Metal-Ligand Coordination Enables Molecular Resist-Based Direct Write Lithography of Metal Halides.
basic_science · Level V
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- Record sourced from PubMed, PMID 42483793.
- Also identified by DOI 10.1002/adma.74077.
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Abstract
Lithographic patterning of semiconductor materials is essential for most modern optoelectronic devices. However, traditional inorganic and nanocrystal derived resists exhibit low electron-dose sensitivity, weak solubility contrast, and limited chemical compatibility, restricting high resolution functional lithography. Here, we present a molecular complex platform that converts ordinary metal halides (MXn; nine compositions) into intrinsically electron beam responsive, solution processable resists for direct write electron beam lithography. Coordination of MX<sub>n</sub> with oleylamine yields metal-ligand complexes with comparatively low dose sensitivity among additive-free inorganic resists (0.81 mC cm<sup>-2</sup>), high contrast (γ = 3.1), and sub-30 nm resolution. Across the tested metal halide library, resist sensitivity shows an exponential dependence on molecular weight, establishing the first universal scaling relationship for molecular resist energetics. Mechanistic studies reveal that electron irradiation induces bond cleavage and coordination network collapse, generating metal halide domains with high structural fidelity. The patterned nanostructures retain optical functionality, nanodots displaying super linear PL excitation (α > 1) characteristics. Furthermore, sequential multilayer writing enables deterministic RGB nano-pixel architectures, exemplified by registered 3.9 × 10<sup>4</sup> pixel full color parrot micrograph. This additive free, tunable molecular resist system provides a high-resolution lithography route for scalable quantum photonic and optoelectronic fabrication.