Photoacid Generator Research Articles

Electronic Effects and Steric Effects for the Design of N-Sulfonate Ester Phthalimide Photoacid Generators with High Acid Production Efficiency and Thermal Stability

Electronic Effects and Steric Effects for the Design of N-Sulfonate Ester Phthalimide Photoacid Generators with High Acid Production Efficiency and Thermal Stability

Photo-responsive Pickering emulsions triggered by in-situ pH modulation using a photoacid generator

HypothesisPickering emulsions that respond to changes in pH by the addition of acid or alkali have been extensively studied, but the development of photo-responsive Pickering emulsions has been more challenging. This study attempts to demonstrate a novel approach to achieve photo-responsiveness in Pickering emulsions by incorporating a photoacid generator (PAG) into the oil phase. Upon UV irradiation, the PAG is expected to release protons (H+), which can then regulate the pH of the emulsion system and control its stability. ExperimentsAmphiphilic colloidal particles obtained by modifying silica particles with poly (2-(dimethylamino)ethyl methacrylate) (SiO2-PDMAEMA) are used to stabilize the Pickering emulsions. The protonation and deprotonation of the SiO2-PDMAEMA particles at different pH values allow for the tuning of emulsion stability. By introducing the PAG into the stable Pickering emulsion system and applying UV irradiation to trigger the in-situ release of H+, the pH of the emulsion is systematically decreased, and the corresponding changes in emulsion stability are investigated. FindingsThe results show that UV irradiation alone cannot induce emulsion instability. However, when PAG is added to the oil phase, the Pickering emulsions exhibit a significant decrease in pH under UV irradiation, ultimately leading to emulsion destabilization and phase separation. At a UV intensity of 20 mW/cm2 for 2 min, the H+ release from the PAG significantly lower the emulsion’s pH, causing the SiO2-PDMAEMA particles to detach from the oil–water interface and resulting in emulsion instability. Higher concentrations of SiO2-PDMAEMA particles in the emulsion require more PAG to induce instability, as confirm by confocal laser scanning microscopy (CLSM) image. This study presents a versatile approach to develop photo-responsive Pickering emulsions which can have potential applications in areas such as drug delivery, cosmetics, and responsive materials.

A novel merocyanine photoacid for visible light-controlled pH modulation

Merocyanine-based photoacids generate high proton concentrations under visible light irradiation. In the past decade, it has been established that these photoacids offer significant advantages over photoacid generators (PAGs) and hydroxyaryl photoacids, enabling better spatiotemporal control of proton transfer reactions in bulk media. In this study, we modified the core structure of the first generation of meroyanine photoacids. We developed a novel photoacid with color tuning capabilities and high solubility in polar organic solvents. Specifically, by incorporating a cationic benzoindolium moiety as an acceptor, we have altered the photoacid’s light absorption properties. Unlike the first generation of indolium-based merocyanine photoacids, this photoacid can now be activated with green light (λmax = 525 nm) as well as blue (λmax = 450 nm) and ultraviolet (λmax = 365 nm) lights. Furthermore, the novel photoacid exhibits high photo stability, photo-acidity (Π = 3.28 ± 0.08) and moderate reverse reaction rate (k = 1.08 × 10−3 ± 0.00017 s−1) in solution. We envision that with improved color tuning capabilities, this class of photoacids will be a more versatile tool for controlling proton-induced reactions in different systems, including biological reactions.

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.

Photoactivated Cyclic Polyphthalaldehyde Microcapsules for Payload Delivery.

Microcapsules with a cyclic polyphthalaldehyde (cPPA) shell and oil core were fabricated by an emulsification process. The low ceiling temperature cPPA shell was made phototriggerable by incorporating a photoacid generator (PAG). Photoactivation of the PAG created a strong acid which catalyzed cPPA depolymerization, resulting in the release of the core payload, as quantified by 1H NMR. The high molecular weight cPPA (197 kDa) yielded uniform spherical microcapsules. The core diameter was 24.8 times greater than the cPPA shell thickness (2.4 to 21.6 μm). Nonionic bis(cyclohexylsulfonyl)diazomethane (BCSD) and N-hydroxynaphthalimide triflate (HNT) PAGs were used as the PAG in the microcapsule shells. BCSD required dual stimuli of UV radiation and post-exposure baking at 60 °C to activate cPPA depolymerization while room temperature irradiation of HNT resulted in instantaneous core release. A 300 s UV exposure (365 nm, 10.8 J/cm2) of the cPPA/HNT microcapsules resulted in 66.5 ± 9.4% core release. Faster core release was achieved by replacing cPPA with a phthalaldehyde/propanal copolymer. A 30 s UV exposure (365 nm, 1.08 J/cm2) resulted in 82 ± 13% core release for the 75 mol % phthalaldehyde/25 mol % propanal copolymer microcapsules. The photoresponsive shell provides a versatile polymer microcapsule technology for on-demand, controlled release of hydrophobic core payloads.

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.

Direct Optical Patterning of Metal-Organic Frameworks via Photoacid-Induced Etching.

Metal-organic frameworks (MOFs) are a class of porous materials constructed from organic linkers and inorganic building blocks. Coordinative competition labilizes some MOFs under harsh chemical conditions because of their weak bonding. However, instability is not always a negative property of a material. In this study, we demonstrated the use of the acidic lability of MOFs for direct optical patterning. The controllable acid release from the photoacid generator at the exposed area causes bond cleavage between the linkers and metal ions/clusters, leading to solubility changes and pattern formation after development. This process avoids redundant steps and possible contamination in traditional photolithography, while maintaining the original properties of patterned MOFs. The preserved porosity and crystallinity promoted the development of MOFs for gas sensors and solid displays.

Photochemical Michael Addition of Indoles to α,β‐Unsaturated Ketones utilizing Arylazo Sulfones as the Photoacid Generators

AbstractThe Michael‐type addition of indoles represents one of the most important C−C bonds forming reactions at their C‐3 position. Herein, we present a mild, versatile and sustainable protocol for the efficient preparation of β‐indolylketones via a Michael addition between indoles and chalcones or α,β‐unsaturated ketones in the presence of substituted arylazo sulfones as photoacid generators (PAGs).

Degradation of Modified Polystyrenes Having Degradable Units by Near Infrared Light Irradiation in The Presence of A Photon Upconversion Nanoparticle and A Photoacid Generator

Degradation of Modified Polystyrenes Having Degradable Units by Near Infrared Light Irradiation in The Presence of A Photon Upconversion Nanoparticle and A Photoacid Generator

Enhancing the Delamination Efficiency of Polyimide-Copper Bilayers with UV/Heat-Activated Foamable Adhesive: Insights and Applications.

This study explores the adhesive properties of copolymers comprising glycidyl methacrylate (GMA) and 3-(trimethoxysilyl)propyl methacrylate (MPTMS), focusing on their suitability for adhesive applications. Peel resistance measurements revealed a substantial impact of the GMA/MPTMS ratio on adhesion capabilities, identifying an optimal ratio of 30/70 for copolymerization with tert-butyl acrylate (tBA) to improve foaming performance. tBA, a foaming monomer activated by a photoacid generator and heat, enhances the copolymerized adhesive's adhesion strength and foamability for postuse delamination. Chemical structure analysis through Nuclear magnetic resonance (NMR) and Fourier-transform infrared spectroscopy (FTIR) confirmed successful polymerization, while rheological properties indicated decreased complex viscosity and adhesive strength with an increasing tBA content. The deprotection of the t-butyl group facilitated foam formation, supported by morphology analysis. These findings provide insights into foamable adhesive development with potential applications in delamination processes and implications for further exploration in polymer adhesion.

PH- and Photoresponsive Liquid Plasticine.

Liquid marbles (LMs) can be prepared by adsorption of hydrophobic particles at the air-liquid interface of a water droplet. LMs have been studied for their application as microreaction vessels. However, their opaqueness poses challenges for internal observation. Liquid plasticines (LPs), akin to LMs, can be prepared by the adsorption of hydrophobic particles with a diameter of 50 nm or less, at the air-liquid interface of a water droplet. Unlike LMs, LPs are transparent, allowing for internal observation, thus presenting promising applications as reactors and culture vessels on a microliter scale. In this study, the surface of silica particles, approximately 20 nm in diameter, was rendered hydrophobic to prepare hydrophobic silica particles (SD0). A small amount of poly(2-(diisopropylamino)ethyl methacrylate) (PDPA) was then grafted onto the surface of SD0, yielding SD1. SD0 particles exhibited consistent hydrophobicity irrespective of the environmental pH atmosphere. Under acidic conditions, SD1 became hydrophilic due to the protonation of pendant tertiary amines in the grafted PDPA chains. However, SD1 alone was unsuitable for LP preparation due to its high surface wettability regardless of atmospheric pH, attributable to the presence of PDPA-grafted chains. Therefore, to prepare pH-responsive LP, SD1 and SD0 were mixed (SD1/SD0 = 3/7). Upon exposure to HCl gas, these LPs ruptured, with the leaked water from the LPs being absorbed by adjacent paper. Moreover, clear LPs, prepared using an aqueous solution containing a water-soluble photoacid generator (PAG), disintegrated upon exposure to light as PAG generated acid, leading to LP breakdown. In summary, pH-responsive LPs, capable of disintegration under acidic conditions and upon light irradiation, were successfully prepared in this study.

Wavelength-Dependent Activation of Photoacids and Bases.

Photoacids and bases allow remote control over pH in reaction solutions, which is of fundamental importance to an array of applications. Herein, we determine the wavelength-by-wavelength resolved photoreactivity of triarylsulfonium hexafluorophosphate salts as a representative photoacid generator and p-(benzoyl)benzyl triethylammonium tetraphenylborate as a photobase generator, constructing a wavelength-resolved photochemical action plot for each of the compounds. We monitor the pH change of the solution on-line within the cavity of the laser vial and demonstrate a marked mismatch between the absorption spectrum of the photoacid and base with the photochemical action plot, unveiling reactivity at very low absorptivities. Our findings are of critical importance for the use of photoacids and bases, unambiguously demonstrating that absorption is no guide to chemical reactivity with critical consequences for the wavelength employed in applications of photoacids and bases.

Multi-color dual wavelength vat photopolymerization 3D printing via spatially controlled acidity

Dual wavelength vat photopolymerization (DW-VP) has emerged as a powerful approach to create multimaterial objects. However, only a limited range of properties have been showcased. In this work, we report the 3D printing (3DP) of multi-color objects from a single resin vat using DW-VP. This was accomplished by concurrently curing resin with visible light and modulating local resin color with 365-nm ultraviolet (UV) light. The key advance was to use a photoacid generator (PAG) in combination with pH responsive dyes in the 3DP resins. The specific color is dictated by the extent of reaction, or local acidity in our case, and controlled by the light dosage and pattern of UV light applied. Multi-color object formation was implemented in two-step processes involving first 3DP to set the object structure, followed by UV exposure, as well as single processes that leveraged DW-VP to create a broad range of vibrant colors and patterns.

Optimization strategy for epoxy cross-linked molecular glass photoresist in EUV lithography

The development of new resist materials is vital for fabrication techniques for next-generation microelectronics. A class of photosensitizer compositions with reactivity differences has been developed that can be used in epoxy cross-linked photoresist formulations for advanced microlithography techniques like extreme ultraviolet lithography (EUVL). With “PDN first, PAG second” combination strategy containing slow photolysis initiators (photoacid generator, PAG) and fast photolysis terminators (photodegradable nucleophile, PDN), photoresists produce photolithographic patterns with dense structure that are insoluble in the developer by epoxy cationic polymerization. This combination enhances chemical contrast between the exposed and non-exposed areas while eliminating the stochastic impact to get a lithographic structure with high mechanical strength. Lithographic formulations have been developed and tested in line-and-space patterning experiments using EUVL, and 18 nm half-pitch (HP) at a dose of 25.2 mJ·cm−2 with a line edge roughness (LER) of 2.8 nm was achieved by the combination strategy. This strategy offers the possibility of achieving higher resolution for photoresists based on a cationic polymerization mechanism.

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.

Exceptional Lithography Sensitivity Boosted by Hexafluoroisopropanols in Photoresists.

Advanced lithography requires highly sensitive photoresists to improve the lithographic efficiency, and it is critical, yet challenging, to develop high-sensitivity photoresists and imaging strategies. Here, we report a novel strategy for ultra-high sensitivity using hexafluoroisopropanol (HFIP)-containing fluoropolymer photoresists. The incorporation of HFIP, with its strong electrophilic property and the electron-withdrawing effect of the fluorine atoms, significantly increases the acidity of the photoresist after exposure, enabling imaging without conventional photoacid generators (PAGs). The HFIP-containing photoresist has been evaluated by electron beam lithography to achieve a trench of ~40 nm at an extremely low dose of 3 μC/cm2, which shows a sensitivity enhancement of ~10 times compared to the commercial system involving PAGs, revealing its high sensitivity and high-resolution features. Our results demonstrate a new type of PAGs and a novel approach to higher-performance imaging beyond conventional photoresist performance tuning.

Friedel–Crafts Alkylation of Indoles with Aldehydes/Ketones Catalyzed by Bromodiarylethene-Based Photoacid Generators

AbstractDiarylethenes (DAEs) with a bromine atom at the ring-closing position catalyze C–C bonding reactions induced by UV or sunlight. Upon photo-irradiation, bromodiarylethenes undergo 6π-electrocyclization (6π-EC), followed by the release of an acid species that catalyzes the double Friedel–Crafts addition of indoles to aldehydes and isatins to form the corresponding triarylmethanes and 3,3′-diarylindolin-2-ones. This protocol is applicable to a wide spectrum of aldehydes and isatins, as well as chalcones as electrophiles. Acid or oxidant-sensitive functional groups, such as ferrocene, 4-methoxyphenyl, thiophene, pyrrole are tolerated. Mechanistic studies show that light is needed to initiate the reaction.

Magnetically Actuated Trigger Transient Soft Actuators Comprising On-Demand Photo-Initiated and Thermo-Degradable Polypropylene Carbonate-Photo-Acid Generator.

Lifetime-reconfigurable soft robots have emerged as a new class of robots, emphasizing the unmet needs of futuristic sustainability and security. Trigger-transient materials that can both actuate and degrade on-demand are crucial for achieving life-reconfigurable soft robots. Here, we propose the use of transient and magnetically actuating materials that can decompose under ultraviolet light and heat, achieved by adding photo-acid generator (PAG) and magnetic particles (Sr-ferrite) to poly(propylene carbonate) (PPC). Chemical and thermal analyses reveal that the mechanism of PPC-PAG decomposition occurs through PPC backbone cleavage by the photo-induced acid. The self-assembled monolayer (SAM) encapsulation of Sr-ferrite preventing the interaction with the PAG allowed the transience of magnetic soft actuators. We demonstrate remotely controllable and degradable magnetic soft kirigami actuators using blocks with various magnetized directions. This study proposes novel approaches for fabricating lifetime-configurable magnetic soft actuators applicable to diverse environments and applications, such as enclosed/sealed spaces and security/military devices.

Reconfigurable Droplet-Droplet Communication Mediated by Photochemical Marangoni Flows.

Droplets are attractive building blocks for dynamic matter that organizes into adaptive structures. Communication among collectively operating droplets opens untapped potential in settings that vary from sensing, optics, protocells, computing, or adaptive matter. Inspired by the transmission of signals among decentralized units in slime mold Physarum polycephalum, we introduce a combination of surfactants, self-assembly, and photochemistry to establish chemical signal transfer among droplets. To connect droplets that float at an air-water interface, surfactant triethylene glycol monododecylether (C12E3) is used for its ability to self-assemble into wires called myelins. We show how the trajectory of these myelins can be directed toward selected photoactive droplets upon UV exposure. To this end, we developed a strategy for photocontrolled Marangoni flow, which comprises (1) the liquid crystalline coating formed at the surface of an oleic acid/sodium oleate (OA/NaO) droplet when in contact with water, (2) a photoacid generator that protonates sodium oleate upon UV exposure and therefore disintegrates the coating, and (3) the surface tension gradient that is generated upon depletion of the surfactant from the air-water interface by the uncoated droplet. Therefore, localized UV exposure of selected OA/NaO droplets results in attraction of the myelins such that they establish reconfigurable connections that self-organize among the C12E3 and OA/NaO droplets. As an example of communication, we demonstrate how the myelins transfer fluorescent dyes, which are selectively delivered in the droplet interior upon photochemical regulation of the liquid crystalline coating.

Hydrolysis-Induced Morphology Evolution of Linear and Bottlebrush Block Copolymers in Thin Films with Acid Vapor or Photoacid Generators

Hydrolysis-Induced Morphology Evolution of Linear and Bottlebrush Block Copolymers in Thin Films with Acid Vapor or Photoacid Generators