Epitaxial growth techniques enable nearly defect free heterostructures with coherent interfaces, which are of utmost importance for high performance electronic devices. While high-vacuum technology-based growth techniques are state-of-the art, here we pursue a purely solution processed approach to obtain nanocrystals with eptaxially coherent and quasi-lattice matched inorganic ligand shells. Octahedral metal-halide clusters, respectively 0-dimensional perovskites, were employed as ligands to match the coordination geometry of the PbS cubic rock-salt lattice. Different clusters (CHNH)[MHal] (M = Pb(II), Bi(III), Mn(II), In(III), Hal = Cl, I) were attached to the nanocrystal surfaces via a scalable phase transfer procedure. The ligand attachment and coherence of the formed PbS/ligand core/shell interface was confirmed by combining the results from transmission electron microscopy, small-angle X-ray scattering, nuclear magnetic resonance spectroscopy and powder X-ray diffraction. The lattice mismatch between ligand shell and nanocrystal core plays a key role in performance. In photoconducting devices the best performance (detectivity of 2 × 10 cm Hz /W with> 110 kHz bandwidth) was obtained with (CHNH)BiI ligands, providing the smallest relative lattice mismatch of ca. -1%. PbS nanocrystals with such ligands exhibited in millimeter sized bulk samples in the form of pressed pellets a relatively high carrier mobility for nanocrystal solids of ∼1.3 cm/(V s), a carrier lifetime of ∼70 μs, and a low residual carrier concentration of 2.6 × 10 cm. Thus, by selection of ligands with appropriate geometry and bond lengths optimized quasi-epitaxial ligand shells were formed on nanocrystals, which are beneficial for applications in optoelectronics.

Metal-halide-perovskites revolutionized the field of thin-film semiconductor technology, due to their favorable optoelectronic properties and facile solution processing. Further improvements of perovskite thin-film devices require structural coherence on the atomic scale. Such perfection is achieved by epitaxial growth, a method that is based on the use of high-end deposition chambers. Here epitaxial growth is enabled via a ≈1000 times cheaper device, a single nozzle inkjet printer. By printing, single-crystal micro-and nanostructure arrays and crystalline coherent thin films are obtained on selected substrates. The hetero-epitaxial structures of methylammonium PbBr 3 grown on lattice matching substrates exhibit similar luminescence as bulk single crystals, but the crystals phase transitions are shifted to lower temperatures, indicating a structural stabilization due to interfacial lattice anchoring by the substrates. Thus, the inkjet-printing of metal-halide perovskites provides improved material characteristics in a highly economical way, as a future cheap competitor to the high-end semiconductor growth technologies.

Colloidal nanocrystals from PbS are successfully applied in highly sensitive infrared photodetectors with various device architectures. Here, we demonstrate all-printed devices with high detectivity (∼10 12 cm Hz 1/2 /W) and a cutoff frequency of >3 kHz. The low material consumption (<0.3 mg per detector) and short processing time (14 s per detector) enabled by the automated printing promises extremely low device costs. To enable all-printed devices, an ink formulation was developed based on nanocrystals stabilized by perovskite-like methylammonium iodobismuthate ligands, which are dispersed in a ternary solvent. Fully inkjet printed devices based on this solvent were achieved with printed silver electrodes and a ZnO interlayer. Considerable improvements were obtained by the addition of small amounts of the polymer poly(vinylpyrrolidone) to the ink. The polymer improved the colloidal stability of the ink and its film-formation properties and thus enabled the scalable printing of single detectors and detector arrays. While photoconductors were shown here, the developed ink will certainly find application in a series of further electronic devices based on nanocrystals from a broad range of materials.

Electrochromic devices operating in the near infrared are being developed as a part of smart windows that can dynamically modulate visible light and heat transmittance of solar irradiation, dependent on weather conditions and personal preferences. Here, doped metal oxide nanocrystals are used to obtain the desired effect in the infrared spectral region. Specifically, the infrared transmittance is electrochemically modulated by control of the carrier concentration in the nanocrystals. While indium tin oxide nanocrystals are already known to provide this effect, the consequence of ligand treatment during preparation of the nanocrystal electrode on the electrochromic properties is studied. The type of ligand treatment is shown to affect the surface morphology, as well as the localized plasmon resonance energy of the nanocrystal films. A short and convenient treatment by ethanedithiol cross‐linking ligands is shown to provide superior results as compared with the formic acid treatment used in the previous work. Future work combining windows based on optimized electrochromic effects in the near infrared combined with those in the visible spectral range will simultaneously improve building energy efficiency and indoor human comfort.

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