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1.
    
While molecular ordering via crystallization is responsible for many of the impressive optoelectronic properties of thin‐film semiconducting polymer devices, crystalline morphology and its crucial influence on performance remains poorly controlled and is usually studied as a passive result of the conditions imposed by film deposition parameters. A method for systematic control over crystalline morphology in conjugated polymer thin films by very precise control of nucleation density and crystal growth conditions is presented. A precast poly(3‐hexylthiophene) film is first swollen into a solution‐like state in well‐defined vapor pressures of a good solvent, while the physical state of the polymer chains is monitored using in situ UV–vis spectroscopy and ellipsometry. Nucleation density is selected by a controlled deswelling of the film or by a self‐seeding approach using undissolved crystalline aggregates that remain in the swollen film. Nucleation densities ranging successively over many orders of magnitude are achieved, extending into the regime of spherulitic domains 10 to 100 μm in diameter, a length scale highly relevant for typical probes of macroscopic charge transport such as field‐effect transistors. This method is presented as a tool for future systematic study of the structure‐function relation in semicrystalline semiconducting polymers in a broad range of applications.  相似文献   

2.
    
Lightweight, flexible, low‐cost, and disposable electronics have transformed modern life and promise to continue to drive a diversity of applications from defense to medicine. For flexible and stretchable devices, the mechanical demands are actually quite great, requiring a material to maintain its ability to undergo elastic deformation, in both tension and compression, through many cycles of deformation. Traditional electronics are fabricated using organic semiconductors, which offer excellent electronic performance, but are often stiff and brittle. Conductive polymers offer potential for electronic materials with high toughness and an ability to deform elastically, making inexpensive, flexible electronics possible in a way no other material can. This paper reports the bulk thermal, electronic, and mechanical properties of a series of conductive polymers based on regioregular poly(3‐alkylthiophenes) (P3ATs) with randomly incorporated polythiophene (PT) in 3:1 (P3AT3‐ran ‐PT1) and 1:1 (P3AT1‐ran ‐PT1) ratios. These random copolymers are synthesized with no added synthetic complexity with respect to the homopolymer, and reproducibly give polymers with dramatically different mechanical and electronic properties. It is shown that random incorporation of the unsubstituted thiophene results in conductive polymers with excellent electronic properties (conductivities up to 500 S/cm, mobilities up to 0.11 cm2 V−1 s−1) and enhanced toughness (up to 760% improvement).  相似文献   

3.
    
Grain boundaries act as bottlenecks to charge transport in devices comprising polycrystalline organic active layers. To improve device performance, the nature and resulting impact of these boundaries must be better understood. The densities and energy levels of shallow traps within and across triethylsilylethynyl anthradithiophene (TES ADT) spherulites are quantified. The trap density is 7 × 1010 cm?2 in devices whose channels reside within a single spherulite and up to 3 × 1011 cm?2 for devices whose channels span a spherulite boundary. The activation energy for charge transport, EA, increases from 34 meV within a spherulite to 50–66 meV across a boundary, depending on the angle of molecular mismatch. Despite being molecular in nature, these EA’s are more akin to those found for charge transport in polymer semiconductors. Presumably, trapped TES ADT at the boundary can electrically connect neighboring spherulites, similar to polymer chains connecting crystallites in polymer semiconductor thin films.  相似文献   

4.
    
Modifying metal electrodes with self‐assembled monolayers (SAMs) has promising applications in organic and molecular electronics. The two key electronic parameters are the modification of the electrode work function because of SAM adsorption and the alignment of the SAM conducting states relative to the metal Fermi level. Through a comprehensive density‐functional‐theory study on a series of organic thiols self‐assembled on Au(111), relationships between the electronic structure of the individual molecules (especially the backbone polarizability and its response to donor/acceptor substitutions) and the properties of the corresponding SAMs are described. The molecular backbone is found to significantly impacts the level alignment; for molecules with small ionization potentials, even Fermi‐level pinning is observed. Nevertheless, independent of the backbone, polar head‐group substitutions have no effect on the level alignment. For the work‐function modification, the larger molecular dipole moments achieved when attaching donor/acceptor substituents to more polarizable backbones are largely compensated by increased depolarization in the SAMs. The main impact of the backbone on the work‐function modification thus arises from its influence on the molecular orientation on the surface. This study provides a solid theoretical basis for the fundamental understanding of SAMs and significantly advances the understanding of structure–property relationships needed for the future development of functional organic interfaces.  相似文献   

5.
Previous investigations of the field‐effect mobility in poly(3‐hexylthiophene) (P3HT) layers revealed a strong dependence on molecular weight (MW), which was shown to be closely related to layer morphology. Here, charge carrier mobilities of two P3HT MW fractions (medium‐MW: Mn = 7 200 g mol?1; high‐MW: Mn = 27 000 g mol?1) are probed as a function of temperature at a local and a macroscopic length scale, using pulse‐radiolysis time‐resolved microwave conductivity (PR‐TRMC) and organic field‐effect transistor measurements, respectively. In contrast to the macroscopic transport properties, the local intra‐grain mobility depends only weakly on MW (being in the order of 10?2 cm2 V?1 s?1) and being thermally activated below the melting temperature for both fractions. The striking differences of charge transport at both length scales are related to the heterogeneity of the layer morphology. The quantitative analysis of temperature‐dependent UV/Vis absorption spectra according to a model of F. C. Spano reveals that a substantial amount of disordered material is present in these P3HT layers. Moreover, the analysis predicts that aggregates in medium‐MW P3HT undergo a “pre‐melting” significantly below the actual melting temperature. The results suggest that macroscopic charge transport in samples of short‐chain P3HT is strongly inhibited by the presence of disordered domains, while in high‐MW P3HT the low‐mobility disordered zones are bridged via inter‐crystalline molecular connections.  相似文献   

6.
    
A strategy is reported to control the morphologies of inkjet‐printed small organic molecule semiconductor by modifying printed surfaces with polymer brushes. Polystyrene (PS) brushes with different chain lengths from 1.66 to 7.35 nm are grafted onto a dielectric surface via surface‐initiated atom transfer radical polymerization to form uniform, hydrophobic surfaces. Single droplets of 6,13‐bis(triisopropylsilylethynyl) pentacene (TIPS‐pentacene) are then inkjet‐printed onto these PS brush‐modified substrates. TIPS‐pentacene crystals are obtained with different morphologies depending on the chain length of the PS brushes. Short PS chains behave like self‐assembled monolayers on the dielectric surface such that small crystals are formed with random orientations. Longer PS chains become partially extended in the solvent altering ink spreading, contact‐line pinning, solute migration, and ultimately crystallization. Large self‐assembled crystals are generated with highly oriented structures. Organic thin film transistors are fabricated by printing single dots of TIPS‐pentacene. The device based on PS brushes of 5.14 nm exhibits the optimal device performances with an average mobility of 0.35 ± 0.23 cm2 V−1 s−1. These results demonstrate that these polymer brushes provide a route toward further understanding inkjet‐printing techniques for high‐performance organic electronics.  相似文献   

7.
    
A synergistic approach combining new material design and interfacial engineering of devices is adopted to produce high efficiency inverted solar cells. Two new polymers, based on an indacenodithieno[3,2‐b]thiophene‐difluorobenzothiadiazole (PIDTT‐DFBT) donor–acceptor (D–A) polymer, are produced by incorporating either an alkyl thiophene (PIDTT‐DFBT‐T) or alkyl thieno[3,2‐b]thiophene (PIDTT‐DFBT‐TT) π‐bridge as spacer. Although the PIDTT‐DFBT‐TT polymer exhibits decreased absorption at longer wavelengths and increased absorption at higher energy wavelengths, it shows higher power conversion efficiencies in devices. In contrast, the thiophene bridged PIDTT‐DFBT‐T shows a similar change in its absorption spectrum, but its low molecular weight leads to reduced hole mobilities and performance in photovoltaic cells. Inverted solar cells based on PIDTT‐DFBT‐TT are explored by modifying the electron‐transporting ZnO layer with a fullerene self‐assembled monolayer and the MoO3 hole‐transporting layer with graphene oxide. This leads to power conversion efficiencies as high as 7.3% in inverted cells. PIDTT‐DFBT‐TT's characteristic strong short wavelength absorption and high efficiency suggests it is a good candidate as a wide band gap material for tandem solar cells.  相似文献   

8.
    
The influence of the interface of the dielectric SiO2 on the performance of bottom‐contact, bottom‐gate poly(3‐alkylthiophene) (P3AT) field‐effect transistors (FETs) is investigated. In particular, the operation of transistors where the active polythiophene layer is directly spin‐coated from chlorobenzene (CB) onto the bare SiO2 dielectric is compared to those where the active layer is first spin‐coated then laminated via a wet transfer process such that the film/air interface of this film contacts the SiO2 surface. While an apparent alkyl side‐chain length dependent mobility is observed for films directly spin‐coated onto the SiO2 dielectric (with mobilities of ≈10?3 cm2 V?1 s?1 or less) for laminated films mobilities of 0.14 ± 0.03 cm2 V?1 s?1 independent of alkyl chain length are recorded. Surface‐sensitive near edge X‐ray absorption fine structure (NEXAFS) spectroscopy measurements indicate a strong out‐of‐plane orientation of the polymer backbone at the original air/film interface while much lower average tilt angles of the polymer backbone are observed at the SiO2/film interface. A comparison with NEXAFS on crystalline P3AT nanofibers, as well as molecular mechanics and electronic structure calculations on ideal P3AT crystals suggest a close to crystalline polymer organization at the P3AT/air interface of films from CB. These results emphasize the negative influence of wrongly oriented polymer on charge carrier mobility and highlight the potential of the polymer/air interface in achieving excellent “out‐of‐plane” orientation and high FET mobilities.  相似文献   

9.
    
The field‐effect transistor (FET) and diode characteristics of poly(3‐alkylthiophene) (P3AT) nanofiber layers deposited from nanofiber dispersions are presented and compared with those of layers deposited from molecularly dissolved polymer solutions in chlorobenzene. The P3AT n‐alkyl‐side‐chain length was varied from 4 to 9 carbon atoms. The hole mobilities are correlated with the interface and bulk morphology of the layers as determined by UV–vis spectroscopy, transmission electron microscopy (TEM) with selected area electron diffraction (SAED), atomic force microscopy (AFM), and polarized carbon K‐edge near edge X‐ray absorption fine structure (NEXAFS) spectroscopy. The latter technique reveals the average polymer orientation in the accumulation region of the FET at the interface with the SiO2 gate dielectric. The previously observed alkyl‐chain‐length‐dependence of the FET mobility in P3AT films results from differences in molecular ordering and orientation at the dielectric/semiconductor interface, and it is concluded that side‐chain length does not determine the intrinsic mobility of P3ATs, but rather the alkyl chain length of P3ATs influences FET diode mobility only through changes in interfacial bulk ordering in solution processed films.  相似文献   

10.
    
An electronegative conjugated compound composed of a newly designed carbonyl‐bridged bithiazole unit and trifluoroacetyl terminal groups is synthesized as a candidate for air‐stable n‐type organic field‐effect transistor (OFET) materials. Cyclic voltammetry measurements reveal that carbonyl‐bridging contributes both to lowering the lowest unoccupied molecular orbital energy level and to stabilizing the anionic species. X‐ray crystallographic analysis of the compound shows a planar molecular geometry and a dense molecular packing, which is advantageous to electron transport. Through these appropriate electrochemical properties and structures for n‐type semiconductor materials, OFET devices based on this compound show electron mobilities as high as 0.06 cm2 V?1 s?1 with on/off ratios of 106 and threshold voltages of 20 V under vacuum conditions. Furthermore, these devices show the same order of electron mobility under ambient conditions.  相似文献   

11.
    
Charge transport is investigated in high‐mobility n‐channel organic field‐effect transistors (OFETs) based on 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), Polyera ActivInk? N2200) with variable‐temperature electrical measurements and charge‐modulation spectroscopy. Results indicate an unusually uniform energetic landscape of sites for charge‐carrier transport along the channel of the transistor as the main reason for the observed high‐electron mobility. Consistent with a lateral field‐independent transport at temperatures down to 10 K, the reorganization energy is proposed to play an important role in determining the activation energy for the mobility. Quantum chemical calculations, which show an efficient electronic coupling between adjacent units and a reorganization energy of a few hundred meV, are consistent with these findings.  相似文献   

12.
    
The mechano‐electrical properties of poly(3‐hexylthiophene) thin films are investigated as a function of their tie‐chain content. Tie chains play an indispensable role in enabling strain‐induced structural alignment and charge‐transport enhancement in the strain direction. In the absence of sufficient tie chains, the external mechanical force cannot induce any significant polymer backbone alignment locally or crystallite reorientation at the mesoscale. These samples instead undergo brittle fracture on deformation, with cracks forming normal to the direction of strain; charge transport in this direction is hindered as a consequence. This mechanistic insight on strain alignment points to the promise of leveraging tie‐chain fraction as a practical tuning knob for effecting the mechano‐electrical properties in conjugated polymer systems.  相似文献   

13.
    
The molecular structure and electrical properties of two n‐type organic small molecules which have the same core but different alkyl chains are compared. The effect of the length of alkyl chains on charge transport along the alkyl‐chain stacking direction (out‐of‐plane) is investigated by a combination of techniques. The results show that a longer alkyl chain corresponds to lower out‐of‐plane mobility (µout‐of‐plane). More importantly, it is found that this effect not only plays a significant role in affecting the performance of diode‐structure devices such as organic light‐emitting diodes (OLEDs) or organic photovoltaics (OPVs), but also has profound influence on the performance of organic field‐effect transistors (OFETs), especially for OFETs which are in staggered configuration.  相似文献   

14.
    
To devise a reliable strategy for achieving specific HOMO and LUMO energy level modulation via alternating donor‐acceptor monomer units, we investigate a series of conjugated polymers (CPs) in which the electron withdrawing power of the acceptor group is varied, while maintaining the same donor group and the same conjugated chain conformation. Through experiment and DFT calculations, good correlation is identified between the withdrawing strength of the acceptor group, the HOMO and LUMO levels, and the degree of orbital localization, which allows reliable design principles for CPs. Increasing the acceptor strength results in an enhanced charge transfer upon combination with a donor monomer and a more pronounced decrease of the LUMO level. Moreover, while HOMO states remain delocalized along the polymer chain, LUMO states are strongly localized at specific bonds within the acceptor group. The degree of LUMO localization increases with increasing polymer length, which results in a further drop of the LUMO level and converges to its final value when the number of repeat units reaches the characteristic conjugation length. Based on these insights we designed PBT8PT, which exhibits 6.78% power conversion efficiency after device optimization via the additive assisted annealing, demonstrating the effectiveness of our predictive design approach.  相似文献   

15.
    
We have fabricated organic field‐effect transistors based on thin films of 2,7‐carbazole oligomeric semiconductors 1,4‐bis(vinylene‐(N‐hexyl‐2‐carbazole))phenylene (CPC), 1,4‐bis(vinylene‐(N′‐methyl‐7′‐hexyl‐2′‐carbazole))benzene (RCPCR), N‐hexyl‐2,7‐bis(vinylene‐(N‐hexyl‐2‐carbazole))carbazole (CCC), and N‐methyl‐2,7‐bis(vinylene‐(7‐hexyl‐N‐methyl‐2‐carbazole))carbazole (RCCCR). The organic semiconductors are deposited by thermal evaporation on bare and chemically modified silicon dioxide surfaces (SiO2/Si) held at different temperatures varying from 25 to 200 °C during deposition. The resulting thin films have been characterized using UV‐vis and Fourier‐transform infrared spectroscopies, scanning electron microscopy, and X‐ray diffraction, and the observed top‐contact transistor performances have been correlated with thin‐film properties. We found that these new π‐conjugated oligomers can form highly ordered structures and reach high hole mobilities. Devices using CPC as the active semiconductor have exhibited mobilities as high as 0.3 cm2 V–1 s–1 with on/off current ratios of up to 107. These features make CPC and 2,7‐carbazolenevinylene‐based oligomers attractive candidates for device applications.  相似文献   

16.
    
In the past few decades, mainly two kind of organic semiconductors, namely small molecules and polymers, have been dealt with. It turns out that the difference between these two categories in terms of charge carrier transport arises from the potentially different morphologies and the molecular packing. There are many studies showing the effect of the chemical structure on the electronic properties. However, in this study, the focus is on the role of processing conditions which is found to be of at least equal importance. To study a range of morphologies and packing in as similar molecules, two systems prepared by “Click”‐type chemistry are chosen, with the major difference between them being the replacement of a flat unit with one that introduces a slight twist to the aromatic skeleton. Through AFM and X‐ray studies, it is shown that the molecule with the potentially flat geometry can exhibit a high degree of π–π stacking, leading to morphologies ranging from polycrystalline to single crystals while the other is always in the amorphous film state. The transport properties are compared using organic field effect transistor (OFETs) in both top and bottom contact configurations.  相似文献   

17.
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18.
    
Polymeric semiconductors have demonstrated great potential in the mass production of low‐cost, lightweight, flexible, and stretchable electronic devices, making them very attractive for commercial applications. Over the past three decades, remarkable progress has been made in donor–acceptor (D–A) polymer‐based field‐effect transistors, with their charge‐carrier mobility exceeding 10 cm2 V?1 s?1. Numerous molecular designs of D–A polymers have emerged and evolved along with progress in understanding the charge transport physics behind their high mobility. In this review, the current understanding of charge transport in polymeric semiconductors is covered along with significant features observed in high‐mobility D–A polymers, with a particular focus on polymeric microstructures. Subsequently, emerging molecular designs with further prospective improvements in charge‐carrier mobility are described. Moreover, the current issues and outlook for future generations of polymeric semiconductors are discussed.  相似文献   

19.
The interaction of spores of Ulva with bioinspired structured surfaces in the nanometer–micrometer size range is investigated using a series of coatings with systematically varying morphology and chemistry, which allows separation of the contributions of morphology and surface chemistry to settlement (attachment) and adhesion strength. Structured surfaces are prepared by layer‐by‐layer spray‐coating deposition of polyelectrolytes. By changing the pH during application of oppositely charged poly(acrylic acid) and polyethylenimine polyelectrolytes, the surface structures are systematically varied, which allows the influence of morphology on the biological response to be determined. In order to discriminate morphological from chemical effects, surfaces are chemically modified with poly(ethylene glycol) and tridecafluoroctyltriethoxysilane. This chemical modification changes the water contact angles while the influence of the morphology is retained. The lowest level of settlement is observed for structures of the order 2 µm. All surfaces are characterized with respect to their wettability, chemical composition, and morphological properties by contact angle measurement, X‐ray photoelectron spectroscopy, scanning electron microscopy, and atomic force microscopy.  相似文献   

20.
    
Organic thin‐film transistors (TFTs) are prepared by vacuum deposition and solution shearing of 2,9‐bis(perfluoroalkyl)‐substituted tetraazaperopyrenes (TAPPs) with bromine substituents at the aromatic core. The TAPP derivatives are synthesized by reacting known unsubstituted TAPPs with bromine in fuming sulphuric acid, and their electrochemical properties are studied in detail by cyclic voltammetry and modelled with density functional theory (DFT) methods. Lowest unoccupied molecular orbital (LUMO) energies and electron affinities indicate that the core‐brominated TAPPs should exhibit n‐channel semiconducting properties. Current‐voltage characteristics of the TFTs established electron mobilities of up to μn = 0.032 cm2 V?1 s?1 for a derivative which was subsequently processed in the fabrication of a complementary ring oscillator on a flexible plastic substrate (PEN).  相似文献   

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