Semicrystalline P3HT Research Articles

Preferential Location of Dopants in the Amorphous Phase of Oriented Regioregular Poly(3‐hexylthiophene‐2,5‐diyl) Films Helps Reach Charge Conductivities of 3000 S cm−1

AbstractDoping polymer semiconductors is a central topic in plastic electronics and especially in the design of novel thermoelectric (TE) materials. In this contribution, it has been demonstrated that doping of oriented semicrystalline P3HT thin films with the dopant tris(4‐bromophenyl)ammoniumyl hexachloroantimonate), known as magic blue (MB), helps reach charge conductivities of 3000 S cm−1 and TE power factors of 170 ± 30 μW mK−2 along the polymer chain direction. A combination of transmission electron microscopy, polarized optical absorption spectroscopy, Rutherford backscattering, and TE property measurements helps clarify the conditions necessary to achieve such high charge conductivities. A comparative study with different dopants demonstrates that the doping mechanism is intimately related to the semicrystalline structure of the polymer and whether crystalline, amorphous or both phases are doped. The highest charge mobilities are observed when the dopant MB is preferentially located in the amorphous phase of P3HT, leaving the structure of P3HT nanocrystals almost unaltered. In this case, the P3HT nanocrystals are doped from their interface with the surrounding amorphous phase. These results indicate that doping preferentially the amorphous phase of semicrystalline polymer semiconductors is an effective strategy to reduce polaron localization, enhance charge mobilities, and improve TE power factors.

Morphological Study of Blend Thin Films of Poly(3-hexylthiophene)-<i>block</i>-polyisobutylene-<i>block</i>-poly(3-hexylthiophene):Poly(3-hexylthiophene) and Their Application to Photovoltaics

The detailed morphological studies of poly(3-hexylthiophene)(P3HT)-b-polyisobutylene(PIB)-b-P3HT:P3HT blend thin films by grazing incidence X-ray scattering (GIXS) were reported. The results of GIXS experiments indicated the formation of phase separation between P3HT and PIB domains even after blending the P3HT homopolymer below 30 wt%. The change in d-spacing values of the phase-separated under strains was suppressed by increasing the weight ratio of the P3HT homopolymer, probably due to the disruption of the microphase separation. The blending the P3HT homopolymer induced the edge-on orientation during the strain process below 75%, probably by improving the interaction between P3HT domains in the blend thin films. The OPV characteristics were obtained with the device structure of ITO/PEDOT:PSS/P3HT-b-PIB-b-P3HT:P3HT:PC61BM/Ca/Al, significantly improving the JSC and FF values by increasing the P3HT homopolymer weight ratio. The excellent elongation behavior of P3HT-b-PIB-b-P3HT:P3HT blend bulk films (P3HT < 30 wt%) could be achieved, probably due to the formation of microphase separation between semi-crystalline P3HT and rubbery PIB domains.

Dopant Diffusion in Sequentially Doped Poly(3-hexylthiophene) Studied by Infrared and Photoelectron Spectroscopy

The diffusivity of dopants in semiconducting polymers is of high interest as it enables methods of sequential doping but also affects device stability. In this study, we investigate the diffusion of a bulky sequentially deposited p-dopant in poly(3-hexylthiophene) (P3HT) thin films using nondestructive in situ infrared (IR) spectroscopy and photoelectron spectroscopy (PES). We probe dopant diffusion into the polymer film at varying coverage by differentially evaluating electron transfer in the bulk and at the surface. Thereby it is possible to determine dopant coverages at which both electron transfer and incorporation of dopants are saturated. By use of PES, neutral and charged dopants can be distinguished, revealing that charged dopants are less mobile in the diffusion process than neutral molecules. We further compare the diffusivity in semicrystalline and fully amorphous P3HT. We find that at high coverage semicrystalline P3HT seems to yield a higher capacity for dopants than fully amorphous P3HT. A t...

Identifying Atomic Scale Structure in Undoped/Doped Semicrystalline P3HT Using Inelastic Neutron Scattering

The greatest advantage of organic materials is the ability to synthetically tune desired properties. However, structural heterogeneity often obfuscates the relationship between chemical structure and functional properties. Inelastic neutron scattering (INS) is sensitive to both local structure and chemical environment and provides atomic level details that cannot be obtained through other spectroscopic or diffraction methods. INS data are composed of a density of vibrational states with no selection rules, which means that every structural configuration is equally weighted in the spectrum. This allows the INS spectrum to be quantitatively decomposed into different structural motifs. We present INS measurements of the semiconducting polymer P3HT doped with F4TCNQ supported by density functional theory calculations to identify two dominant families of undoped crystalline structures and one dominant doped structural motif, in spite of considerable heterogeneity. The differences between the undoped and doped ...

Spectroscopic Investigations of Three-Phase Morphology Evolution in Polymer: Fullerene Solar Cell Blends

Nanoscale morphology is critical to determining the device efficiency of bulk heterojunction organic solar cells, and the ideal structure is often described as a three-phase network with one well-mixed phase for efficient charge separation and two purer phases for efficient charge transport. In order to understand such nanoscale morphology, we have performed detailed spectroscopic investigations and identified the three-phase morphology evolution in one of the classic blend systems, P3HT:PCBM. The impact of different phases on polymer molecular (chain conformational) order and blend thermal and optical properties were monitored in situ using resonant Raman, absorption, and photoluminescence spectroscopy techniques. Semicrystalline P3HT was found to accommodate up to ∼25% PCBM (by weight) in its amorphous phase, with very little impact on either polymer molecular order or aggregation. Higher concentrations of PCBM resulted in a greater proportion of amorphous mixed phase and reduced polymer molecular order...

Local structure of semicrystalline P3HT films probed by nanofocused diffraction

Local structure of semicrystalline P3HT films probed by nanofocused diffraction

Local structure of semicrystalline P3HT films probed by nanofocused coherent X-rays.

The hidden structural properties of semicrystalline polymer films are revealed by nanofocused X-ray scattering studies. X-ray cross-correlation analysis (XCCA) is employed to diffraction patterns from blends of poly(3-hexylthiophene) (P3HT) with gold nanoparticles (AuNPs). Spatially resolved maps of orientational distribution of crystalline domains allow us to distinguish sample regions of predominant face-on morphology, with a continuous transition to edge-on morphology. The average size of crystalline domains was determined to be of the order of 10 nm. As compared to pristine P3HT film, the P3HT/AuNPs blend is characterized by substantial ordering of crystalline domains, which can be induced by Au nanoparticles. The inhomogeneous structure of the polymer film is clearly visualized on the spatially resolved nanoscale 2D maps obtained using XCCA. Our results suggest that the observed changes of the polymer matrix within crystalline regions can be attributed to nanoconfinement in the presence of gold nanoparticles.

The effects of structural disorders and microstructural mechanisms on semi-crystalline P3HT behavior

Semiconducting conjugated polymers, such as P3HT, have applications for photovoltaic and flexible electronics. However, charge transport is sensitive to the mechanical behavior of the donor P3HT. A computational framework has, therefore, been used to identify the microstructural mechanisms, at different physical scales, that affect behavior. The approach accounts for the microstructure as an interrelated three-phase model that is physically representative of crystalline domains, an amorphous interphase, and tie-chain bridging regions. Based on our predictions, the face-on packing crystalline orientations had higher toughness in comparison with the edge-on packing orientations that had higher strengths due to local dislocation-density interaction mechanisms. The higher inelastic deformation, associated with face-on orientations, disrupted the conjugation structure in the crystalline phase, and this could affect charge. These predictions indicate that the behavior of P3HT polymers can be optimized by controlling the packing orientations, the crystallinity, the entangled chain density, and the tie chain interconnectivity.

Direct Correlation Between Electric and Structural Properties During Solidification of Poly(3‐hexylthiophene) Drop‐Cast Films

Structural and electrical properties of semicrystalline P3HT cast films onto Si/SiO(2) surface are studied during the solidification under applied electric field in lateral OFET geometry. During evaporation of the solvent, the formation of P3HT crystallites is monitored simultaneously by time-resolved X-ray diffraction and by source-drain current measurements. The electrical current is reaching its maximum in two pronounced regimes already before complete solidification of the polymer as detected by X-ray diffraction intensities. The monitored complex time dependence of current and X-ray intensities reveals a highest conducting level for the gel-like state.

Mapping the 3D distribution of CdSe nanocrystals in highly oriented and nanostructured hybrid P3HT–CdSe films grown by directional epitaxial crystallization

Highly oriented and nanostructured hybrid thin films made of regioregular poly(3-hexylthiophene) and colloidal CdSe nanocrystals are prepared by a zone melting method using epitaxial growth on 1,3,5-trichlorobenzene oriented crystals. The structure of the films has been analyzed by X-ray diffraction using synchrotron radiation, electron diffraction and 3D electron tomography to afford a multi-scale structural and morphological description of the highly structured hybrid films. A quantitative analysis of the reconstructed volumes based on electron tomography is used to establish a 3D map of the distribution of the CdSe nanocrystals in the bulk of the films. In particular, the influence of the P3HT-CdSe ratio on the 3D structure of the hybrid layers has been analyzed. In all cases, a bi-layer structure was observed. It is made of a first layer of pure oriented semi-crystalline P3HT grown epitaxially on the TCB substrate and a second P3HT layer containing CdSe nanocrystals uniformly distributed in the amorphous interlamellar zones of the polymer. The thickness of the P3HT layer containing CdSe nanoparticles increases gradually with increasing content of NCs in the films. A growth model is proposed to explain this original transversal organization of CdSe NCs in the oriented matrix of P3HT.

Relation between Microstructure and Charge Transport in Polymers of Different Regioregularity

A methodology to link an atomistic description of a polymeric semiconductor with the experimental electrical characteristics of real devices is proposed. Microscopic models of poly(3-hexylthiophene) (P3HT) of different regioregularity are generated using molecular dynamics and their electronic structure determined via an approximate quantum chemistry scheme. The resulting density of trap states and distribution of localized and delocalized states is then compared with that obtained from thin film transistor measurements of P3HT at different regioregularities. The two complementary methodologies provide a converging description of the electron transport in semicrystalline P3HT and the role of regioregularity. States at the valence band edge are localized, but delocalized “band-like” states are thermally accessible and quantitatively characterized. Both theory and experiment agree that contrary to a commonly held belief the trap density and the DOS shape are little affected by the presence of regioregularity defects.

X-ray radiation damage of organic semiconductor thin films during grazing incidence diffraction experiments

Since modern synchrotrons with highly intense X-ray beams are in use to investigate organic materials, the stability of soft matter materials during beam exposure is a crucial issue. Grazing incidence X-ray diffraction and specular X-ray reflectivity measurements were performed on thin films of organic semiconducting materials, like poly(3-hexylthiophene) (P3HT), sexithiophene and pentacene. These films were irradiated with an average flux density between 1015 and 1016photons/(smm2) and evidenced a different stability in synchrotron X-ray radiation. The semi-crystalline P3HT showed a clear intensity decrease of the 100 Bragg peak and 020 Bragg peak compared to the rather stable diffraction features of the molecular crystals sexithiophene and pentacene. The difference in synchrotron X-ray radiation stability is explained by the interaction of the X-ray beam with the individual chemical components in the molecules as well as by the different crystallinities of the materials. Furthermore, the semi-crystalline P3HT film exhibited an increase of film thickness after irradiation and the surface roughness slightly decreased. To summarize, this study shows a strong influence of synchrotron X-ray radiation to specific organic thin films like e.g. P3HT, while others like pentacene and sexithiophene are observed as quite stable.

Spectroscopic and electrical evaluation of poly(3-hexylthiophene) nanotubules made using template wetting nanofabrication

The unique properties of conjugated polymer nanostructures as compared to thin films of the same materials have fueled the investigation of a number of different polymer nanofabrication techniques. Here we examine the optoelectronic properties of poly(3-hexylthiophene)P3HT nanotubules made using one of the simplest of these techniques, template wetting nanofabrication. Comparison is made with results from our previous study in which in poly(2-methoxy-5-(2́-ethylhexyloxy)-1,4-phenylene vinylene) (MEH-PPV) nanotubules prepared in this manner were shown to have dramatically different properties in comparison with thin films due to increased molecular order in the nanostructures. With semicrystalline P3HT, the differences are much more subtle, we believe due to the greater inherent order in this material. In P3HT nanotubules, a small bathochromic shift (∼0.05 eV) in the onset of Uv–vis absorption was observed indicating increased long range order and a greater effective conjugation length in the polymer. Polarized FTIR spectroscopy indicated a small degree of preferential alignment of the inter-ring C–C bond with the axis of the nanotubules as the stretching vibration for this bond showed a dichroic ratio of 1.73. The degree of increased conjugation length and chain alignment in P3HT nanotubules indicated by both the UV–vis and polarized FTIR spectra were much smaller than that previously observed for MEH-PPV. No significant improvement in mobility as measured from the current voltage characteristics of simple single carrier devices based on the P3HT nanotubules was observed, in sharp contrast to previously studied MEH-PPV where more than an order of magnitude increase was seen. Unlike in amorphous MEH-PPV, the increase in molecular order suggested by spectral data was insufficient to significantly impact mobility of semicrystalline P3HT when using template wetting nanofabrication for either of the 100 or 200 nm nanotubules examined.