Two-photon excitation provides a means of activating chemical or physical processes with high spatial resolution in three dimensions and has made possible the development of three-dimensional fluorescence imaging, optical data storage, and lithographic microfabrication. These applications take advantage of the fact that the two-photon absorption probability depends quadratically on intensity, so under tight-focusing conditions, the absorption is confined at the focus to a volume of order λ3 (where λ is the laser wavelength). Any subsequent process, such as fluorescence or a photoinduced chemical reaction, is also localized in this small volume. Although three-dimensional data storage and microfabrication have been illustrated using two-photon-initiated polymerization of resins incorporating conventional ultraviolet-absorbing initiators, such photopolymer systems exhibit low photosensitivity as the initiators have small two-photon absorption cross-sections (δ). Consequently, this approach requires high laser power, and its widespread use remains impractical. Here we report on a class of π;-conjugated compounds that exhibit large δ (as high as 1, 250 × 10−50 cm4 s per photon) and enhanced two-photon sensitivity relative to ultraviolet initiators. Two-photon excitable resins based on these new initiators have been developed and used to demonstrate a scheme for three-dimensional data storage which permits fluorescent and refractive read-out, and the fabrication of three-dimensional micro-optical and micromechanical structures, including photonic-bandgap-type structures.

Two-photon polymerization initiators for three-dimensional optical data storage and microfabrication

Soft materials capable of transforming between three-dimensional (3D) shapes in response to stimuli such as light, heat, solvent, electric and magnetic fields have applications in diverse areas such as flexible electronics1,2, soft robotics3,4 and biomedicine5–7. In particular, magnetic fields offer a safe and effective manipulation method for biomedical applications, which typically require remote actuation in enclosed and confined spaces8–10. With advances in magnetic field control
 11
 , magnetically responsive soft materials have also evolved from embedding discrete magnets
 12
 or incorporating magnetic particles
 13
 into soft compounds to generating nonuniform magnetization profiles in polymeric sheets14,15. Here we report 3D printing of programmed ferromagnetic domains in soft materials that enable fast transformations between complex 3D shapes via magnetic actuation. Our approach is based on direct ink writing
 16
 of an elastomer composite containing ferromagnetic microparticles. By applying a magnetic field to the dispensing nozzle while printing
 17
 , we reorient particles along the applied field to impart patterned magnetic polarity to printed filaments. This method allows us to program ferromagnetic domains in complex 3D-printed soft materials, enabling a set of previously inaccessible modes of transformation, such as remotely controlled auxetic behaviours of mechanical metamaterials with negative Poisson’s ratios. The actuation speed and power density of our printed soft materials with programmed ferromagnetic domains are orders of magnitude greater than existing 3D-printed active materials. We further demonstrate diverse functions derived from complex shape changes, including reconfigurable soft electronics, a mechanical metamaterial that can jump and a soft robot that crawls, rolls, catches fast-moving objects and transports a pharmaceutical dose.

Printing ferromagnetic domains for untethered fast-transforming soft materials

Control of spontaneously emitted light lies at the heart of quantum optics. It is essential for diverse applications ranging from miniature lasers and light-emitting diodes, to single-photon sources for quantum information, and to solar energy harvesting. To explore such new quantum optics applications, a suitably tailored dielectric environment is required in which the vacuum fluctuations that control spontaneous emission can be manipulated. Photonic crystals provide such an environment: they strongly modify the vacuum fluctuations, causing the decay of emitted light to be accelerated or slowed down, to reveal unusual statistics, or to be completely inhibited in the ideal case of a photonic bandgap. Here we study spontaneous emission from semiconductor quantum dots embedded in inverse opal photonic crystals. We show that the spectral distribution and time-dependent decay of light emitted from excitons confined in the quantum dots are controlled by the host photonic crystal. Modified emission is observed over large frequency bandwidths of 10%, orders of magnitude larger than reported for resonant optical microcavities. Both inhibited and enhanced decay rates are observed depending on the optical emission frequency, and they are controlled by the crystals’ lattice parameter. Our experimental results provide a basis for all-solid-state dynamic control
of optical quantum systems.

Controlling the dynamics of spontaneous emission from quantum dots by photonic crystals

Even though the mesoporous-type perovskite solar cell (PSC) is known for high efficiency, its planar-type counterpart exhibits lower efficiency and hysteretic response. Herein, we report success in suppressing hysteresis and record efficiency for planar-type devices using EDTA-complexed tin oxide (SnO2) electron-transport layer. The Fermi level of EDTA-complexed SnO2 is better matched with the conduction band of perovskite, leading to high open-circuit voltage. Its electron mobility is about three times larger than that of the SnO2. The record power conversion efficiency of planar-type PSCs with EDTA-complexed SnO2 increases to 21.60% (certified at 21.52% by Newport) with negligible hysteresis. Meanwhile, the low-temperature processed EDTA-complexed SnO2 enables 18.28% efficiency for a flexible device. Moreover, the unsealed PSCs with EDTA-complexed SnO2 degrade only by 8% exposed in an ambient atmosphere after 2880 h, and only by 14% after 120 h under irradiation at 100 mW cm−2. The development of high efficiency planar-type perovskite solar cell has been lagging behind the mesoporous-type counterpart. Here Yang et al. modify the oxide based electron transporting layer with organic acid and obtain planar-type cells with high certified efficiency of 21.5% and decent stability.

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High efficiency planar-type perovskite solar cells with negligible hysteresis using EDTA-complexed SnO2

Superwettability is a special case of the wetting phenomenon among liquids, gases, and solids. The superhydrophobic/superhydrophilic effect discovered initially has undergone a century of development based on materials science and biomimetics. With the rapid development of research on anti-wetting materials, superoleophobic/superoleophilic surfaces have been fabricated to repel organic liquids besides water. Further studies of underwater superoleophobic/superoleophilic/superaerophobic/superaerophilic materials provide an alternative way to fabricate anti-wetting surfaces rather than lowering the surface energy. Owing to a series of efforts on the studying of extreme wettabilities, a mature superwettability system gradually evolved and has since become a vibrant area of active research, covering topics of superhydrophobicity/superhydrophilicity, superoleophobicity/superoleophilicity in gas or under liquid, superaerophobicity/superaerophilicity under liquid, and combinations of these states. The kinetic stu...

Bioinspired Interfaces with Superwettability: From Materials to Chemistry

Three-dimensional (3D) metal-halide perovskite solar cells (PSCs) have demonstrated exceptional high efficiency. However, instability of the 3D perovskite is the main challenge for industrialization. Incorporation of some long organic cations into perovskite crystal to terminate the lattice, and function as moisture and oxygen passivation layer and ion migration blocking layer, is proven to be an effective method to enhance the perovskite stability. Unfortunately, this method typically sacrifices charge-carrier extraction efficiency of the perovskites. Even in 2D-3D vertically aligned heterostructures, a spread of bandgaps in the 2D due to varying degrees of quantum confinement also results in charge-carrier localization and carrier mobility reduction. A trade-off between the power conversion efficiency and stability is made. Here, by introducing 2D C6 H18 N2 O2 PbI4 (EDBEPbI4 ) microcrystals into the precursor solution, the grain boundaries of the deposited 3D perovskite film are vertically passivated with phase pure 2D perovskite. The phases pure (inorganic layer number n = 1) 2D perovskite can minimize photogenerated charge-carrier localization in the low-dimensional perovskite. The dominant vertical alignment does not affect charge-carrier extraction. Therefore, high-efficiency (21.06%) and ultrastable (retain 90% of the initial efficiency after 3000 h in air) planar PSCs are demonstrated with these 2D-3D mixtures.

Phase Pure 2D Perovskite for High-Performance 2D–3D Heterostructured Perovskite Solar Cells

Inkjet printing patterned photonic crystal domes for wide viewing-angle displays by controlling the sliding three phase contact line

Dopamine-crosslinked TiO2/perovskite layer for efficient and photostable perovskite solar cells under full spectral continuous illumination

Conductive microcables embedded in a transparent film are fabricated by inkjet printing silver-nanoparticle ink into a liquid poly(dimethylsiloxane) (PDMS) precursor substrate. By controlling the spreading of the ink droplet and the rheological properties of the liquid substrate, transparent multilayer circuits composed of high-resolution embedded cables are achieved using a commercial inkjet printer. This facile strategy provides a new avenue for inkjet printing of highly integrated and transparent electronics.

Fabrication of Transparent Multilayer Circuits by Inkjet Printing.

The preparation of fine 3D microstructures is an attractive issue; however, it is limited at large-area fabrication process and fineness morphology manipulation. Here, we propose a strategy to fabricate controllable 3D structures and morphologies from one single droplet via ink-jet printing. Based on the surface energy difference between the hydrophilic patterns and hydrophobic surface, the three phase contact line of a droplet contained nanoparticles is forced to pin on the patterned hydrophilic points and asymmetrically dewets on the hydrophobic surface, which leads to various morphologies. Through the regulation of pinning patterns and solution properties, the 3D morphology can be well manipulated. This strategy to control the 3D morphology of nanoparticle assembly based on hydrophilic patterns would be of great importance for fabricating controllable 3D structures.

Fengyu Li

Papers

Phase Pure 2D Perovskite for High-Performance 2D–3D Heterostructured Perovskite Solar Cells

Inkjet printing patterned photonic crystal domes for wide viewing-angle displays by controlling the sliding three phase contact line

Dopamine-crosslinked TiO2/perovskite layer for efficient and photostable perovskite solar cells under full spectral continuous illumination

Fabrication of Transparent Multilayer Circuits by Inkjet Printing.

Printing Patterned Fine 3D Structures by Manipulating the Three Phase Contact Line