Lithographic Performance Research Articles

Improving the Lithography Sensitivity of Atomically Precise Tin-Oxo Nanoclusters via Heterometal Strategy.

Tin-oxo clusters are increasingly recognized as promising materials for nanolithography technology due to their unique properties, yet their structural impacts on lithography performance remain underexplored. This work explores the structural impacts of heterometal strategies on the performance of tin-oxo clusters in nanolithography, focusing on various metal dopants and their coordination geometries. Specifically, SnOC-1(In), SnOC-1(Al), SnOC-1(Fe), and SnOC-2 were synthesized and characterized. These clusters demonstrate excellent solubility, dispersibility, and stability, facilitating the preparation of high-quality films via spin-coating for lithographic applications. Notably, this work innovatively employs Atomic Force Microscopy-based Infrared Spectroscopy (AFM-IR), neutron reflectivity (NR), and X-ray reflectivity (XRR) measurements to confirm film homogeneity. Upon electron beam lithography (EBL), all four materials achieve 50 nm line patterns, with SnOC-1(In) demonstrating the highest lithography sensitivity. This enhanced sensitivity is attributed to indium dopants, which possess superior EUV absorption capabilities and unsaturated coordination environments. Further studies on exposure mechanisms indicated that Sn-C bond cleavage generates butyl free radicals, promoting network formations that induce solubility-switching behaviors for lithography. These findings underscore the efficacy of tailored structural design and modulation of cluster materials through heterometal strategies in enhancing lithography performance, offering valuable insights for future material design and applications.

Improving the Lithography Sensitivity of Atomically Precise Tin‐Oxo Nanoclusters via Heterometal Strategy

AbstractTin‐oxo clusters are increasingly recognized as promising materials for nanolithography technology due to their unique properties, yet their structural impacts on lithography performance remain underexplored. This work explores the structural impacts of heterometal strategies on the performance of tin‐oxo clusters in nanolithography, focusing on various metal dopants and their coordination geometries. Specifically, SnOC‐1(In), SnOC‐1(Al), SnOC‐1(Fe), and SnOC‐2 were synthesized and characterized. These clusters demonstrate excellent solubility, dispersibility, and stability, facilitating the preparation of high‐quality films via spin‐coating for lithographic applications. Notably, this work innovatively employs Atomic Force Microscopy‐based Infrared Spectroscopy (AFM‐IR), neutron reflectivity (NR), and X‐ray reflectivity (XRR) measurements to confirm film homogeneity. Upon electron beam lithography (EBL), all four materials achieve 50 nm line patterns, with SnOC‐1(In) demonstrating the highest lithography sensitivity. This enhanced sensitivity is attributed to indium dopants, which possess superior EUV absorption capabilities and unsaturated coordination environments. Further studies on exposure mechanisms indicated that Sn−C bond cleavage generates butyl free radicals, promoting network formations that induce solubility‐switching behaviors for lithography. These findings underscore the efficacy of tailored structural design and modulation of cluster materials through heterometal strategies in enhancing lithography performance, offering valuable insights for future material design and applications.

Quartz crystal microbalance analysis of effects of surfactants on dissolution kinetics of poly(4-hydroxystyrene) partially protected with t-butoxycarbonyl group

Abstract Surfactants comprise water-repellent and water-attracting moieties and have been used to improve the lithographic performance of resist materials. However, the effects of surfactants on the dissolution kinetics of these materials are still unclear. In this study, the effects of surfactants on the dissolution kinetics of partially-protected poly(4-hydroxystyrene) (PHS) in 0.26 N tetramethylammonium hydroxide aqueous solution was investigated using a quartz crystal microbalance method. Anionic (sodium n-octanonate, sodium 1-hexanesulfonate, n-dodecylbenzenesulfonic acid, and sodium n-dodecyl sulfate), cationic (methylamine hydrochloride, dodecyltrimethylammonium chloride, and 30% ammonium lauryl sulfate solution), nonionic (sorbitan monooleate, polyoxyethylene(23)lauryl ether, and polyoxyethylene(10)hydrogenated castor oil), and amphoteric (35% lauryl dimethylaminoacetic acid solution) surfactants were examined. The surfactant significantly affected the dissolution kinetics of the PHS films. The surfactant effects were significantly reduced by protecting the hydroxyl groups of PHS. The effect of the surfactant on the dissolution kinetics depended on the surfactant rather than on the surfactant type.

A strategy to prepare high Tg and low CTE solder resist using alkali-soluble photosensitive polyimide

Photosensitive Solder resist (SR) materials require a high glass transition temperature (Tg > 170 °C) and a coefficient of thermal expansion matching that of copper (CTE≈17 ppm/°C) to meet the demands of manufacturing processes and application reliability. However, the commonly used epoxy resin in SR materials exhibits insufficient mechanical and thermal properties, failing to meet these requirements adequately. To address this issue, alkali-soluble photosensitive poly (amic ester) (PAE) materials were synthesized. By grafting a low-temperature curing accelerator, 6-([1,1′-biphenyl]–4-yl)–4-chloroquinoline (NQL), onto the hydroxyl groups of the PAE, the resultant grafted PAE resin was blended with an alkali-soluble photosensitive modified epoxy resin (APE) to enhance the mechanical and thermal properties of the SR composite. Research indicates that due to the low-temperature curing effect and electrostatic interactions of NQL, SR-2 (with a 10% PAE addition) exhibits a Tg of 183 °C and a CTE of 16 ppm/°C, while SR-3 (with a 30% PAE addition) achieves a Tg of 204 °C and a CTE of 20 ppm/°C. Furthermore, with the PAE addition of 5%, the lithography quality of SR is enhanced, enabling SR-1 to achieve a pattern resolution of up to 40 μm. The modification method involving PSPI blending has been shown to enhance the thermal stability, dimensional stability, and lithographic performance of SR, indicating significant potential applications in solder resist materials.

Influence of Chemical Structures on E-Beam Lithography Performance of Polysilsesquioxanes.

Hydrogenated silsesquioxane (HSQ) is a key inorganic electron beam resist, celebrated for its sub-10 nm resolution and etching resistance, but it faces challenges with stability and sensitivity. Our innovative study has comprehensively assessed the lithographic performance of three functionalized polysilsesquioxane (PSQ) resist series─olefins, halogenated alkanes, and alkanes─under electron beam lithography (EBL). We discovered that the addition of olefin groups, such as in the HMP-30 formulation with 30% propyl acrylate, remarkably increased the sensitivity to 0.6 μC/cm2. The inclusion of halogenated aromatic and hydrogen-substituted methyl groups further enhanced sensitivity and contrast, with HClBN-50 achieving a 22.9 nm resolution pattern. At the same time, the storage of PSQ resists was significantly improved compared to commercial HSQ with increasing alkane group content. Crucially, our research has unveiled the lithography reaction mechanism, highlighting how group encapsulation and steric hindrance influence PSQ performance. This insight is groundbreaking, offering a deeper understanding of the molecular structure-performance relationship and laying the groundwork for developing next-generation electron beam resists with superior sensitivity, resolution, and contrast for microelectronics manufacturing.

Novel Etch-Resistant Molecular Glass Photoresist Based on Pyrene Derivatives for Electron Beam Lithography.

Novel t-butyloxycarbonyl-protected molecular glass photoresists with pyrene as the core (Pyr-8Boc and Pyr-4Boc) were designed and synthesized. The thermal stability and film-forming ability were measured to assess their applicability for lithography. Pyr-Boc (Pyr-8Boc and Pyr-4Boc) photoresists were evaluated by high-resolution electron beam lithography (EBL), acting as chemically amplified resists. Pyr-4Boc showed a better lithography performance, achieving 25 nm line/space patterns at the dose of 50 μC/cm2. Under SF6/O2 plasma, the etch selectivity of the Pyr-4Boc photoresist to silicon was 12.3, which is twice that of the commercially available poly(methyl methacrylate) photoresist (950 k). The lithography mechanism of EBL was further investigated. Theoretical calculations of HOMO/LUMO orbital energies, cyclic voltammetry, and fluorescence quenching experiments were conducted to confirm the electron-transfer reactions between the Pyr-Boc and photoacid generator. The study provides an option of high sensitivity and etch-resistant photoresist for EBL.

A comprehensive study on three typical photoacid generators using photoelectron spectroscopy and abinitio calculations.

Conducting a comprehensive molecular-level evaluation of a photoacid generator (PAG) and its subsequent impact on lithography performance can facilitate the rational design of a promising 193nm photoresist tailored to specific requirements. In this study, we integrated spectroscopy and computational techniques to meticulously investigate the pivotal factors of three prototypical PAG anions, p-toluenesulfonate (pTS-), 2-(trifluoromethyl)benzene-1-sulfonate (TFMBS-), and triflate (TF-), in the lithography process. Our findings reveal a significant redshift in the absorption spectra caused by specific PAG anions, attributed to their involvement in electronic transition processes, thereby enhancing the transparency of the standard PAG cation, triphenylsulfonium (TPS+), particularly at ∼193nm. Furthermore, the electronic stability of PAG anions can be enhanced by solvent effects with varying degrees of strength. We observed the lowest vertical detachment energy of 6.6eV of pTS- in PGMEA solution based on the polarizable continuum model, which prevents anion loss at 193nm lithography. In addition, our findings indicate gas-phase proton affinity values of 316.4 kcal/mol for pTS-, 308.1 kcal/mol for TFMBS-, and 303.2 kcal/mol for TF-, which suggest the increasing acidity strength, yet even the weakest acid pTS- is still stronger than strong acid HBr. The photolysis of TPS+-based PAG, TPS+·pTS-, generated an excited state leading to homolysis bond cleavage with the lowest reaction energy of 83 kcal/mol. Overall, the PAG anion pTS- displayed moderate acidity, possessed the lowest photolysis reaction energy, and demonstrated an appropriate redshift. These properties collectively render it a promising candidate for an effective acid producer.

DMD digital lithography optimization based on a hybrid genetic algorithm and improved exposure model

An efficient method to optimize digital micromirror device (DMD) lithography was proposed using a hybrid genetic algorithm integrated with an improved exposure model. The improved exposure model significantly refines traditional approaches by incorporating advanced parameters not previously considered, including the cross-transfer coefficient, detailed light source functions, and impulse response functions. These enhancements provide a comprehensive assessment of the entire optical imaging system’s impact on lithography quality and more accurately simulate the interactions of light with the photoresist. The hybrid method combines the robust optimization capabilities of genetic algorithms (GA) with this sophisticated exposure model, facilitating precise micromirror configurations and optimizing light distribution for specific lithographic patterns. This integration results in substantial improvements in lithographic precision, with improvements of up to 84% for hexagonal star patterns, 83% for arrow patterns, and 85% for embedded figure patterns. These advancements enhance imaging quality, reduce optical proximity distortions, and improve overall lithography performance, offering crucial insights into the precision and efficiency improvement of microelectronics fabrication processes.

Design and production of mesh patterned photoelectrode with maskless laser lithography and device performance of perovskite derived/ZnO NRAs based photodetector

Design and production of mesh patterned photoelectrode with maskless laser lithography and device performance of perovskite derived/ZnO NRAs based photodetector

Additive-Assisted Forming High-Quality Thin Films of Sn-Oxo Cluster for Nanopatterning.

Recently, metal-oxo clusters (MOCs) have attracted significant interest in fabricating nanoscale patterns in semiconductors via lithography. However, many MOCs are highly crystalline, making it difficult for them to form films and hindering subsequent nanopatterning processes. In this study, we developed a novel and simple method to enhance the film-forming ability of aromatic tetranuclear Sn-oxo clusters by adding additives. Theoretical calculations and Fourier-transform infrared (FTIR) analysis revealed the formation of intermolecular hydrogen bonds between the Sn-oxo clusters and additives, which induced a crystal-gel phase transition at -20 °C, thereby inhibiting the easy crystallization of the Sn-oxo clusters. High-quality and uniform thin films with surface roughness below 0.3 nm were prepared via spin coating. The obtained thin films exhibited good lithographic performance under deep ultraviolet (DUV), electron beam, and extreme-ultraviolet irradiation without a photo acid generator/photoinitiator, and 13- and 21 nm-wide line patterns were obtained on the films via electron-beam and extreme-ultraviolet lithographies. This study will pave the way for the further investigation of novel MOCs for advanced lithography and other thin-film applications.

Zn-Ti oxo cluster photoresists for EUV Lithography: Cluster structure and lithographic performance

Low reflectivity of multilayer mirror–induced low efficiency of existing extreme ultraviolet lithography (EUVL) has triggered the search for photoresists with heightened sensitivity. For this purpose, considerable research has focused on elements with high extreme ultraviolet (EUV) absorption, leading to considerable advancements. Solubility alteration, often resulting from ligand variations after exposure, is influenced by the cluster structure, markedly impacting lithography sensitivity. Herein, three Ti-based metal clusters, Ti6O4(OEt)8(OMc)8 (T-2), Zn2Ti4O4(OiPr)2(OMc)10 (TZ-1), and Zn4Ti2O2(OAc)2(OBu)2(OMc)10 (TZ-2), are designed and synthesized to elucidate the effects of the structure on lithography. These mixed metal–oxo clusters derived from Ti6O4(OR)8(OOCR)8 and stabilized by identical ligands exhibit structural diversity. The increase in the number of zinc atoms results in marked alterations in the oxo core, thereby triggering alterations in ligand coordination modes. These variations confer metal clusters with different solubility and lithographic properties. Analysis of the photochemical reaction mechanism and theoretical calculations reveal a reactive tridentate ligand coordination mode that considerably improves lithography sensitivity. Therefore, changing the ligand coordination mode by designing a mixed metal–oxo core holds promise for discovering new photoresists for EUV lithography.

A novel non-chemically amplified resist based on polystyrene-iodonium derivatives for electron beam lithography

To break the resolution limitation of traditional resists, more work is needed on non-chemically amplified resists (non-CARs). Non-CARs based on iodonium salt modified polystyrene (PS-I) were prepared with controllable molecular weight and structure. The properties of the resist can be adjusted by the uploading of iodonium salts on the polymer chain, the materials with a higher proportion of iodonium salts show better lithography performance. By comparing contrast curves and quality of the lithographic patterns, the optimum developing condition of 4-methyl-2-pentanone and ethyl alcohol (v:v = 1:7) was selected. The high-resolution stripes of 15 nm half-pitch (HP) can be achieved by PS-I0.58 in e-beam lithography (EBL). PS-I0.58 shows the advanced lithography performance in the patterns of 16 nm HP and 18 nm HP stripes with low line edge roughness (3.0 nm and 2.4 nm). The resist shows excellent potential for further pattern transfer, the etch selectivity of resist PS-I0.58 to the silicon was close to 12:1. The lithographic mechanism of PS-I was investigated by experimental and theoretical calculation, which indicates the polarity of materials changes results in the solubility switch. This work provides a new option and useful guidelines for the development of high-resolution resist.

Absolute density measurement of hydrogen radicals in XUV induced plasma for tin contamination cleaning via laser-induced fluorescence

Effective cleaning of tin contamination on the collecting mirrors in extreme ultraviolet source is one of the key techniques to improve throughput and cost performance of extreme ultraviolet lithography. Hydrogen radicals produced in hydrogen plasma that is induced by wideband extreme ultraviolet radiation are expected to be utilized for in situ tin contamination cleaning in extreme ultraviolet sources. In this Letter, we clarified absolute density and cleaning ability of the hydrogen radicals produced by intense extreme ultraviolet pulse through ground state population density measurement by laser-induced fluorescence technique. The experimentally obtained radical parameters coincided well with simulation results and collisional radiative model. It was found that the extreme ultraviolet induced plasma was in quasi-steady state with abundant amount of hydrogen radicals in ground state. Further, it was found that the in situ tin contamination cleaning in extreme ultraviolet lithography source would become more practical with increase in operational parameters, such as extreme ultraviolet emission intensity, gas pressure, and radical production cross section.

Dissociative photoionization of phenyl triflate, a photoacid generator for photolithography, at 92 eV.

The dissociative photoionization of phenyl triflate (C6H5OSO2CF3), a neutral photoacid generator used in photolithography, was investigated in a gas phase experiment employing extreme ultraviolet (EUV) synchrotron radiation at 92eV and photoelectron-photoion coincidence detection. The interaction of EUV photons with the molecule leads almost exclusively to dissociation, which is dominated by a sequential fragmentation mechanism, in which SO2, CF3, CO, and C2H2 are lost. For lithographic purposes, the lack of the observation of a fragment that could serve as a precursor for the formation of triflic acid means that the effective photoacid generator concentration in a photoresist is reduced, impacting its patterning performance in EUV lithography. A better understanding of the dissociative photoionization of photoresist components and proxies thereof can provide a crucial handle that guides the design of photoresists for the upcoming technology nodes with ever decreasing feature sizes for more powerful computer chips.

DMD maskless lithography optimization based on an improved genetic algorithm

In this paper, we propose an effective method for optimizing mask design using an enhanced genetic algorithm (GA), significantly boosting digital micromirror device (DMD) maskless lithography performance. After a thorough evaluation of various optimization techniques, we determined that the simulated annealing-enhanced GA (SA-GA) offers superior improvements in lithography simulations, thus optimizing mask design more effectively. Our findings reveal that this method achieves up to 88% and 75% enhancement in simulation accuracy for circular and heart-shaped patterns, respectively, surpassing the results of conventional Hopkins lithography simulations. The remarkable effect of improved GA in enhancing the quality of DMD digital lithography shows that it will have great potential in micro-fabrication applications, and paves the way for the realization of high-fidelity and efficient DMD digital lithography technology, which has excellent versatility and adaptability in the field of microelectronics manufacturing.

Extreme Ultraviolet Lithographic Performance and Reaction Mechanism of Polymeric Resist─Utilizing Radical- and Acid-Amplified Cross-Linking

Extreme Ultraviolet Lithographic Performance and Reaction Mechanism of Polymeric Resist─Utilizing Radical- and Acid-Amplified Cross-Linking

Curvilinear data representation and its impact on file size and lithographic performance

Curvilinear data representation and its impact on file size and lithographic performance

Understanding and Control of Polymer Distribution in Photoresists Using Liquid Chromatography for Enhanced Lithography Performance

Understanding and Control of Polymer Distribution in Photoresists Using Liquid Chromatography for Enhanced Lithography Performance

Synthesis of poly (amic ester) with controlled molecular weight for photosensitive polyimide in advanced package

Photosensitive polyimide (PSPI) with excellent lithography patterning and superior comprehensive properties have emerged as a very promising material for the advanced electronic package in IC field. Thereinto, poly (amic ester) (PAE) with highly sensitive groups and suitable molecular weight becomes the most important component in PSPI. Herein, a series of PAEs are synthesized by 4,4-oxydiphthalic anhydride, 4,4′-oxydianiline, and 2-hydroxyethyl methacrylate. The molecular weight of PAE was carefully controlled by using phthalic anhydride as the end-capping agent ranging from 9 000–20 000 g/mol. With the cooperation of photoinitiator and crosslinker, high-performance PSPIs were obtained. The results showed that the PAE with a molecular weight of 15 000 g/mol showed the best performance of lithography with resolution of 10 µm. The further increase of the molecular weight resulted the residues after developing, while lower molecular weight exhibited partially imidization during the pre-baking process, leading to a decrease in the solubility of PAE, as well. Additionally, as-prepared PSPIs also performed excellent thermal, mechanical, and dielectric properties, showing tensile strength of 120 MPa, elongation at break of 8%, glass transition temperature and the temperature of 5% weight loss of 260 °C and 430 °C, respectively. All these results exhibit a great application potential for high performance advanced packaging.

Development of EUV interference lithography for 25 nm line/space patterns

In this study, we present the performance of an extreme ultraviolet interference lithography (EUV-IL) setup that was reconstructed at Taiwan Light Source 21B2 EUV beamline in the National Synchrotron Radiation Research Center (NSRRC), Taiwan. An easy-to-perform fabrication method to produce a high-quality transmission grating mask and a simple design of experimental setup for EUV-IL were developed. The current EUV-IL setup is capable of fabricating line/space patterns down to 25 nm half-pitch in hydrogen silsesquioxane (HSQ) resist. Preliminary exposure results revealed that optimized slit width and exposure time significantly improved line/space pattern quality. The current EUV-IL tool at NSRRC can be used for nano-patterning and resist screening to advance the next generation of semiconductor devices.