Design of a positive-tone water-soluble resist

Havard, Jennifer M.; Fréchet, Jean M. J.; Pasini, Dario; Mar, Brenda; Yamada, Shintaro; Medeiros, David R.; Willson, C. Grant

doi:10.1117/12.275844

Cited by 6 publications

(14 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Poly(2-isopropenyl-2-oxazoline) (PiPOx) has emerged as a promising versatile platform in the development of various functional polymeric materials. To date, PiPOx has been used successfully in the development of coatings, − a positive-tone water-soluble resist, − novel low-toxicity polymer crosslinkers, brush polymers, − fluorescent polymers, thermoresponsive polymers, hydrogel materials, − and amphiphilic block copolymers . PiPOx can be obtained with well-defined characteristics via several polymerization techniques such as free or controlled radical polymerization, ,− anionic polymerization, ,, and metal-mediated group transfer polymerization. , PiPOx can be tailored toward the various reported applications through either the cationic ring-opening polymerization of the reactive 2-oxazoline side-chain functionality or the ring-opening addition reaction of carboxylic acids or thiols to 2-oxazoline side chains.…”

Section: Introductionmentioning

confidence: 99%

In Vitro Assessment of the Hydrolytic Stability of Poly(2-isopropenyl-2-oxazoline)

Jerca

Hoogenboom

2021

Biomacromolecules

View full text Add to dashboard Cite

Poly(2-isopropenyl-2-oxazoline) (PiPOx) is emerging as a promising, versatile polymer platform to design functional materials and particularly biomaterials that rely on the hydrophilic character of the 2-oxazoline side units. To be able to assess the applicability of PiPOx in a biomedical context, it is essential to understand its stability and degradation behavior in physiological conditions. In the present work, the hydrolytic stability of PiPOx was systematically investigated as a function of pH during incubation in various buffers. PiPOx was found to be stable in deionized water (pH 6.9), to have good stability in basic conditions (pH 8 and 9), to be satisfactorily stable in neutral conditions (pH 7.4), and to have moderate to low stability in acidic conditions (decreases drastically from pH 6 to pH 1.2). At pH 4, PiPOx formed a crosslinked network in a timeframe of hours, while at pH 1.2, PiPOx was transformed to a water-soluble poly(N-(2-hydroxyethyl)methacrylamide) type of structure over the course of 2 weeks. In vitro stability assays were performed in phosphate-buffered saline (pH 7.4), simulated body fluid (SBF) (pH 7.4), simulated saliva (pH 6.4), simulated intestinal fluid (pH 6.8), and plasma (pH 7.4) revealing that PiPOx is stable in these SBFs up to 1 week of incubation. When incubated in simulated gastric fluid (pH 1.2), PiPOx exhibited a similar degradation behavior to that observed in the buffer at pH 1.2, rendering a water-soluble structure. The presented results on the stability of PiPOx will be important for future use of PiPOx for the development of drug-delivery systems and biomedical applications, such as hydrogels.

show abstract

Section: Introductionmentioning

confidence: 99%

In Vitro Assessment of the Hydrolytic Stability of Poly(2-isopropenyl-2-oxazoline)

Jerca

Hoogenboom

2021

Biomacromolecules

View full text Add to dashboard Cite

show abstract

“…Fréchet, Willson, and co-workers described a positive-tone system based on a pre-cross-linked poly(acrylic acid)/divinyl ether composition. 15 Later, a negative-tone system based on a sugar-modified poly(acrylate) appeared. 16…”

Section: Introductionmentioning

confidence: 99%

“…Frećhet, Willson, and co-workers described a positive-tone system based on a pre-cross-linked poly(acrylic acid)/divinyl ether composition. 15 Later, a negative-tone system based on a sugar-modified poly(acrylate) appeared. 16 We aimed to develop water-soluble vinyl addition norbornene photopolymer compositions to take advantage of this benign solvent as well as the expected higher etch resistance that norbornene vinyl addition polymers provide.…”

Section: ■ Introductionmentioning

confidence: 99%

“…In the late 1990s, two publications reported routes to both positive- and negative-tone chemically amplified photopolymer compositions that used water as a solvent and as a developer after imagewise exposure. Fréchet, Willson, and co-workers described a positive-tone system based on a pre-cross-linked poly(acrylic acid)/divinyl ether composition . Later, a negative-tone system based on a sugar-modified poly(acrylate) appeared …”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Sugar-Functional Vinyl Addition Poly(norbornene)–Photopatternable Poly(norbornenyl gluconamide) Compositions Developed with Water

et al. 2018

View full text Add to dashboard Cite

The norbornenyl gluconamide (NBGA) monomer can be polymerized by a number of palladium catalysts to give water-soluble, vinyl addition poly(NBGA). Depending on the catalyst used, the reaction conditions, and the chain-transfer additives employed, high-molecular-weight polymers can be obtained. These polymers can be thermally cross-linked at ca. 190 °C or at ca. 150 °C when the difunctional glutaraldehyde is added. A photopatternable composition is formed by the addition of a water-soluble diazide when the poly(NBGA) molecular weight is sufficiently high. After image-wise exposure, negative-tone patterns are revealed by water development. A detailed analysis of NBGA monomer structures by high-resolution nuclear magnetic resonance techniques including pure shift is reported showing that two diastereomers of each endo- and exo-isomer are formed from the reaction of norbornene methylamine and δ-gluconolactone.

show abstract

“…Photopolymers, used in applications ranging from state-of-the-art semiconductor devices to lower resolution circuit boards, flat-panel displays, or antireflective coatings, have traditionally been cast from organic solvents and developed in solvents or aqueous solutions containing organic bases . We have recently initiated a study of environmentally enhanced photopolymers that may be both cast and developed in pure water only …”

Section: Introductionmentioning

confidence: 99%

Photoresists with Reduced Environmental Impact: Water-Soluble Resists Based on Photo-Cross-Linking of a Sugar-Containing Polymethacrylate

Havard¹,

Vladimirov²,

Fréchet³

et al. 1998

Macromolecules

Self Cite

View full text Add to dashboard Cite

A family of water-soluble, negative-tone, high-resolution, chemically amplified photoresists based on partially or fully deprotected poly(1,2:5,6-di-O-isopropylidene-3-O-methacryloyl-α-d-glucofuranose) is described. Both the molecular weight of the parent ketal-protected polymer and the extent of its deprotection to a water-soluble polymer containing 3-O-methacryloyl-d-glucopyranose repeat units must be carefully controlled to provide good coating and imaging properties. The two ketal protecting groups of the poly(1,2:5,6-di-O-isopropylidene-α-d-glucofuranose) have different reactivity, and their complete removal requires long reaction times under hydrolytic conditions. The detailed deprotection chemistry of the polymer is readily understood through model studies with the fully and partially protected analogues of the polymer pendant groups: 1,2:5,6-di-O-isopropylidene-α-d-glucofuranose and 1,2-isopropylidene-α-d-glucopyranose. When combined with a water-soluble photochemical precursor of acid such as (4-methoxyphenyl)dimethylsulfonium trifluoromethanesulfonate, films of the deprotected or partially deprotected poly(1,2:5,6-di-O-isopropylidene-3-O-methacryloyl-α-d-glucofuranose) undergo acid-catalyzed cross-linking. The enhanced performance of the partially deprotected polymers over that of poly(3-O-methacryloyl-d-glucopyranose) suggests that the presence of remaining hydrophobic groups that afford water dispersibility rather than full solubility may be key to their performance. Imaged negative-tone features as small as 0.2 μm are obtained with these materials that have sensitivities of ca. 30 mJ/cm2 with wholly aqueous casting and processing.

show abstract

Design of a positive-tone water-soluble resist

Cited by 6 publications

References 0 publications

In Vitro Assessment of the Hydrolytic Stability of Poly(2-isopropenyl-2-oxazoline)

In Vitro Assessment of the Hydrolytic Stability of Poly(2-isopropenyl-2-oxazoline)

Sugar-Functional Vinyl Addition Poly(norbornene)–Photopatternable Poly(norbornenyl gluconamide) Compositions Developed with Water

Photoresists with Reduced Environmental Impact: Water-Soluble Resists Based on Photo-Cross-Linking of a Sugar-Containing Polymethacrylate

Contact Info

Product

Resources

About