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Low‐Temperature Synthesis of Stable CaZn 2 P 2 Zintl Phosphide Thin Films as Candidate Top AbsorbersAbstract The development of tandem photovoltaics and photoelectrochemical solar cells requires new absorber materials with bandgaps in the range of ≈1.5–2.3 eV, for use in the top cell paired with a narrower‐gap bottom cell. An outstanding challenge is finding materials with suitable optoelectronic and defect properties, good operational stability, and synthesis conditions that preserve underlying device layers. This study demonstrates the Zintl phosphide compound CaZn2P2as a compelling candidate semiconductor for these applications. Phase‐pure, ≈500 nm‐thick CaZn2P2thin films are prepared using a scalable reactive sputter deposition process at growth temperatures as low as 100 °C, which is desirable for device integration. Ultraviolet‐visible spectroscopy shows that CaZn2P2films exhibit an optical absorptivity of ≈104 cm−1at ≈1.95 eV direct bandgap. Room‐temperature photoluminescence (PL) measurements show near‐band‐edge optical emission, and time‐resolved microwave conductivity (TRMC) measurements indicate a photoexcited carrier lifetime of ≈30 ns. CaZn2P2is highly stable in both ambient conditions and moisture, as evidenced by PL and TRMC measurements. Experimental data are supported by first‐principles calculations, which indicate the absence of low‐formation‐energy, deep intrinsic defects. Overall, this study shall motivate future work integrating this potential top cell absorber material into tandem solar cells.more » « less
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Abstract Durable and conductive interfaces that enable chronic and high‐resolution recording of neural activity are essential for understanding and treating neurodegenerative disorders. These chronic implants require long‐term stability and small contact areas. Consequently, they are often coated with a blend of conductive polymers and are crosslinked to enhance durability despite the potentially deleterious effect of crosslinking on the mechanical and electrical properties. Here the grafting of the poly(3,4 ethylenedioxythiophene) scaffold, poly(styrenesulfonate)‐b‐poly(poly(ethylene glycol) methyl ether methacrylate block copolymer brush to gold, in a controlled and tunable manner, by surface‐initiated atom‐transfer radical polymerization (SI‐ATRP) is described. This “block‐brush” provides high volumetric capacitance (120 F cm─3), strong adhesion to the metal (4 h ultrasonication), improved surface hydrophilicity, and stability against 10 000 charge–discharge voltage sweeps on a multiarray neural electrode. In addition, the block‐brush film showed 33% improved stability against current pulsing. This approach can open numerous avenues for exploring specialized polymer brushes for bioelectronics research and application.more » « less
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ABSTRACT A key bottleneck to solar fuels is the absence of stable and strongly absorbing photoelectrode materials for the oxygen evolution reaction (OER). Modern approaches generally trade off between stable but weakly absorbing materials, such as wide bandgap oxides, or strongly absorbing materials that rely on encapsulation for stability and are weakly catalytic, such as the III‐V family of semiconductors. Of interest are materials like transition metal phosphides, such as FeP2, that are known to undergo beneficial in situ surface transformations in the oxidative environment of OER, though stability has remained a primary hurdle. Here, we report on CaCd2P2, a Zintl phase visible‐light absorber with favorable 1.6 eV bandgap, that we identified using high‐throughput computational screening. Using a combination of photoelectrochemical measurements, microscopy, and spectroscopy, we show that CaCd2P2undergoes a light‐stabilized surface transformation that renders it stable under alkaline OER conditions. We also show that the well known OER catalyst CoPi can act as a stable co‐catalyst in synergy with the modified in situ CaCd2P2surface. The light‐induced stabilizing transformation that CaCd2P2undergoes is in sharp contrast to the photocorrosion commonly observed in visible light‐absorbing photoelectrodes. The broader AM2P2family of Zintl phases offers a significant opportunity to explore stabilizing interface chemistry and re‐design the manner in which low‐bandgap semiconductors are used for photoelectrochemical energy conversion.more » « lessFree, publicly-accessible full text available March 1, 2027
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