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1.
Adv Mater ; : e2000063, 2020 May 04.
Artigo em Inglês | MEDLINE | ID: mdl-32363687

RESUMO

Precise control of the microstructure in organic semiconductors (OSCs) is essential for developing high-performance organic electronic devices. Here, a comprehensive charge transport characterization of two recently reported rigid-rod conjugated polymers that do not contain single bonds in the main chain is reported. It is demonstrated that the molecular design of the polymer makes it possible to achieve an extended linear backbone structure, which can be directly visualized by high-resolution scanning tunneling microscopy (STM). The rigid structure of the polymers allows the formation of thin films with uniaxially aligned polymer chains by using a simple one-step solution-shear/bar coating technique. These aligned films show a high optical anisotropy with a dichroic ratio of up to a factor of 6. Transport measurements performed using top-gate bottom-contact field-effect transistors exhibit a high saturation electron mobility of 0.2 cm2 V-1 s-1 along the alignment direction, which is more than six times higher than the value reported in the previous work. This work demonstrates that this new class of polymers is able to achieve mobility values comparable to state-of-the-art n-type polymers and identifies an effective processing strategy for this class of rigid-rod polymer system to optimize their charge transport properties.

2.
Nat Mater ; 19(5): 491-502, 2020 May.
Artigo em Inglês | MEDLINE | ID: mdl-32296138

RESUMO

Conjugated polymers and molecular semiconductors are emerging as a viable semiconductor technology in industries such as displays, electronics, renewable energy, sensing and healthcare. A key enabling factor has been significant scientific progress in improving their charge transport properties and carrier mobilities, which has been made possible by a better understanding of the molecular structure-property relationships and the underpinning charge transport physics. Here we aim to present a coherent review of how we understand charge transport in these high-mobility van der Waals bonded semiconductors. Specific questions of interest include estimates for intrinsic limits to the carrier mobilities that might ultimately be achievable; a discussion of the coupling between charge and structural dynamics; the importance of molecular conformations and mesoscale structural features; how the transport physics of conjugated polymers and small molecule semiconductors are related; and how the incorporation of counterions in doped films-as used, for example, in bioelectronics and thermoelectric devices-affects the electronic structure and charge transport properties.

3.
Phys Rev Lett ; 124(2): 027204, 2020 Jan 17.
Artigo em Inglês | MEDLINE | ID: mdl-32004034

RESUMO

There is a growing interest in utilizing the distinctive material properties of organic semiconductors for spintronic applications. Here, we explore the injection of pure spin current from Permalloy into a small molecule system based on dinaphtho[2,3-b:2,3-f]thieno[3,2-b]thiophene (DNTT) at ferromagnetic resonance. The unique tunability of organic materials by molecular design allows us to study the impact of interfacial properties on the spin injection efficiency systematically. We show that both the spin injection efficiency at the interface and the spin diffusion length can be tuned sensitively by the interfacial molecular structure and side chain substitution of the molecule.

4.
J Am Chem Soc ; 142(2): 652-664, 2020 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-31851506

RESUMO

The polymer indacenodithiophene-co-benzothiadiazole (IDT-BT) has been thoroughly studied for its use in p-type organic thin-film transistors over the course of the past decade. While a variety of modifications have been made to its structure, few analogues have been able to match or surpass the hole mobility that can be obtained by IDT-BT. Here, we discuss the rationale behind the chemical modifications that have been utilized and suggest design principles toward high-mobility indacenodithiophene-based polymers. It is clear that planarizing intramolecular interactions, which exist between the peripheral thiophene of the IDT unit and the benzothiadiazole, are imperative for achieving high hole mobilities in this relatively amorphous polymer. Moreover, despite the less ordered backbones of the extended fused-ring cores that have recently been utilized (TIF-BT and TBIDT-BT), high mobilities were still attained in these polymers owing to additional interchain charge transfer. Thus, maintaining the beneficial thiophene-benzothiadiazole intramolecular interactions, while further extending the IDT core to promote interchain charge transfer, is a logical strategy toward high-mobility p-type polymers.

5.
ACS Nano ; 13(12): 13716-13727, 2019 Dec 24.
Artigo em Inglês | MEDLINE | ID: mdl-31738516

RESUMO

Optoelectronic devices based on conjugated polymers often rely on multilayer device architectures, as it is difficult to design all the different functional requirements, in particular the need for efficient luminescence and fast carrier transport, into a single polymer. Here we study the photophysics of a recently discovered class of conjugated polymers with high charge carrier mobility and low degree of energetic disorder and investigate whether it is possible in this system to achieve by molecular design a high photoluminescence quantum yield without sacrificing carrier mobility. Tracing exciton dynamics over femtosecond to microsecond time scales, we show that nearly all nonradiative exciton recombination arises from interactions between chromophores on different chains. We evaluate the temperature dependence and role of electron-phonon coupling leading to fast internal conversion in systems with strong interchain coupling and the extent to which this can be turned off by varying side chain substitution. By sterically decreasing interchain interaction, we present an effective approach to increase the fluorescence quantum yield of low-energy gap polymers. We present a red-NIR-emitting amorphous polymer with the highest reported film luminescence quantum efficiency of 18% whose mobility concurrently exceeds that of amorphous-Si. This is a key result toward the development of single-layer optoelectronic devices that require both properties.

6.
J Am Chem Soc ; 141(47): 18806-18813, 2019 Nov 27.
Artigo em Inglês | MEDLINE | ID: mdl-31613619

RESUMO

A fused donor, thienobenzo[b]indacenodithiophene (TBIDT), was designed and synthesized using a novel acid-promoted cascade ring closure strategy, and then copolymerized with a benzothiadiazole (BT) monomer. The backbone of TBIDT is an expansion of the well-known indacenodithiophene (IDT) unit and was expected to enhance the charge carrier mobility by improving backbone planarity and facilitating short contacts between polymer chains. However, the optimized field-effect transistors demonstrated an average saturation hole mobility of 0.9 cm2 V-1 s-1, lower than the performance of IDT-BT (∼1.5 cm2 V-1 s-1). Mobilities extracted from time-resolved microwave conductivity measurements were consistent with the trend in hole mobilities in organic field-effect transistor devices. Scanning tunneling microscopy measurements and computational modeling illustrated that TBIDT-BT exhibits a less ordered microstructure in comparison to IDT-BT. This reveals that a regular side-chain packing density, independent of conformational isomers, is critical to avoid local free volume due to irregular packing, which can host trapping impurities. DFT calculations indicated that TBIDT-BT, despite containing a larger, planar unit, showed less stabilization of planar backbone geometries in comparison to IDT-BT. This is due to the reduced electrostatic stabilizing interactions between the peripheral thiophene of the fused core and the BT unit, resulting in a reduction of the barrier to rotation around the single bond. These insights provide a greater understanding of the general structure-property relationships required for semiconducting polymer repeat units to ensure optimal backbone planarization, as illustrated with IDT-type units, guiding the design of novel semiconducting polymers with extended fused backbones for high-performance field-effect transistors.

7.
Adv Mater ; 31(43): e1902407, 2019 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-31512304

RESUMO

Molecular vibrations play a critical role in the charge transport properties of weakly van der Waals bonded organic semiconductors. To understand which specific phonon modes contribute most strongly to the electron-phonon coupling and ensuing thermal energetic disorder in some of the most widely studied high-mobility molecular semiconductors, state-of-the-art quantum mechanical simulations of the vibrational modes and the ensuing electron-phonon coupling constants are combined with experimental measurements of the low-frequency vibrations using inelastic neutron scattering and terahertz time-domain spectroscopy. In this way, the long-axis sliding motion is identified as a "killer" phonon mode, which in some molecules contributes more than 80% to the total thermal disorder. Based on this insight, a way to rationalize mobility trends between different materials and derive important molecular design guidelines for new high-mobility molecular semiconductors is suggested.

8.
ACS Energy Lett ; 4(9): 2301-2307, 2019 Sep 13.
Artigo em Inglês | MEDLINE | ID: mdl-31544151

RESUMO

Mixed lead-tin halide perovskites have sufficiently low bandgaps (∼1.2 eV) to be promising absorbers for perovskite-perovskite tandem solar cells. Previous reports on lead-tin perovskites have typically shown poor optoelectronic properties compared to neat lead counterparts: short photoluminescence lifetimes (<100 ns) and low photoluminescence quantum efficiencies (<1%). Here, we obtain films with carrier lifetimes exceeding 1 µs and, through addition of small quantities of zinc iodide to the precursor solutions, photoluminescence quantum efficiencies under solar illumination intensities of 2.5%. The zinc additives also substantially enhance the film stability in air, and we use cross-sectional chemical mapping to show that this enhanced stability is because of a reduction in tin-rich clusters. By fabricating field-effect transistors, we observe that the introduction of zinc results in controlled p-doping. Finally, we show that zinc additives also enhance power conversion efficiencies and the stability of solar cells. Our results demonstrate substantially improved low-bandgap perovskites for solar cells and versatile electronic applications.

9.
Phys Chem Chem Phys ; 21(35): 19521-19528, 2019 Sep 21.
Artigo em Inglês | MEDLINE | ID: mdl-31463496

RESUMO

Spintronics, as a relatively new scientific field, is developing rapidly together with our understanding of spin related phenomena and spin manipulation. One of the challenges in the field is spin injection, which has been achieved optically in inorganic crystalline semiconductors, but not yet in organic semiconductors. Here, we introduce an approach whereby we apply group theory and computational methods to design molecular materials in which spin can be injected optically via circularly polarized light (CPL). Our approach is based on the use of group theory and double group theory to identify families of molecules whose symmetry satisfies design rules for optical excitation of triplets of particular properties. Employing such screening prior to detailed calculation can accelerate design by first identifying any structures that fail some criterion on grounds of symmetry. Here, we show using group theory and computational methods that particular families of molecules possess a low lying triplet state that can be excited with circularly polarized light causing spin polarization of an excited electron. Such structures are of potential interest for organic or molecular spintronics. We present an efficient procedure to identify candidate point groups and determine the excited state symmetry using group theory, before full calculation of excited states using relativistic quantum chemistry.

10.
Adv Mater ; 31(35): e1902618, 2019 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-31293012

RESUMO

Optoelectronic devices based on metal halide perovskites, including solar cells and light-emitting diodes, have attracted tremendous research attention globally in the last decade. Due to their potential to achieve high carrier mobilities, organic-inorganic hybrid perovskite materials can enable high-performance, solution-processed field-effect transistors (FETs) for next-generation, low-cost, flexible electronic circuits and displays. However, the performance of perovskite FETs is hampered predominantly by device instabilities, whose origin remains poorly understood. Here, perovskite single-crystal FETs based on methylammonium lead bromide are studied and device instabilities due to electrochemical reactions at the interface between the perovskite and gold source-drain top contacts are investigated. Despite forming the contacts by a gentle, soft lamination method, evidence is found that even at such "ideal" interfaces, a defective, intermixed layer is formed at the interface upon biasing of the device. Using a bottom-contact, bottom-gate architecture, it is shown that it is possible to minimize such a reaction through a chemical modification of the electrodes, and this enables fabrication of perovskite single-crystal FETs with high mobility of up to ≈15 cm2 V-1 s-1 at 80 K. This work addresses one of the key challenges toward the realization of high-performance solution-processed perovskite FETs.

11.
Nat Commun ; 10(1): 2614, 2019 06 13.
Artigo em Inglês | MEDLINE | ID: mdl-31197152

RESUMO

Efficient conjugated polymer optoelectronic devices benefit from concomitantly high luminescence and high charge carrier mobility. This is difficult to achieve, as interchain interactions, which are needed to ensure efficient charge transport, tend also to reduce radiative recombination and lead to solid-state quenching effects. Many studies detail strategies for reducing these interactions to increase luminescence, or modifying chain packing motifs to improve percolation charge transport; however achieving these properties together has proved elusive. Here, we show that properly designed amorphous donor-alt-acceptor conjugated polymers can circumvent this problem; combining a tuneable energy gap, fast radiative recombination rates and luminescence quantum efficiencies >15% with high carrier mobilities exceeding 2.4 cm2/Vs. We use photoluminescence from exciton states pinned to close-crossing points to study the interplay between mobility and luminescence. These materials show promise towards realising advanced optoelectronic devices based on conjugated polymers, including electrically-driven polymer lasers.

12.
Nat Commun ; 10(1): 2122, 2019 05 09.
Artigo em Inglês | MEDLINE | ID: mdl-31073179

RESUMO

Charge transport in conjugated polymer semiconductors has traditionally been thought to be limited to a low-mobility regime by pronounced energetic disorder. Much progress has recently been made in advancing carrier mobilities in field-effect transistors through developing low-disorder conjugated polymers. However, in diodes these polymers have to date not shown much improved mobilities, presumably reflecting the fact that in diodes lower carrier concentrations are available to fill up residual tail states in the density of states. Here, we show that the bulk charge transport in low-disorder polymers is limited by water-induced trap states and that their concentration can be dramatically reduced through incorporating small molecular additives into the polymer film. Upon incorporation of the additives we achieve space-charge limited current characteristics that resemble molecular single crystals such as rubrene with high, trap-free SCLC mobilities up to 0.2 cm2/Vs and a width of the residual tail state distribution comparable to kBT.

13.
Adv Sci (Weinh) ; 6(7): 1801189, 2019 Apr 03.
Artigo em Inglês | MEDLINE | ID: mdl-30989018

RESUMO

For newly developed semiconductors, obtaining high-performance transistors and identifying carrier mobility have been hot and important issues. Here, large-area fabrications and thorough analysis of InGaZnO transistors with enhanced current by simple encapsulations are reported. The enhancement in the drain current and on-off ratio is remarkable in the long-channel devices (e.g., 40 times in 200 µm long transistors) but becomes much less pronounced in short-channel devices (e.g., 2 times in 5 µm long transistors), which limits its application to the display industry. Combining gated four-probe measurements, scanning Kelvin-probe microscopy, secondary ion mass spectrometry, X-ray photoelectron spectroscopy, and device simulations, it is revealed that the enhanced apparent mobility up to several tens of times is attributed to the stabilized hydrogens in the middle area forming a degenerated channel area while that near the source-drain contacts are merely doped, which causes artifact in mobility extraction. The studies demonstrate the use of hydrogens to remarkably enhance performance of oxide transistors by inducing a new mode of device operation. Also, this study shows clearly that a thorough analysis is necessary to understand the origin of very high apparent mobilities in thin-film transistors or field-effect transistors with advanced semiconductors.

14.
Sci Adv ; 5(2): eaav2012, 2019 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-30793032

RESUMO

One source of instability in perovskite solar cells (PSCs) is interfacial defects, particularly those that exist between the perovskite and the hole transport layer (HTL). We demonstrate that thermally evaporated dopant-free tetracene (120 nm) on top of the perovskite layer, capped with a lithium-doped Spiro-OMeTAD layer (200 nm) and top gold electrode, offers an excellent hole-extracting stack with minimal interfacial defect levels. For a perovskite layer interfaced between these graded HTLs and a mesoporous TiO2 electron-extracting layer, its photoluminescence yield reaches 15% compared to 5% for the perovskite layer interfaced between TiO2 and Spiro-OMeTAD alone. For PSCs with graded HTL structure, we demonstrate efficiency of up to 21.6% and an extended power output of over 550 hours of continuous illumination at AM1.5G, retaining more than 90% of the initial performance and thus validating our approach. Our findings represent a breakthrough in the construction of stable PSCs with minimized nonradiative losses.

15.
Nat Commun ; 10(1): 962, 2019 02 22.
Artigo em Inglês | MEDLINE | ID: mdl-30796250

RESUMO

The original version of this Article contained an error in the spelling of the author Dan Credgington, which was incorrectly given as Dan Credington. This has now been corrected in both the PDF and HTML versions of the Article.

16.
Adv Mater ; 31(10): e1806697, 2019 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-30667548

RESUMO

Organic semiconductors (OSCs) have been widely studied due to their merits such as mechanical flexibility, solution processability, and large-area fabrication. However, OSC devices still have to overcome contact resistance issues for better performances. Because of the Schottky contact at the metal-OSC interfaces, a non-ideal transfer curve feature often appears in the low-drain voltage region. To improve the contact properties of OSCs, there have been several methods reported, including interface treatment by self-assembled monolayers and introducing charge injection layers. Here, a selective contact doping of 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4 -TCNQ) by solid-state diffusion in poly(2,5-bis(3-hexadecylthiophen-2-yl)thieno[3,2-b]thiophene) (PBTTT) to enhance carrier injection in bottom-gate PBTTT organic field-effect transistors (OFETs) is demonstrated. Furthermore, the effect of post-doping treatment on diffusion of F4 -TCNQ molecules in order to improve the device stability is investigated. In addition, the application of the doping technique to the low-voltage operation of PBTTT OFETs with high-k gate dielectrics demonstrated a potential for designing scalable and low-power organic devices by utilizing doping of conjugated polymers.

17.
ACS Nano ; 13(2): 1645-1654, 2019 Feb 26.
Artigo em Inglês | MEDLINE | ID: mdl-30604954

RESUMO

Two-dimensional (2D) lead halide perovskites with long-chain ammonium halides display high photoluminescence quantum yields (PLQYs), because of their size and dielectric confinement, which hold promise for a high-efficiency and low-cost light-emitting diode (LED). However, the presence of an insulating organic long-chain spacer cation (L) dramatically deteriorates the charge transport properties along the out-of-plane nanoplatelet direction or adjacent nanocrystals, which would limit the device performance of the LED. To overcome this issue, we successfully incorporate small alkaline ions such as sodium (Na+) to replace the long organic molecule. Grazing incidence X-ray diffraction measurements verify 2D layer formation with a preferred crystallite orientation. In addition, the incorporated sodium salt also generates amorphous sodium lead bromide (NaPbBr3) in perovskite as spacers to form a nanocrystal-like halide perovskite film. The PLQY is dramatically improved in the sodium-incorporated film because of its enhanced photoluminescence lifetime. Upon incorporation of a low concentration of an organic additive, this two-dimensional-three-dimensional (2D-3D) perovskite can achieve a compact and uniform film. Therefore, a 2D-3D perovskite achieves a high external quantum efficiency of 15.9% with good operational stability. We develop a type of 2D-3D halide perovskite with various inorganic ions as spacers for promising high-performance optoelectronic devices.

18.
Nat Commun ; 9(1): 3892, 2018 09 24.
Artigo em Inglês | MEDLINE | ID: mdl-30250032

RESUMO

Organometal halide perovskites (OHP) are promising materials for low-cost, high-efficiency light-emitting diodes. In films with a distribution of two-dimensional OHP nanosheets and small three-dimensional nanocrystals, an energy funnel can be realized that concentrates the excitations in highly efficient radiative recombination centers. However, this energy funnel is likely to contain inefficient pathways as the size distribution of nanocrystals, the phase separation between the OHP and the organic phase. Here, we demonstrate that the OHP crystallite distribution and phase separation can be precisely controlled by adding a molecule that suppresses crystallization of the organic phase. We use these improved material properties to achieve OHP light-emitting diodes with an external quantum efficiency of 15.5%. Our results demonstrate that through the addition of judiciously selected molecular additives, sufficient carrier confinement with first-order recombination characteristics, and efficient suppression of non-radiative recombination can be achieved while retaining efficient charge transport characteristics.

19.
Nat Commun ; 9(1): 2933, 2018 07 26.
Artigo em Inglês | MEDLINE | ID: mdl-30050114

RESUMO

Self-assembly of monolayers of functional molecules on dielectric surfaces is a promising approach for the development of molecular devices proposed in the 1970s. Substrate chemically bonded self-assembled monolayers of semiconducting conjugated molecules exhibit low mobility. And self-assembled monolayer molecular crystals are difficult to scale up and limited to growth on substrates terminated by hydroxyl groups, which makes it difficult to realize sophisticated device functions, particularly for those relying on n-type electron transport, as electrons suffer severe charge trapping on hydroxyl terminated surfaces. Here we report a gravity-assisted, two-dimensional spatial confinement method for bottom-up growth of high-quality n-type single-crystalline monolayers over large, centimeter-sized areas. We demonstrate that by this method, n-type monolayer molecular crystals with high field-effect mobility of 1.24 cm2 V-1 s-1 and band-like transport characteristics can be grown on hydroxyl-free polymer surface. Furthermore, we used these monolayer molecular crystals to realize high-performance crystalline, gate-/light-tunable lateral organic p-n diodes.

20.
Adv Mater ; : e1801874, 2018 Jul 18.
Artigo em Inglês | MEDLINE | ID: mdl-30022541

RESUMO

The exploration of a wide range of molecular structures has led to the development of high-performance conjugated polymer semiconductors for flexible electronic applications including displays, sensors, and logic circuits. Nevertheless, many conjugated polymer field-effect transistors (OFETs) exhibit nonideal device characteristics and device instabilities rendering them unfit for industrial applications. These often do not originate in the material's intrinsic molecular structure, but rather in external trap states caused by chemical impurities or environmental species such as water. Here, a highly efficient mechanism is demonstrated for the removal of water-induced traps that are omnipresent in conjugated polymer devices even when processed in inert environments; the underlying mechanism is shown, by which small-molecular additives with water-binding nitrile groups or alternatively water-solvent azeotropes are capable of removing water-induced traps leading to a significant improvement in OFET performance. It is also shown how certain polymer structures containing strong hydrogen accepting groups will suffer from poor performances due to their high susceptibility to interact with water molecules; this allows the design guidelines for a next generation of stable, high-performing conjugated polymers to be set forth.

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