Citation: Zeqi YU, Zuohu ZHOU, Lei ZHANG. Lithographic performance and mechanism of bromine-containing zirconium-oxo cluster photoresists[J]. Chinese Journal of Inorganic Chemistry, ;2026, 42(11): 2389-2398. doi: 10.11862/CJIC.20260208 shu

Lithographic performance and mechanism of bromine-containing zirconium-oxo cluster photoresists

Institute of Modern Optics, College of Electronic Information and Optical Engineering, Nankai University, Tianjin 300350, China

Corresponding author: Lei ZHANG, zhanglei3915@nankai.edu.cn
Received Date: 9 June 2026
Revised Date: 21 September 2026

Figures(5)

This paper investigates the relationship between the crystal structures and solubility characteristics of 2-bromoisobutyric acid-coordinated zirconium-oxo clusters, namely Zr₅O₄[BrC(CH₃)₂COO]₁₀(OⁿPr)₂(ⁿPrOH)₄ (named Zr₅Br₁₀) and Zr₆O₄(OH)₄(OOCC(CH₃)₂Br)₁₂ (named Zr₆Br₁₂), and evaluates the electron beam lithography performance of Zr₅Br₁₀ for the first time. Structural analysis reveals that molecular symmetry plays an important role in regulating cluster solubility: the low-symmetry Zr₅Br₁₀ exhibits excellent film-forming ability, whereas the highly symmetric Zr₆Br₁₂ is extremely insoluble. During the patterning process, the lithographic performance of Zr₅Br₁₀ films is highly dependent on development dynamics. In a low-polarity “poor solvent” (n-heptane) system, the film achieved ultra-high sensitivity (38.1 μC·cm^-2) and excellent contrast (12.5). X-ray photoelectron spectroscopy (XPS) characterization further unveils the negative-tone cross-linking mechanism of this photoresist, where electron beam-induced decarboxylation and C—Br bond cleavage lead to the in-situ rearrangement of newly formed active metal centers, forming an insoluble three-dimensional Zr—O—Zr network.
- metal-oxo cluster,
- photoresist,
- electron beam lithography,
- development dynamics,
- cross-linking mechanism,
- bromine-containing ligand
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