Molecular bixbyite-like In<sub>12</sub>-oxo clusters with tunable functionalization sites for lithography patterning applications

Yi, Xiaofeng; Wang, Di; Li, Fan; Zhang, Jian; Zhang, Lei

doi:10.1039/d1sc04491e

Cited by 17 publications

(20 citation statements)

References 34 publications

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“…Finally, the applications of the coordinationdelayed-hydrolysis strategy could be extended. On one hand, it can be used to synthesize oxo clusters of other easily hydrolyzed metal ions (some progress has already been made in Al-oxo clusters, 60 Sn-oxo clusters, 61 and In-oxo clusters 62 ). On the other hand, besides clusters, it might also be conducive to the synthesis of materials difficult to crystallize by other conventional methods, for example, Ti-based metal− organic frameworks (Ti-MOFs).…”

Section: Discussionmentioning

confidence: 99%

Coordination-Delayed-Hydrolysis Method for the Synthesis and Structural Modulation of Titanium-Oxo Clusters

Zhang

Fan

et al. 2022

Acc. Chem. Res.

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Conspectus Atomically precise titanium-oxo clusters (TOCs) are the structure and reactivity model compounds of technically important TiO2 materials, which could help build structure–property relationships and achieve property modulation at the molecular level. However, the traditional formation of TOCs has relied on the poorly controllable hydrolysis of titanium alkoxide in the solvent for a long time, limiting the development of TOC structural chemistry to a great extent. In addition, easily hydrolyzable alkoxy groups would be still coordinated on the surface of the TOCs generated by this method, making the clusters sensitive and unstable to the moisture. To achieve controllable preparation of TOCs, we believe it is crucial to attenuate the hydrolysis of titanium ions in the formation process of a cluster. To this end, we have recently applied an effective coordination-delayed-hydrolysis (CDH) strategy for TOC synthesis, which provides powerful tools for tuning their structures. In this Account, at the beginning, a brief introduction to the coordination-delayed-hydrolysis strategy is supplied, and its predominant features for constructing novel TOCs are highlighted. In subsequent sections, we discuss how the applied chelating organic/inorganic ligands (named hydrolysis delayed ligands) influence the hydrolysis process of Ti4+ ions to form a large family of TOCs with various nuclearities and core structures. Various hydrolysis delayed ligands have been explored, ranging from common O-donor ligands (carboxylate, phenol, or sulfate) to rarely used N-donor ligands (pyrazole) or bifunctional O/N-donor ones (quinoline, oxime, or alkanolamine). Breakthroughs in the symmetry, configuration, and cluster nuclei of TOCs have been accordingly achieved. Then, we show that this CDH method can be used to tune the surface structure of TOCs by modifying functional organic ligands. As a result, the physicochemical properties of TOCs, especially optical band gaps, can be optimized, and their stability under ambient conditions is significantly improved. In addition, we illustrate that the reversible bonds between hydrolysis delayed ligands and Ti ions further allows us to introduce active heterometal ions or clusters upon or inside the Ti–O cores to prepare heterometallic TOCs with unprecedented structures and properties. In particular, noble metal (Ag ions or clusters) has been incorporated into Ti–O clusters for the first time. As a summary, the coordination-delayed-hydrolysis strategy has realized the controllable hydrolysis of Ti4+ ions to some extent, breaking through the limitations of traditional synthesis methods and producing fruitful results in the field of titanium-oxo clusters. It is believed that this CDH method would also be effective for synthesizing oxo clusters of other easily hydrolyzed metal ions (Al3+, Sn4+, In3+, etc.) to afford significant contribution for the cluster community.

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Section: Discussionmentioning

confidence: 99%

Coordination-Delayed-Hydrolysis Method for the Synthesis and Structural Modulation of Titanium-Oxo Clusters

Zhang

Fan

et al. 2022

Acc. Chem. Res.

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“…[1][2][3][4] The EUV scanner is an indispensable lithography tool to produce modern semiconductors with 20 nm half pitch (HP) for 7 nm or smaller nodes. One major reason is that the efficiency of EUV absorptions of transition metal complexes such as Zn, [5][6][7] Sn, [8][9][10][11] Hf, [12][13][14][15][16][17][18] Zr, [19][20][21][22][23][24] Co 25 and In 26 is much higher than those of polymer-based photoresists by 2-3 fold. In the context of metal-based photoresists, hafnium oxide photoresists (Scheme 1) are particularly notable because of high Hf density, rendering their EUV lithographic patterns very impressive.…”

Section: Introductionmentioning

confidence: 99%

Partial decarboxylation of hafnium oxide clusters for high resolution lithographic applications

et al. 2022

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“…During the past few decades, the semiconductor world has witnessed the astonishing evolution of electronic chips with the shrinking of the node size at a faster rate than expected. Among several technological aspects responsible for such amazing developments, the remarkable progress in the area of lithography where resist technology plays an important role has been a critical factor. − Coping with the fast-changing semiconductor nodes has been a grand challenge for resist developers.…”

Section: Introductionmentioning

confidence: 99%

Macrocycle Network-Aided Nanopatterning of Inorganic Resists on Silicon

Nandi

Khillare

Moinuddin

et al. 2022

ACS Appl. Nano Mater.

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Inorganic resists have emerged as promising candidates in semiconductor industries to realize sub-10 nm node technology. However, controlling vertical shrinkage of resist films during the pattern development process, particularly for ultralow thin film applications, is among the highly pressing limitations of inorganic resists along with pattern roughness and poor resist shelf-life characteristics. Tin-based clusters and small molecules have been recently introduced as resist materials. They possess a high absorption coefficient and fast solubility transitions under irradiation exposure. As we investigated, n-butylstannoic acid (BTA) showed ∼38% vertical shrinkage when its film was exposed with deep ultraviolet photons (DUV, ∼254 nm) and could pattern features of ∼120 nm. We hypothesized and experimentally validated an approach that provided control on shrinkage issues, along with improving its patterning potential to sub-15 nm regime. In our approach, BTA was embedded into a polyhydroxy organic host matrix composed of noria (water-wheel-like macrocycle) derivatives. The rigid molecular cage structure and photo-inert nature of noria (N-Me) were utilized as the host matrix that apprehended the inorganic resist material within its intermolecular space. Ultrathin films (∼20 nm) were coated on silicon, and various nanofeatures including 10 nm lines, meshlike grids with 10 nm width, complex patterns, and so forth were patterned using electron beam and helium ion beam lithography. Most importantly, we were able to drastically reduce the vertical shrinkage to ∼13% with respect to initial thickness, which substantiates the potential of our hypothesis. We also noticed good shelf-life (6 months), good etch resistance, and low line edge roughness (LER)/line width roughness (LWR) for the developed resist composition.

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Molecular bixbyite-like In₁₂-oxo clusters with tunable functionalization sites for lithography patterning applications

Abstract: Indium oxides have been widely applied in many technology areas, but their utilization in lithography has not been developed. Herein, we illustrated a family of unprecedented In12-oxo clusters with general...

Cited by 17 publications

References 34 publications

Coordination-Delayed-Hydrolysis Method for the Synthesis and Structural Modulation of Titanium-Oxo Clusters

Coordination-Delayed-Hydrolysis Method for the Synthesis and Structural Modulation of Titanium-Oxo Clusters

Partial decarboxylation of hafnium oxide clusters for high resolution lithographic applications

Macrocycle Network-Aided Nanopatterning of Inorganic Resists on Silicon

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Molecular bixbyite-like In12-oxo clusters with tunable functionalization sites for lithography patterning applications

Abstract: Indium oxides have been widely applied in many technology areas, but their utilization in lithography has not been developed. Herein, we illustrated a family of unprecedented In12-oxo clusters with general...

Cited by 17 publications

References 34 publications

Coordination-Delayed-Hydrolysis Method for the Synthesis and Structural Modulation of Titanium-Oxo Clusters

Coordination-Delayed-Hydrolysis Method for the Synthesis and Structural Modulation of Titanium-Oxo Clusters

Partial decarboxylation of hafnium oxide clusters for high resolution lithographic applications

Macrocycle Network-Aided Nanopatterning of Inorganic Resists on Silicon

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Product

Resources

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Molecular bixbyite-like In₁₂-oxo clusters with tunable functionalization sites for lithography patterning applications