Inkjet printing of single-crystal films
TL;DR: It is shown that mixing fine droplets of an antisolvent and a solution of an active semiconducting component within a confined area on an amorphous substrate can trigger the controlled formation of exceptionally uniform single-crystal or polycrystalline thin films that grow at the liquid–air interfaces.
Abstract: Printing electronic devices using semiconducting 'ink' is seen as a promising route to cheap, large-area and flexible electronics, but the performance of such devices suffers from the relatively poor crystallinity of the printed material. Hiromi Minemawari and colleagues have developed an inkjet-based printing technique involving controlled mixing on a surface of two solutions — the semiconductor (C8-BTBT) in its solvent and a liquid in which the semiconductor is insoluble. The products of this antisolvent crystallization technique are thin semiconductor films with exceptionally high and uniform crystallinity. The use of single crystals has been fundamental to the development of semiconductor microelectronics and solid-state science1. Whether based on inorganic2,3,4,5 or organic6,7,8 materials, the devices that show the highest performance rely on single-crystal interfaces, with their nearly perfect translational symmetry and exceptionally high chemical purity. Attention has recently been focused on developing simple ways of producing electronic devices by means of printing technologies. ‘Printed electronics’ is being explored for the manufacture of large-area and flexible electronic devices by the patterned application of functional inks containing soluble or dispersed semiconducting materials9,10,11. However, because of the strong self-organizing tendency of the deposited materials12,13, the production of semiconducting thin films of high crystallinity (indispensable for realizing high carrier mobility) may be incompatible with conventional printing processes. Here we develop a method that combines the technique of antisolvent crystallization14 with inkjet printing to produce organic semiconducting thin films of high crystallinity. Specifically, we show that mixing fine droplets of an antisolvent and a solution of an active semiconducting component within a confined area on an amorphous substrate can trigger the controlled formation of exceptionally uniform single-crystal or polycrystalline thin films that grow at the liquid–air interfaces. Using this approach, we have printed single crystals of the organic semiconductor 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT) (ref. 15), yielding thin-film transistors with average carrier mobilities as high as 16.4 cm2 V−1 s−1. This printing technique constitutes a major step towards the use of high-performance single-crystal semiconductor devices for large-area and flexible electronics applications.
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TL;DR: In this paper, the state-of-the-art in organic field effect transistors (OFETs) are reviewed in light of requirements for demanding future applications, in particular active-matrix addressing for flexible organic light-emitting diode (OLED) displays.
Abstract: Over the past 25 years, organic field-effect transistors (OFETs) have witnessed impressive improvements in materials performance by 3–4 orders of magnitude, and many of the key materials discoveries have been published in Advanced Materials. This includes some of the most recent demonstrations of organic field-effect transistors with performance that clearly exceeds that of benchmark amorphous silicon-based devices. In this article, state-of-the-art in OFETs are reviewed in light of requirements for demanding future applications, in particular active-matrix addressing for flexible organic light-emitting diode (OLED) displays. An overview is provided over both small molecule and conjugated polymer materials for which field-effect mobilities exceeding > 1 cm2 V–1 s–1 have been reported. Current understanding is also reviewed of their charge transport physics that allows reaching such unexpectedly high mobilities in these weakly van der Waals bonded and structurally comparatively disordered materials with a view towards understanding the potential for further improvement in performance in the future.
1,992 citations
TL;DR: In this article, an approach to prepare perovskite films of high electronic quality by using poly(methyl methacrylate) (PMMA) as a template to control nucleation and crystal growth is presented.
Abstract: The past several years have witnessed the rapid emergence of a class of solar cells based on mixed organic–inorganic halide perovskites. Today’s state-of-the-art perovskite solar cells (PSCs) employ various methods to enhance nucleation and improve the smoothness of the perovskite films formed via solution processing. However, the lack of precise control over the crystallization process creates a risk of forming unwanted defects, for example, pinholes and grain boundaries. Here, we introduce an approach to prepare perovskite films of high electronic quality by using poly(methyl methacrylate) (PMMA) as a template to control nucleation and crystal growth. We obtain shiny smooth perovskite films of excellent electronic quality, as manifested by a remarkably long photoluminescence lifetime. We realize stable PSCs with excellent reproducibility showing a power conversion efficiency (PCE) of up to 21.6% and a certified PCE of 21.02% under standard AM 1.5G reporting conditions. Controlling the crystallization process of perovskite films is crucial to obtaining high efficiency in perovskite solar cells. Bi et al. propose the use of poly(methyl methacrylate) as a template for the controlled nucleation and growth of perovskite crystals achieving efficiency of 21.6%.
1,626 citations
TL;DR: A simple vacuum flash–assisted solution processing method is devised to obtain shiny, smooth, crystalline perovskite films of high electronic quality over large areas, which enables the realization of highly efficient large-area PSCs for practical deployment.
Abstract: Metal halide perovskite solar cells (PSCs) currently attract enormous research interest because of their high solar-to-electric power conversion efficiency (PCE) and low fabrication costs, but their practical development is hampered by difficulties in achieving high performance with large-size devices. We devised a simple vacuum flash-assisted solution processing method to obtain shiny, smooth, crystalline perovskite films of high electronic quality over large areas. This enabled us to fabricate solar cells with an aperture area exceeding 1 square centimeter, a maximum efficiency of 20.5%, and a certified PCE of 19.6%. By contrast, the best certified PCE to date is 15.6% for PSCs of similar size. We demonstrate that the reproducibility of the method is excellent and that the cells show virtually no hysteresis. Our approach enables the realization of highly efficient large-area PSCs for practical deployment.
1,586 citations
TL;DR: This Perspective analyzes some of the most exciting strategies recently suggested in the design and structural organization of π-functional materials for transistor and solar cell applications and places emphasis on the interplay between molecular structure, self-assembling properties, nanoscale and mesoscale ordering, and device efficiency parameters.
Abstract: Organic electronics are broadly anticipated to impact the development of flexible thin-film device technologies. Among these, solution-processable π-conjugated polymers and small molecules are proving particularly promising in field-effect transistors and bulk heterojunction solar cells. This Perspective analyzes some of the most exciting strategies recently suggested in the design and structural organization of π-functional materials for transistor and solar cell applications. Emphasis is placed on the interplay between molecular structure, self-assembling properties, nanoscale and mesoscale ordering, and device efficiency parameters. A critical look at the various approaches used to optimize both materials and device performance is provided to assist in the identification of new directions and further advances.
1,301 citations
TL;DR: Some of the major milestones along the way are highlighted to provide a historical view of OFET development, introduce the integrated molecular design concepts and process engineering approaches that lead to the current success, and identify the challenges ahead to make OFETs applicable in real applications.
Abstract: The past couple of years have witnessed a remarkable burst in the development of organic field-effect transistors (OFETs), with a number of organic semiconductors surpassing the benchmark mobility of 10 cm2/(V s). In this perspective, we highlight some of the major milestones along the way to provide a historical view of OFET development, introduce the integrated molecular design concepts and process engineering approaches that lead to the current success, and identify the challenges ahead to make OFETs applicable in real applications.
1,216 citations
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TL;DR: Self-assembling processes are common throughout nature and technology and involve components from the molecular to the planetary scale and many different kinds of interactions.
Abstract: Self-assembly is the autonomous organization of components into patterns or structures without human intervention. Self-assembling processes are common throughout nature and technology. They involve components from the molecular (crystals) to the planetary (weather systems) scale and many different kinds of interactions. The concept of self-assembly is used increasingly in many disciplines, with a different flavor and emphasis in each.
6,491 citations
TL;DR: In this article, the authors ascribe the characteristic pattern of the deposition to a form of capillary flow in which pinning of the contact line of the drying drop ensures that liquid evaporating from the edge is replenished by liquid from the interior.
Abstract: When a spilled drop of coffee dries on a solid surface, it leaves a dense, ring-like deposit along the perimeter (Fig 1a) The coffee—initially dispersed over the entire drop—becomes concentrated into a tiny fraction of it Such ring deposits are common wherever drops containing dispersed solids evaporate on a surface, and they influence processes such as printing, washing and coating1,2,3,4,5 Ring deposits also provide a potential means to write or deposit a fine pattern onto a surface Here we ascribe the characteristic pattern of the deposition to a form of capillary flow in which pinning of the contact line of the drying drop ensures that liquid evaporating from the edge is replenished by liquid from the interior The resulting outward flow can carry virtually all the dispersed material to the edge This mechanism predicts a distinctive power-law growth of the ring mass with time—a law independent of the particular substrate, carrier fluid or deposited solids We have verified this law by microscopic observations of colloidal fluids
5,553 citations
TL;DR: A model interface is examined between two insulating perovskite oxides—LaAlO3 and SrTiO3—in which the termination layer at the interface is controlled on an atomic scale, presenting a broad opportunity to tailor low-dimensional charge states by atomically engineered oxide heteroepitaxy.
Abstract: Polarity discontinuities at the interfaces between different crystalline materials (heterointerfaces) can lead to nontrivial local atomic and electronic structure, owing to the presence of dangling bonds and incomplete atomic coordinations. These discontinuities often arise in naturally layered oxide structures, such as the superconducting copper oxides and ferroelectric titanates, as well as in artificial thin film oxide heterostructures such as manganite tunnel junctions. If polarity discontinuities can be atomically controlled, unusual charge states that are inaccessible in bulk materials could be realized. Here we have examined a model interface between two insulating perovskite oxides--LaAlO3 and SrTiO3--in which we control the termination layer at the interface on an atomic scale. In the simple ionic limit, this interface presents an extra half electron or hole per two-dimensional unit cell, depending on the structure of the interface. The hole-doped interface is found to be insulating, whereas the electron-doped interface is conducting, with extremely high carrier mobility exceeding 10,000 cm2 V(-1) s(-1). At low temperature, dramatic magnetoresistance oscillations periodic with the inverse magnetic field are observed, indicating quantum transport. These results present a broad opportunity to tailor low-dimensional charge states by atomically engineered oxide heteroepitaxy.
3,977 citations
"Inkjet printing of single-crystal f..." refers background in this paper
...0(8)u, V 5 1357(4) Å(3)—is consistent with that of the bulk crystal(22)....
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TL;DR: The formation of a Wigner solid or charge-density-wave state with triangular symmetry is suggested as a possible explanation for the formation of the Hall plateau in magnetotransport of high-mobility, two-dimensional electrons as mentioned in this paper.
Abstract: A quantized Hall plateau of ${\ensuremath{\rho}}_{\mathrm{xy}}=\frac{3h}{{e}^{2}}$, accompanied by a minimum in ${\ensuremath{\rho}}_{\mathrm{xx}}$, was observed at $Tl5$ K in magnetotransport of high-mobility, two-dimensional electrons, when the lowest-energy, spin-polarized Landau level is $\frac{1}{3}$ filled. The formation of a Wigner solid or charge-density-wave state with triangular symmetry is suggested as a possible explanation.
3,528 citations
"Inkjet printing of single-crystal f..." refers background in this paper
...We consider that the following characteristics of the film formation process are important to achieve high-quality single-crystal film: (1) the liquid–air interfaces need to be ideal locations for diffusion and self-organization of organic molecules (as for Langmuir–Blodgett films(25)) and (2) the gradual growth of single-crystal films is only possible because of the fluidic nature of the microliquid droplet in which laminar flow dominates over turbulent flow(26)....
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TL;DR: It is shown that the use of substrate surface energy patterning to direct the flow of water-based conducting polymer inkjet droplets enables high-resolution definition of practical channel lengths of 5 micrometers, and high mobilities were achieved.
Abstract: Direct printing of functional electronic materials may provide a new route to low-cost fabrication of integrated circuits. However, to be useful it must allow continuous manufacturing of all circuit components by successive solution deposition and printing steps in the same environment. We demonstrate direct inkjet printing of complete transistor circuits, including via-hole interconnections based on solution-processed polymer conductors, insulators, and self-organizing semiconductors. We show that the use of substrate surface energy patterning to direct the flow of water-based conducting polymer inkjet droplets enables high-resolution definition of practical channel lengths of 5 micrometers. High mobilities of 0.02 square centimeters per volt second and on-off current switching ratios of 10 5 were achieved.
3,190 citations