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1.
Adv Mater ; 36(36): e2403783, 2024 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-39023001

RESUMO

In 2D noble metals like copper, the carrier scattering at grain boundaries has obscured the intrinsic nature of electronic transport. However, it is demonstrated that the intrinsic nature of transport by hole carriers in 2D copper can be revealed by growing thin films without grain boundaries. As even a slight deviation from the twin boundary is perceived as grain boundaries by electrons, it is only through the thorough elimination of grain boundaries that the hidden hole-like attribute of 2D single-crystal copper can be unmasked. Two types of Fermi surfaces, a large hexagonal Fermi surface centered at the zone center and the triangular Fermi surface around the zone corner, tightly matching to the calculated Fermi surface topology, confirmed by angle-resolved photoemission spectroscopy (ARPES) measurements and vivid nonlinear Hall effects of the 2D single-crystal copper account for the presence of hole carriers experimentally. This breakthrough suggests the potential to manipulate the majority carrier polarity in metals by means of grain boundary engineering in a 2D geometry.

2.
Adv Mater ; 35(42): e2210564, 2023 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-37548080

RESUMO

Copper surfaces that exhibit a wide range of achromatic colors while still metallic have not been studied, despite advancements in antireflection coatings. A series of achromatic copper films grown with [111] preferred orientation by depositing 3D porous nanostructures is introduced via coherent/incoherent atomic sputtering epitaxy. The porous copper nanostructures self-regulate the giant oxidation resistance by constructing a curved surface that generates a series of monoatomic steps, followed by shrinkage of the lattice spacing of one or two surface layers. First-principles calculations confirm that these structural components cooperatively increase the energy barrier against oxygen penetration. The achromaticity of the single-crystalline porous copper films is systematically tuned by geometrical parameters such as pore size distribution and 3D linkage. The optimized achromatic copper films with high oxidation resistance show an unusual switching effect between superhydrophilicity and superhydrophobicity. The tailored 3D porous nanostructures can be a candidate material for numerous applications, such as antireflection coatings, microfluidic devices, droplet tweezers, and reversible wettability switches.

4.
Nature ; 603(7901): 434-438, 2022 03.
Artigo em Inglês | MEDLINE | ID: mdl-35296844

RESUMO

Oxidation can deteriorate the properties of copper that are critical for its use, particularly in the semiconductor industry and electro-optics applications1-7. This has prompted numerous studies exploring copper oxidation and possible passivation strategies8. In situ observations have, for example, shown that oxidation involves stepped surfaces: Cu2O growth occurs on flat surfaces as a result of Cu adatoms detaching from steps and diffusing across terraces9-11. But even though this mechanism explains why single-crystalline copper is more resistant to oxidation than polycrystalline copper, the fact that flat copper surfaces can be free of oxidation has not been explored further. Here we report the fabrication of copper thin films that are semi-permanently oxidation resistant because they consist of flat surfaces with only occasional mono-atomic steps. First-principles calculations confirm that mono-atomic step edges are as impervious to oxygen as flat surfaces and that surface adsorption of O atoms is suppressed once an oxygen face-centred cubic (fcc) surface site coverage of 50% has been reached. These combined effects explain the exceptional oxidation resistance of ultraflat Cu surfaces.

5.
Nanoscale ; 13(17): 8275-8282, 2021 May 07.
Artigo em Inglês | MEDLINE | ID: mdl-33890603

RESUMO

There has been growing interest in organic-inorganic hybrid perovskites as a promising candidate for optoelectronic applications due to their superior physical properties. Despite this, most of the reported perovskite devices based on polycrystalline thin films suffer immensely from poor stability and high trap density owing to grain boundaries limiting their performance. Perovskite single crystal structures have been recently explored to construct stable devices and reduce the trap density compared to their thin-film counterparts. We present a novel method of growing sizable CH3NH3PbBr3 single crystals based on the high solubility characteristic of hybrid perovskites at low temperatures within inverse temperature crystallization. We compared both the crystallinity of perovskite single crystal structures and optoelectronic charge transport of single crystal photodetectors as a function of dissolution temperature. The performance of the photodetector fabricated with our large-scaled single crystal with high quality demonstrated low trap density, high mobility, and high photoresponse.

6.
Adv Mater ; 33(15): e2007345, 2021 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-33751679

RESUMO

Stochastic inhomogeneous oxidation is an inherent characteristic of copper (Cu), often hindering color tuning and bandgap engineering of oxides. Coherent control of the interface between metal and metal oxide remains unresolved. Coherent propagation of an oxidation front in single-crystal Cu thin film is demonstrated to achieve a full-color spectrum for Cu by precisely controlling its oxide-layer thickness. Grain-boundary-free and atomically flat films prepared by atomic-sputtering epitaxy allow tailoring of the oxide layer with an abrupt interface via heat treatment with a suppressed temperature gradient. Color tuning of nearly full-color red/green/blue indices is realized by precise control of the oxide-layer thickness; the samples cover ≈50.4% of the standard red/green/blue color space. The color of copper/copper oxide is realized by the reconstruction of the quantitative yield color from the oxide "pigment" (complex dielectric functions of Cu2 O) and light-layer interference (reflectance spectra obtained from the Fresnel equations) to produce structural color. Furthermore, laser-oxide lithography is demonstrated with micrometer-scale linewidth and depth through local phase transformation to oxides embedded in the metal, providing spacing necessary for semiconducting transport and optoelectronics functionality.

7.
RSC Adv ; 8(18): 9895-9900, 2018 Mar 05.
Artigo em Inglês | MEDLINE | ID: mdl-35540802

RESUMO

Understanding the electronic band structure and density of states (DOS) of a material and their relationship to the associated electronic transport properties is the starting point for optimizing the performance of a device and its technological applications. In a hydrogenated Zn0.8Co0.2O (ZnCoO:H) film with an inverted thin-film transistor structure, we found ambipolar behavior, which is shown in many field-effect devices based on graphene, graphene nanoribbons, and organic semiconductors. In this study, to obtain information on the DOS of ZnCoO:H to explain the ambipolar behavior in terms of the carrier density and type, resistivity and magnetoresistance measurements of a ZnCoO:H film were performed at 5 K. Our proposed DOS representation of ZnCoO:H explains qualitatively the experimental observations of carrier density modulation and ambipolar behavior. First-principles calculations of the DOS of ZnCoO:H were in good agreement with the proposed DOS representation. Through a comparison of first-principles calculations and experimental data, evidence for the existence of Co-H-Co in ZnCoO:H is suggested.

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