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Title: Radiopaque Resists for Two-Photon Lithography To Enable Submicron 3D Imaging of Polymer Parts via X-ray Computed Tomography

Abstract

Two-photon lithography (TPL) is a high-resolution additive manufacturing (AM) technique capable of producing arbitrarily complex three-dimensional (3D) microstructures with features 2–3 orders of magnitude finer than human hair. This process finds numerous applications as a direct route toward the fabrication of novel optical and mechanical metamaterials, miniaturized optics, microfluidics, biological scaffolds, and various other intricate 3D parts. As TPL matures, metrology and inspection become a crucial step in the manufacturing process to ensure that the geometric form of the end product meets design specifications. X-ray-based computed tomography (CT) is a nondestructive technique that can provide this inspection capability for the evaluation of complex internal 3D structure. However, polymeric photoresists commonly used for TPL, as well as other forms of stereolithography, poorly attenuate X-rays due to the low atomic number (Z) of their constituent elements and therefore appear relatively transparent during imaging. We present the development of optically clear yet radiopaque photoresists for enhanced contrast under X-ray CT. We have synthesized iodinated acrylate monomers to formulate high-Z photoresist materials that are capable of forming 3D microstructures with sub-150 nm features. In addition, we have developed a formulation protocol to match the refractive index of the photoresists to the immersion medium ofmore » the objective lens so as to enable dip-in laser lithography, a direct laser writing technique for producing millimeter-tall structures. Our radiopaque photopolymer then resists increase X-ray attenuation by a factor of more than 10 times without sacrificing the sub-150 nm feature resolution or the millimeter-scale part height. Thus, our resists can successfully replace existing photopolymers to generate AM parts that are suitable for inspection via X-ray CT. By providing the “feedstock” for radiopaque AM parts, our resist formulation is expected to play a critical role in enabling fabrication of functional polymer parts to tight design tolerances.« less

Authors:
ORCiD logo [1];  [1];  [2];  [2];  [3];  [3];  [3];  [3];  [2]
  1. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Materials Engineering Division, Materials Science Division
  2. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Materials Engineering Division
  3. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Materials Science Division
Publication Date:
Research Org.:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1417282
Report Number(s):
LLNL-JRNL-732780
Journal ID: ISSN 1944-8244
Grant/Contract Number:
AC52-07NA27344; AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 10; Journal Issue: 1; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 77 NANOSCIENCE AND NANOTECHNOLOGY; 42 ENGINEERING; additive manufacturing; direct laser writing; multiphoton polymerization; photopolymer; radiopacity; X-ray CT

Citation Formats

Saha, Sourabh K., Oakdale, James S., Cuadra, Jefferson A., Divin, Chuck, Ye, Jianchao, Forien, Jean-Baptiste, Bayu Aji, Leonardus B., Biener, Juergen, and Smith, William L. Radiopaque Resists for Two-Photon Lithography To Enable Submicron 3D Imaging of Polymer Parts via X-ray Computed Tomography. United States: N. p., 2017. Web. doi:10.1021/acsami.7b12654.
Saha, Sourabh K., Oakdale, James S., Cuadra, Jefferson A., Divin, Chuck, Ye, Jianchao, Forien, Jean-Baptiste, Bayu Aji, Leonardus B., Biener, Juergen, & Smith, William L. Radiopaque Resists for Two-Photon Lithography To Enable Submicron 3D Imaging of Polymer Parts via X-ray Computed Tomography. United States. doi:10.1021/acsami.7b12654.
Saha, Sourabh K., Oakdale, James S., Cuadra, Jefferson A., Divin, Chuck, Ye, Jianchao, Forien, Jean-Baptiste, Bayu Aji, Leonardus B., Biener, Juergen, and Smith, William L. 2017. "Radiopaque Resists for Two-Photon Lithography To Enable Submicron 3D Imaging of Polymer Parts via X-ray Computed Tomography". United States. doi:10.1021/acsami.7b12654.
@article{osti_1417282,
title = {Radiopaque Resists for Two-Photon Lithography To Enable Submicron 3D Imaging of Polymer Parts via X-ray Computed Tomography},
author = {Saha, Sourabh K. and Oakdale, James S. and Cuadra, Jefferson A. and Divin, Chuck and Ye, Jianchao and Forien, Jean-Baptiste and Bayu Aji, Leonardus B. and Biener, Juergen and Smith, William L.},
abstractNote = {Two-photon lithography (TPL) is a high-resolution additive manufacturing (AM) technique capable of producing arbitrarily complex three-dimensional (3D) microstructures with features 2–3 orders of magnitude finer than human hair. This process finds numerous applications as a direct route toward the fabrication of novel optical and mechanical metamaterials, miniaturized optics, microfluidics, biological scaffolds, and various other intricate 3D parts. As TPL matures, metrology and inspection become a crucial step in the manufacturing process to ensure that the geometric form of the end product meets design specifications. X-ray-based computed tomography (CT) is a nondestructive technique that can provide this inspection capability for the evaluation of complex internal 3D structure. However, polymeric photoresists commonly used for TPL, as well as other forms of stereolithography, poorly attenuate X-rays due to the low atomic number (Z) of their constituent elements and therefore appear relatively transparent during imaging. We present the development of optically clear yet radiopaque photoresists for enhanced contrast under X-ray CT. We have synthesized iodinated acrylate monomers to formulate high-Z photoresist materials that are capable of forming 3D microstructures with sub-150 nm features. In addition, we have developed a formulation protocol to match the refractive index of the photoresists to the immersion medium of the objective lens so as to enable dip-in laser lithography, a direct laser writing technique for producing millimeter-tall structures. Our radiopaque photopolymer then resists increase X-ray attenuation by a factor of more than 10 times without sacrificing the sub-150 nm feature resolution or the millimeter-scale part height. Thus, our resists can successfully replace existing photopolymers to generate AM parts that are suitable for inspection via X-ray CT. By providing the “feedstock” for radiopaque AM parts, our resist formulation is expected to play a critical role in enabling fabrication of functional polymer parts to tight design tolerances.},
doi = {10.1021/acsami.7b12654},
journal = {ACS Applied Materials and Interfaces},
number = 1,
volume = 10,
place = {United States},
year = 2017,
month =
}

Journal Article:
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