The lateral spatial resolution (LSR) in two-photon induced polymerization was improved to 80nm by using an anthracene derivative (9,10-bis-pentyloxy-2,7-bis[2-(4-dimethylamino-phenyl)-vinyl]anthracene (BPDPA)) as a highly sensitive and efficient photoinitiator. Photocurable resin containing 0.18mol% BPDPA exhibited a low polymerization threshold of 0.64mW at 800nm. Theoretical calculations showed that the LSR can be increased by reducing the laser power, indicating that the LSR could be improved using more sensitive initiators in the future.
A series of C(2v) symmetrical two-photon absorption compounds with anthracene core, 2,7-bis[2-(4-substituted phenyl)-vinyl]-9,10-dipentyloxyanthracenes designated as I, II and III (the substituted groups at the 4-position of phenyl of I, II and III were dimethylamino, methyl and cyano, respectively) were designed and synthesized as initiators in two-photon induced polymerization (TPIP). The anthracene ring was modified by linking vinylphenyl groups to the 2,7-position to extend conjugation system length and two pentyloxy groups to the 9,10-position to serve as electronic donors. Two-photon absorption cross section of I was around 300 GM, which was much larger than the 10 GM of II and 29 GM of III at 800 nm. I of 0.18% molar ratio in resin composed of methacrylic acid and dipentaerythritol hexaacrylate exhibited a dramatically low threshold of 0.64 mW compared with commercial photoinitiator benzil at a scanning speed 10 μm s(-1). Moreover, the threshold of photoinitiator I was only increased to 2.53 mW at a scanning speed of 1000 μm s(-1). The dependency of threshold on the concentration and exposure time was in accordance with theoretical calculation. Finally, a reasonable mechanism of the two-photon initiating process was proposed. This study provides good prospects for developing low threshold photoinitiator in TPIP.
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