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Metal-Ligand Coordination Enables Molecular Resist-Based Direct Write Lithography of Metal Halides
Prakash Sarkar1, Gurupada Ghorai1, Harihar Mondal1
1School of Applied & Interdisciplinary Sciences, Indian Association for the Cultivation of Science (IACS), Kolkata, India.
None:
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 MXn with oleylamine yields metal-ligand complexes with comparatively low dose sensitivity among additive-free inorganic resists (0.81 mC cm-2), 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 × 104 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.
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