skip to main content


The NSF Public Access Repository (NSF-PAR) system and access will be unavailable from 11:00PM ET on Friday, December 15 until 2:00 AM ET on Saturday, December 16 due to maintenance. We apologize for the inconvenience.

Title: Doping molecular organic semiconductors by diffusion from the vapor phase
Thin films of amorphous small molecule semiconductors are widely used in organic light emitting displays and have promising applications in solar cells and thermoelectric devices. Adding dopants increases the conductivity of organic semiconductors, but high concentrations of dopants can disrupt their structural ordering, alter the shape of the electronic density of states in the material, and increase the effects of Coulomb interactions on charge transport. Electrical doping of the solution processable hole-transport material 2,2′,7,7′-tetrakis[ N , N -di(4-methoxyphenyl)amino]-9,9′-spirobifluorene (spiro-OMeTAD) was studied with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F 4 TCNQ) as a p-type dopant. Infiltration of F 4 TCNQ from the vapor phase into films of spiro-OMeTAD provided a route to highly doped films with up to 39 ± 2 mol% doping. Structural characterization confirmed that the films remain amorphous even at the highest doping levels with no apparent phase separation. We quantitatively determined the carrier concentration using UV-Vis spectroscopy to interpret the evolution of the electrical conductivity. Over the range of carrier concentrations (10 19 –10 20 1 cm −3 ), the electrical conductivity increased no more than linearly with carrier concentration, while the thermopower had a small increase with carrier concentration. The trends in conductivity and thermopower were related to the unique electronic structure of spiro-OMeTAD, which is able to support two carriers per molecule. Temperature-dependent conductivity measurements were used to further analyze the transport mechanism.  more » « less
Award ID(s):
Author(s) / Creator(s):
; ; ; ;
Date Published:
Journal Name:
Materials Chemistry Frontiers
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Doping is required to increase the electrical conductivity of organic semiconductors for uses in electronic and energy conversion devices. The limited number of commonly used p-type dopants suggests that new dopants or doping mechanisms could improve the efficiency of doping and provide new means for processing doped polymers. Drawing on Lewis acid–base pair chemistry, we combined Lewis acid dopant B(C 6 F 5 ) 3 (BCF) with the weak Lewis base benzoyl peroxide (BPO). The detailed behavior of p-type doping of the model polymer poly(3-hexylthiophene) (P3HT) with this Lewis acid–base pair in solution was examined. Solution 19 F-NMR spectra confirmed the formation of the expected counterion, as well as side products from reactions with solvent. BCF : BPO was also found to efficiently dope a range of semiconducting polymers with varying chemical structures demonstrating that the BCF : BPO combination has an effective electron affinity of at least 5.3 eV. In thin films of regioregular P3HT cast from the doped solutions, delocalized polarons formed due to the large counterions leading to a large polaron-counterion distance. At and above 0.2 eq. BCF : BPO doping, amorphous areas of the film became doped, disrupting the structural order of the films. Despite the change in structural order, thin films of regioregular P3HT doped with 0.2 eq. BCF : BPO had a conductivity of 25 S cm −1 . This study demonstrates the effectiveness of a two-component Lewis acid–base doping mechanism and suggests additional two-component Lewis acid–base chemistries should be explored. 
    more » « less
  2. Abstract

    The thermoelectric properties of semiconducting polymers are influenced by both the carrier concentration and the morphology that sets the pathways for charge transport. A combination of optical, morphological, and electrical characterization is used to assess the effect of the role of disorder on the thermoelectric properties of thin films of poly(3‐hexylthiophene) (P3HT) doped with 2,3,5,6‐tetrafluoro‐7,7,8,8‐tetracyanoquinodimethane (F4TCNQ). Controlled morphologies are formed by casting blends of regioregular (RR‐P3HT) and regiorandom (RRa‐P3HT) and then subsequently doped with F4TCNQ from the vapor phase. Optical spectroscopy and X‐ray scattering show that vapor phase doping induces order in the disordered regions of thin films and increases the long‐range connectivity of the film. The thermoelectric properties are assessed as a function of composition and it is shown that while the Seebeck coefficient is affected by structural ordering, the electrical conductivity and power factor are more strongly correlated with the long‐range connectivity of ordered domains.

    more » « less
  3. null (Ed.)
    In the past decade, great efforts have been devoted to the development of organic–inorganic hybrid perovskites for achieving efficient photovoltaics, but less attention has been paid to their thermoelectric applications. In this study, for the first time, we report the thermoelectric performance of 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ) doped NH 2 CHNH 2 SnI 3 (FASnI 3 ) thin films. It is found that the electrical conductivities of the F4-TCNQ doped FASnI 3 thin films increase and then decrease along with increased doping levels of F4-TCNQ. Systematic studies indicate that enhanced electrical conductivities are attributed to the increased charge carrier concentrations and mobilities and superior film morphologies of the F4-TCNQ doped FASnI 3 thin films, and decreased electrical conductivities originate from the cracks and poor film morphology of the F4-TCNQ doped FASnI 3 thin films induced by excess F4-TCNQ dopants. The quantitative thermal conductivity scanning thermal microscopy studies reveal that the F4-TCNQ doped FASnI 3 thin films exhibit ultralow thermal conductivities. Moreover, the thermoelectric performance of the F4-TCNQ doped FASnI 3 thin films is investigated. It is found that the F4-TCNQ doped FASnI 3 thin films exhibit a Seebeck coefficient of ∼310 μV K −1 , a power factor of ∼130 μW m −1 K −2 and a ZT value of ∼0.19 at room temperature. All these results demonstrate that our studies open a door for exploring cost-effective less-toxic organic–inorganic hybrid perovskites in heat-to-electricity conversion applications at room temperature. 
    more » « less
  4. null (Ed.)
    Amorphous oxide semiconductors (AOSs), specifically those based on ternary cation systems such as Ga-, Si-, and Hf-doped InZnO, have emerged as promising material candidates for application in next-gen transparent electronic and optoelectronic devices. Third cation-doping is a common method used during the manufacturing of amorphous oxide thin film transistors (TFTs), primarily with the intention of suppressing carrier generation during the fabrication of the channel layer of a transistor. However, the incorporation of a third cation species has been observed to negatively affect the carrier transport properties of the thin film, as it may act as an additional scattering center and subsequently lower the carrier mobility from ∼20–40 cm 2 V −1 s −1 of In 2 O 3 or a binary cation system ( i.e. , InZnO) to ∼1–10 cm 2 V −1 s −1 . This study investigates the structural, electrical, optoelectronic, and chemical properties of the ternary cation material system, InAlZnO (IAZO). The optimized carrier mobility (Hall Effect) of Al-doped InZnO is shown to remain as high as ∼25–45 cm 2 V −1 s −1 . Furthermore, Al incorporation in InZnO proves to enhance the amorphous phase stability under thermal stresses when compared to baseline InZnO films. Thin film transistors integrating optimized IAZO as the channel layer are shown to demonstrate promisingly high field effect mobilities (∼18–20 cm 2 V −1 s −1 ), as well as excellent drain current saturation and high drain current on/off ratios (>10 7 ). The high mobility and improved amorphous phase stability suggest strong potential for IAZO incorporation in the next generation of high performance and sustainable optoelectronic devices such as transparent displays. 
    more » « less
  5. Abstract

    One of the most effective ways to tune the electronic properties of conjugated polymers is to dope them with small‐molecule oxidizing agents, creating holes on the polymer and molecular anions. Undesirably, strong electrostatic attraction from the anions of most dopants localizes the holes created on the polymer, reducing their mobility. Here, a new strategy utilizing a substituted boron cluster as a molecular dopant for conjugated polymers is employed. By designing the cluster to have a high redox potential and steric protection of the core‐localized electron density, highly delocalized polarons with mobilities equivalent to films doped with no anions present are obtained. AC Hall effect measurements show that P3HT films doped with these boron clusters have conductivities and polaron mobilities roughly an order of magnitude higher than films doped with F4TCNQ, even though the boron‐cluster‐doped films have poor crystallinity. Moreover, the number of free carriers approximately matches the number of boron clusters, yielding a doping efficiency of ≈100%. These results suggest that shielding the polaron from the anion is a critically important aspect for producing high carrier mobility, and that the high polymer crystallinity required with dopants such as F4TCNQ is primarily to keep the counterions far from the polymer backbone.

    more » « less