained by the increase in length of the molecule, in this case by one benzene ring, which results in an increase in intralayer interactions relative to interlayer interactions.     

Fullerene Additives Convert Ambipolar Transport to p‐Type Transport while Improving the Operational Stability of Organic Thin Film Transistors

Many high charge carrier mobility (μ) active layers within organic field‐effect transistor (OFET) configurations exhibit non‐linear current–voltage characteristics that may drift with time under applied bias and, when applying conventional equations for ideal FETs, may give inconsistent μ values. This study demonstrates that the introduction of electron deficient fullerene acceptors into thin films comprised of the high‐mobility semiconducting polymer PCDTPT suppresses an undesirable “double‐slope” in the current–voltage characteristics, improves operational stability, and changes ambipolar transport to unipolar transport. Examination of other high μ polymers shows general applicability. This study also shows that one can further reduce instability by tuning the relative electron affinity of the polymer and fullerene by creating blends containing different fullerene derivatives and semiconductor polymers. One can obtain hole μ values up to 5.6 cm² V^–1 s^–1 that are remarkably stable over multiple bias‐sweeping cycles. The results provide a simple, solution‐processable route to dictate transport properties and improve semiconductor durability in systems that display similar non‐idealities.     

Solution processable TIPS-benzodithiophene small molecules with improved semiconducting properties in organic field effect transistors

Four soluble triisopropylsilylethynyl benzodithiophene (TIPS-BDT) derivatives containing allylphenylene (TIPS-BDT-VP), allyloxyphenylene (TIPS-BDT-AOP), fluorophenylene (TIPS-BDT-FP) and thiophene (TIPS-BDT-T) aromatics as end cappers were synthesized by Suzuki or Stille coupling. A comparable study of the relationship between the molecular structure and the device performance is done by measurements of the electrochemical, thermal and optical properties of these materials. These small molecules exhibit an increased solubility and could be employed as the active component by spin-coating from solution in organic field effect transistors on flexible PET-foils. All small molecules showed good film-forming properties and high field effect transistor performance. A hole mobility of up to 0.09 cm²/Vs with high on/off current ratio of 10⁶ was determined for TIPS-BDT-FP. This mobility is only one order of magnitude lower in comparison to the today best solution processable material (e.g. TIPS-Pentacene). For the syntheses of novel semiconducting materials, both small molecules and polymers, a TIPS-BDT core is a potential precursor.     

Ambipolar organic transistors based on isoindigo derivatives

Structural and transistor properties of isoindigo derivatives are investigated. The unsubstituted isoindigo affords two polymorphs in addition to the reported brickwork structure; one has a stacking structure analogous to indigo, and another consists of nonplanar molecules. The unsubstituted isoindigo exhibits ambipolar transistor properties with the hole and electron mobilities more than 0.01 cm²/Vs, and 6.6′-diphenylisoindigo shows ambipolar transistor properties with the hole/electron mobilities of 0.037/0.027 cm²/Vs. Isoindigo derivatives with electron withdrawing groups show only electron transport, indicating that the lower limit of the HOMO level showing the hole transport is −5.7 eV.     

A Cruciform Electron Donor–Acceptor Semiconductor with Solid‐State Red Emission: 1D/2D Optical Waveguides and Highly Sensitive/Selective Detection of H2S Gas

In this paper, a new cruciform donor–acceptor molecule 2,2'‐((5,5'‐(3,7‐dicyano‐2,6‐bis(dihexylamino)benzo[1,2‐b:4,5‐b']difuran‐4,8‐diyl)bis(thiophene‐5,2‐diyl))bis (methanylylidene))dimalononitrile ( BDFTM ) is reported. The compound exhibits both remarkable solid‐state red emission and p‐type semiconducting behavior. The dual functions of BDFTM are ascribed to its unique crystal structure, in which there are no intermolecular face‐to‐face π–π interactions, but the molecules are associated by intermolecular CN…π and H‐bonding interactions. Firstly, BDFTM exhibits aggregation‐induced emission; that is, in solution, it is almost non‐emissive but becomes significantly fluorescent after aggregation. The emission quantum yield and average lifetime are measured to be 0.16 and 2.02 ns, respectively. Crystalline microrods and microplates of BDFTM show typical optical waveguiding behaviors with a rather low optical loss coefficient. Moreover, microplates of BDFTM can function as planar optical microcavities which can confine the emitted photons by the reflection at the crystal edges. Thin films show an air‐stable p‐type semiconducting property with a hole mobility up to 0.0015 cm²V^?1s^?1. Notably, an OFET with a thin film of BDFTM is successfully utilized for highly sensitive and selective detection of H₂S gas (down to ppb levels).     

Effect of Spacer Length of Siloxane‐Terminated Side Chains on Charge Transport in Isoindigo‐Based Polymer Semiconductor Thin Films

A series of isoindigo‐based conjugated polymers (PII2F‐C_mSi, m = 3–11) with alkyl siloxane‐terminated side chains are prepared, in which the branching point is systematically “moved away” from the conjugated backbone by one carbon atom. To investigate the structure–property relationship, the polymer thin film is subsequently tested in top‐contact field‐effect transistors, and further characterized by both grazing incidence X‐ray diffraction and atomic force microscopy. Hole mobilities over 1 cm² V^?1 s^?1 is exhibited for all soluble PII2F‐C_mSi (m = 5–11) polymers, which is 10 times higher than the reference polymer with same polymer backbone. PII2F‐C₉Si shows the highest mobility of 4.8 cm² V^?1 s^?1, even though PII2F‐C₁₁Si exhibits the smallest π–π stacking distance at 3.379 Å. In specific, when the branching point is at, or beyond, the third carbon atoms, the contribution to charge transport arising from π–π stacking distance shortening becomes less significant. Other factors, such as thin‐film microstructure, crystallinity, domain size, become more important in affecting the resulting device's charge transport.     

Solution‐Processed High‐Performance Tetrathienothiophene‐Based Small Molecular Blends for Ambipolar Charge Transport

Four soluble dialkylated tetrathienoacene ( TTAR) ‐based small molecular semiconductors featuring the combination of a TTAR central core, π‐conjugated spacers comprising bithiophene ( bT ) or thiophene ( T ), and with/without cyanoacrylate ( CA ) end‐capping moieties are synthesized and characterized. The molecule DbT‐TTAR exhibits a promising hole mobility up to 0.36 cm² V^?1 s^?1 due to the enhanced crystallinity of the microribbon‐like films. Binary blends of the p‐type DbT‐TTAR and the n‐type dicyanomethylene substituted dithienothiophene‐quinoid ( DTTQ‐11 ) are investigated in terms of film morphology, microstructure, and organic field‐effect transistor (OFET) performance. The data indicate that as the DbT‐TTAR content in the blend film increases, the charge transport characteristics vary from unipolar (electron‐only) to ambipolar and then back to unipolar (hole‐only). With a 1:1 weight ratio of DbT‐TTAR DTTQ‐11 in the blend, well‐defined pathways for both charge carriers are achieved and resulted in ambipolar transport with high hole and electron mobilities of 0.83 and 0.37 cm² V^?1 s^?1, respectively. This study provides a viable way for tuning microstructure and charge carrier transport in small molecules and their blends to achieve high‐performance solution‐processable OFETs.     

High Bulk Electron Mobility Diketopyrrolopyrrole Copolymers with Perfluorothiophene

The question of designing high electron mobility polymers by increasing the planarization using diffusive nonbonding heteroatom interactions in diketopyrrolopyrrole polymers is addressed in this. For this, three different diketopyrrolo[3,4‐c]pyrrole (DPP) derivatives with thienyl‐, 2‐pyridinyl‐, and phenyl‐flanked cores are copolymerized with an electron‐rich thiophene unit as well as an electron‐deficient 3,4‐difluorothiophene unit as comonomer to obtain diverse polymeric DPPs which vary systematically in their structures. The crystallinity differs significantly with clear trends on varying both flanking unit and comonomer. The optical gap and energy levels depend more on the nature of the flanking aryl units rather than on fluorination. Additionally, the charge transport properties are compared using different methods to differentiate between interface or orientation effects and bulk charge carrier transport. In organic field effect transistor devices with very high electron as well as hole mobilities (up to 0.6 cm² V^?1 s^?1) are obtained and fluorination leads to a more pronounced n‐type nature in all polymers, resulting in ambipolar behavior in otherwise p‐type materials. In contrast, space‐charge limited current measurements show a strong influence of the flanking units only on electron mobilities. Especially, the elegant synthetic strategy of combining pyridyl flanking units with difluorothiophene as the comonomer culminates in a record bulk electron mobility of 4.3 × 10^?3 cm² V^?1 s^?1 in polymers.     

Half‐Fused Diketopyrrolopyrrole‐Based Conjugated Donor–Acceptor Polymer for Ambipolar Field‐Effect Transistors

A novel building block, denoted as half‐fused diketopyrrolopyrrole (DPP) (9‐(3‐octadecylhenicosyl)‐8‐(thiophen‐2‐yl)‐7H‐pyrrolo[3,4‐a]thieno[3,2‐g]indolizine‐7,10(9H)‐dione), in which one of the flanking thiophene units is fused to one of the DPP rings via a carbon‐carbon double bond at the N‐position is reported. The half‐fused DPP is successfully utilized as an electron acceptor to prepare the conjugated donor–acceptor polymer PTFDFT , which exhibits ambipolar semiconducting behavior in ambient air. Theoretical calculations and absorption spectral studies show that the backbone of PTFDFT is more planar compared to the reference polymer with conventional DPP units. As a result, PTFDFT shows a narrow bandgap and low lowest unoccupied molecular orbital level. The more planar backbone with fewer side chains favors the dense packing of the polymer chains of PTFDFT with a short π–π stacking distance (3.49 Å). Grazing‐incidence wide‐angle X‐ray scattering data further confirm the predominant edge‐on packing mode of the PTFDFT polymer chains on the substrate. As expected, the PTFDFT thin film shows excellent ambipolar semiconducting properties under ambient conditions, reaching 2.23 and 1.08 cm² V^?1 s^?1 for the n‐ and p‐channels, respectively. In addition, complementary‐like inverter with gain value as high as 141 is successfully constructed using the PTFDFT thin film.     

Tuning the Charge Carrier Polarity of Organic Transistors by Varying the Electron Affinity of the Flanked Units in Diketopyrrolopyrrole‐Based Copolymers

Fine‐tuning of the charge carrier polarity in organic transistors is an important step toward high‐performance organic complementary circuits and related devices. Here, three new semiconducting polymers, namely, pDPF‐DTF2, pDPSe‐DTF2, and pDPPy‐DTF2, are designed and synthesized using furan, selenophene, and pyridine flanking group‐based diketopyrrolopyrrole cores, respectively. Upon evaluating their electrical properties in transistor devices, the best performance has been achieved for pDPSe‐DTF2 with the highest and average hole mobility of 1.51 and 1.22 cm² V^?1 s^?1, respectively. Most intriguingly, a clear charge‐carrier‐polarity change is observed when the devices are measured under vacuum. The pDPF‐DTF2 polymer exhibits a balanced ambipolar performance with the µ_h/µ_e ratio of 1.9, whereas pDPSe‐DTF2 exhibits p‐type dominated charge carrier transport properties with the µ_h/µ_e ratio of 26.7. Such a charge carrier transport change is due to the strong electron‐donating nature of the selenophene. Furthermore, pDPPy‐DTF2 with electron‐withdrawing pyridine flanking units demonstrates unipolar n‐type charge transport properties with an electron mobility as high as 0.20 cm² V^?1 s^?1. Overall, this study demonstrates a simple yet effective approach to switch the charge carrier polarity in transistors by varying the electron affinity of flanking groups of the diketopyrrolopyrrole unit.     

Charge-Carrier Transport in Thin Films of π-Conjugated Thiopheno-Azomethines

In this work, we explored the capacity of π-conjugated thiopheno-azomethines in the form of thin films for use in organic electronic applications. The charge-carrier transport properties of the π-conjugated thiopheno-azomethines were obtained in field-effect transistor configuration after the characterization of the film forming properties by fluorescence hyperspectral imaging and atomic force microscopy. We observed a semiconducting behavior for the azomethines investigated, being an oligomer thiophene triad, consisting of two azomethine bonds, and its polymer counterpart, consisting of about 15 azomethines bonds. The charge transport properties of an analogous thiophene vinylene triad were also examined for validating the mobility measurements, because such compounds are known to have hole transport properties. The azomethine triad was found to have a hole mobility of 3 × 10⁻⁵ cm²/Vs.     

Ortho‐ vs Bay‐Functionalization: A Comparative Study on Tetracyano‐Terrylenediimides

In this paper n‐type semiconductors synthesized via selective fourfold cyanation of the ortho‐ and bay‐positions (2,5,10,13‐ and 1,6,9,14‐positions respectively) of teyrrylenediimides are reported. A detailed study about the impact of the diverse functionalization topologies on the optoelectronic properties, self‐organization from solution, solid‐state packing, and charge carrier transport in field‐effect transistors is presented. The ortho‐substitution preserves the planarity of the core and favors high order in solution processed films. However, the strong intermolecular interactions lead to a microstructure with large aggregates and pronounced grain boundaries which lower the charge carrier transport in transistors. In contrast, the well‐soluble bay‐functionalized terrylenediimide forms only disordered films which surprisingly result in n‐type average mobilities of 0.17 cm²/Vs after drop‐casting with similar values in air. Processing by solvent vapor diffusion enhances the transport to 0.65 cm²/Vs by slight improvement of the order and surface arrangement of the molecules. This mobility is comparable to highest n‐type conductivities measured for solution processed PDI derivatives demonstrating the high potential of TDI‐based semiconductors.     

Favorable Molecular Orientation Enhancement in Semiconducting Polymer Assisted by Conjugated Organic Small Molecules

A bimodal texturing effect of semiconducting polymers is investigated by incorporating conjugated small molecules to significantly improve the charge transport characteristics via formation of 3D transport pathways. Solution blending of the electron‐transporting polymer, poly{[N,N′‐bis(2‐octyldodecyl)‐naphthalene‐1,4,5,8‐bis(dicarboximide)‐2,6‐diyl]‐alt‐5,5′‐(2,2′‐bithiophene)} (P(NDI2OD‐T2)), with small molecular crystals of tetrathiafulvalene and tetracyanoquinodimethane is used, and the thin film microstructures are studied using a combination of atomic force microscopy, transmission electron microscopy, 2D grazing incidence X‐ray diffraction, and surface‐sensitive near‐edge X‐ray absorption fine structure. Blended thin films show edge‐on and face‐on bimodal texture with long‐range order and microstructure packing orientation preferable for electron transport through the channel in organic field‐effect transistors, which is confirmed by high electron mobility 1.91 cm² V^?1 s^?1, small contact resistance, and low energetic disorder according to temperature dependence of the field‐effect mobility. Structural changes suggest a 3D network charge transport model via lamella packing and bimodal orientation of the semiconducting polymers.     

Nature of Charge Carriers in a High Electron Mobility Naphthalenediimide Based Semiconducting Copolymer

The nature of charge carriers in recently developed high mobility semiconducting donor‐acceptor polymers is debated. Here, localization due to charge relaxation is investigated in a prototypal system, a good electron transporting naphthalenediimide based copolymer, by means of current‐voltage I‐V electrical characteristics and charge modulation spectroscopy (CMS) in top‐gate field‐effect transistors (FETs), combined with density functional theory (DFT) and time dependent DFT (TDDFT) calculations. In particular, pristine copolymer films are compared with films that underwent a melt‐annealing process, the latter leading to a drastic change of the microstructure. Despite the packing modification, which involves also the channel region, both the electron mobility and the energy of polaronic transitions are substantially unchanged upon melt‐annealing. The polaron absorption features can be rationalized and reproduced by TDDFT calculations for isolated charged oligomers. Therefore, it is concluded that in such a high electron mobility copolymer the charge transport process involves polaronic species which are intramolecular in nature and, from a more general point of view, that interchain delocalization of the polaron is not necessary to sustain charge mobilities in the 0.1 to 1 cm² V^{– 1} s^–1 range. These findings contribute to the rationalization of the charge transport process in the recently developed class of donor‐acceptor π‐conjugated copolymers featuring high charge mobilities and complex morphologies.     

A Versatile Method to Fabricate Highly In‐Plane Aligned Conducting Polymer Films with Anisotropic Charge Transport and Thermoelectric Properties: The Key Role of Alkyl Side Chain Layers on the Doping Mechanism

A general method is proposed to produce oriented and highly crystalline conducting polymer layers. It combines the controlled orientation/crystallization of polymer films by high‐temperature rubbing with a soft‐doping method based on spin‐coating a solution of dopants in an orthogonal solvent. Doping rubbed films of regioregular poly(3‐alkylthiophene)s and poly(2,5‐bis(3‐dodecylthiophen‐2‐yl)thieno[3,2‐b ]thiophene) with 2,3,5,6‐tetrafluoro‐7,7,8,8‐tetracyanoquinodimethane (F₄TCNQ) yields highly oriented conducting polymer films that display polarized UV–visible–near‐infrared (NIR) absorption, anisotropy in charge transport, and thermoelectric properties. Transmission electron microscopy and polarized UV–vis–NIR spectroscopy help understand and clarify the structure of the films and the doping mechanism. F₄TCNQ^? anions are incorporated into the layers of side chains and orient with their long molecular axis perpendicular to the polymer chains. The ordering of dopant molecules depends closely on the length and packing of the alkyl side chains. Increasing the dopant concentration results in a continuous variation of unit cell parameters of the doped phase. The high orientation results in anisotropic charge conductivity (σ) and thermoelectric properties that are both enhanced in the direction of the polymer chains (σ = 22 ± 5 S cm^?1 and S = 60 ± 2 µV K^?1). The method of fabrication of such highly oriented conducting polymer films is versatile and is applicable to a large palette of semiconducting polymers.     

Double Doping of Semiconducting Polymers Using Ion-Exchange with a Dianion

The interactions between counterions and electronic carriers in electrically doped semiconducting polymers are important for delocalization of charge carriers, electronic conductivity, and thermal stability. The introduction of a dianions in semiconducting polymers leads to double doping where there is one counterion for two charge carriers. Double doping minimizes structural distortions, but changes the electrostatic interactions between the carriers and counterions. Polymeric ionic liquids (PIL) with croconate dianions are helpful to investigate the role of the counterion in p-type semiconducting polymers. PILs prevent diffusion of the cation into the semiconducting polymers during ion exchange. The redox-active croconate dianions undergo ion exchange with doped semiconducting polymers depending on their ionization energy. Croconate dianions are found to reduce doped films of poly(3-hexyl thiophene), but undergo ion exchange with a polythiophene with tetraethylene glycol side chains, P(g₄2T-T), that has a lower ionization energy. The croconate dianion maintains crystalline order in P(g₄2T-T) and leads to a lower activation energy for the electrical conductivity than PF₆⁻ counterions. The control of the doping level with croconate allows optimization of the thermoelectric performance of the semiconducting polymer. The thermal stability of the doped films of P(g₄2T-T) is found to depend strongly on the nature of the counterion.