Charge Shielding-Oriented Design of Zinc-Based Nanoparticle Liquids for Controlled Nanofabrication.

Metal-containing nanoparticles possess nanoscale sizes, but the exploitation of their nanofeatures in nanofabrication processes remains challenging. Herein, we report the realization of a class of zinc-based nanoparticle liquids and their potential for applications in controlled nanofabrication. Utilizing the metal-core charge shielding strategy, we prepared nanoparticles that display glass-to-liquid transition behavior with glass transition temperature far below room temperature (down to -50.9 °C). Theoretical calculations suggest the outer surface of these unusual nanoparticles is almost neutral, thus leading to interparticle interactions weak enough to give them liquefaction characteristics. Such features endow them with extraordinarily high dispersibility and excellent film-forming capabilities. Twenty-two types of nanoparticles synthesized by this strategy have all shown good lithographic properties in the mid-ultraviolet, electron beam, or extreme ultraviolet light, and these nanoparticle liquids have achieved controlled top-down nanofabrication with predesigned 18 or 16 nm patterns. This proposed strategy is synthetically scalable and structurally extensible and is expected to inspire the design of entirely new forms of nanomaterials.

Theoretical Insights into the Solubility Polarity Switch of Metal-Organic Nanoclusters for Nanoscale Patterning.

Metal-organic nanoclusters(MOCs) are being increasingly used as prospective photoresist candidates for advanced nanoscale lithography technologies. However, insight into the irradiation-induced solubility switching process remains unclear. Hereby, the theoretical study employing density functional theory (DFT) calculations of the alkene-containing zirconium oxide MOC photoresists is reported, which is rationally synthesized accordingly, to disclose the mechanism of the nanoscale patterning driven by the switch of solubility from the acid-catalyzed or electron-triggered ligand dissociation. By evaluating the dependence of MOCs' imaging process on photoacid, lithographies of photoresists with and without photoacid generators after exposure to ultraviolet (UV), electron beam, and soft X-ray, it is revealed that photoacid is essential in UV lithography, but it demonstrates little effect on exposure dose in high-energy lithography. Furthermore, theoretical studies using DFT simulations to investigate the plausible photoacid-catalyzed, electron-triggered dissociation, and accompanying radical reaction are performed, and a mechanism is demonstrated that the nanoscale patterning of this type of MOCs is driven by the solubility switch resulting from dissociation-induced strong electrostatic interaction and low-energy barrier radical polymerization with other species. This study can give insights into the chemical mechanisms of patterning, and guide the rational design of photoresists to realize high resolution and high sensitivity.

Sulfonium-Functionalized Polystyrene-Based Nonchemically Amplified Resists Enabling Sub-13 nm Nanolithography.

Nonchemically amplified resists based on triphenyl sulfonium triflate-modified polystyrene (PSTS) were prepared by a facile method of modification of polystyrene with sulfonium groups. The uploading of the sulfonium group can be well-controlled by changing the feed ratio of raw materials, resulting in PSTS0.5 and PSTS0.7 resists with sulfonium ratios of 50 and 70%, respectively. The optimum developer (methyl isobutyl ketone/ethanol = 1:7) is obtained by analyzing contrast curves of electron beam lithography (EBL). PSTS0.7 exhibits a better resolution (18 nm half-pitch (HP)) than the PSTS0.5 resist (20 nm HP) at the same developing conditions for EBL. This novel resist platform was further evaluated by extreme ultraviolet lithography, and patterning performance down to 13 nm HP at a dose of 186 mJ cm-2 with a line edge roughness of 2.8 nm was achieved. Our detailed study of the reaction and patterning mechanism suggests that the decomposition of the polar triflate and triphenyl sulfonium groups into nonpolar sulfide or polystyrene plays an important role in the solubility switch.

Molecular Glass Resists Based on Tetraphenylsilane Derivatives: Effect of Protecting Ratios on Advanced Lithography.

A series of t-butyloxycarbonyl (t-Boc) protected tetraphenylsilane derivatives (TPSi-Boc x , x = 60, 70, 85, 100%) were synthesized and used as resist materials to investigate the effect of t-Boc protecting ratio on advanced lithography. The physical properties such as solubility, film-forming ability, and thermal stability of TPSi-Boc x were examined to assess the suitability for application as candidates for positive-tone molecular glass resist materials. The effects of t-Boc protecting ratio had been studied in detail by electron beam lithography. The results suggest that the TPSi-Boc x resist with different t-Boc protecting ratios exhibit a significant change in contrast, pattern blur, and the density of bridge defect. The TPSi-Boc70% resist achieves the most excellent patterning capability. The extreme ultraviolet (EUV) lithography performance on TPSi-Boc70% was evaluated by using the soft X-ray interference lithography. The results demonstrate that the TPSi-Boc70% resist can achieve excellent patterning capability down to 20 nm isolated lines at 8.7 mJ/cm2 and 25 nm dense lines at 14.5 mJ/cm2. This study will help us to understand the relationship between the t-Boc protecting ratio and the patterning ability and supply useful guidelines for designing molecular resists.

Fluorine-Rich Zinc Oxoclusters as Extreme Ultraviolet Photoresists: Chemical Reactions and Lithography Performance.

The absorption of extreme ultraviolet (EUV) radiation by a photoresist strongly depends on its atomic composition. Consequently, elements with a high EUV absorption cross section can assist in meeting the demand for higher photon absorbance by the photoresist to improve the sensitivity and reduce the photon shot noise induced roughness. In this work, we enhanced the EUV absorption of the methacrylic acid ligands of Zn oxoclusters by introducing fluorine atoms. We evaluated the lithography performance of this fluorine-rich material as a negative tone EUV photoresist along with extensive spectroscopic and microscopic studies, providing deep insights into the underlying mechanism. UV-vis spectroscopy studies demonstrate that the presence of fluorine in the oxocluster enhances its stability in the thin films to the ambient atmosphere. However, the EUV photoresist sensitivity (D 50) of the fluorine-rich oxocluster is decreased compared to its previously studied methacrylic acid analogue. Scanning transmission X-ray microscopy and in situ X-ray photoelectron spectroscopy in combination with FTIR and UV-vis spectroscopy were used to gain insights into the chemical changes in the material responsible for the solubility switch. The results support decarboxylation of the ligands and subsequent radical-induced polymerization reactions in the thin film upon EUV irradiation. The rupture of carbon-fluorine bonds via dissociative electron attachment offers a parallel way of generating radicals. The mechanistic insights obtained here will be applicable to other hybrid materials and potentially pave the way for the development of EUV materials with better performance.

Fluorescent Labeling to Investigate Nanopatterning Processes in Extreme Ultraviolet Lithography.

Extreme ultraviolet (EUV) lithography uses 13.5 nm light to reach the sub-20 nm resolution. However, the process of pattern formation induced by this high-energy light is not well-understood. In this work, we provide an inorganic EUV photoresist with fluorescence properties by introducing a carbazole derivative as a ligand, and we study its effect on the patterning process. Using the fluorescence properties, changes in the emission of the material after EUV exposure could be tracked by means of spectroscopy and microscopy. The resist sensitivity was substantially reduced by the incorporation of the carbazole benzoate ligands, which is attributed to hole trapping and steric hindrance. After EUV irradiation of the resist films, infrared, UV-visible absorption, and fluorescence spectroscopies showed that the carbazole units were still mostly intact, although their fluorescence intensity was lowered. Our work shows that fluorescent labeling can provide relevant mechanistic insights in the patterning process of resists, potentially with a molecular resolution.