Abstract

A remarkable recent progress in two-photon photopolymerization is the achievement of fabrication resolution around tens of nanometers, establishing a femtosecond laser as a nanofabrication tool. However, how the superresolution has been made possible is still under arguement. We propose a concept of polymer network permeability to solvents, meaning a structure-loosened nanopolymer state that allows free penetration of small molecules to interpret the mechanism. Experimentally, we found proof showing existence of the state, including an unusually large volume shrinkage rate (>60%), shape-memory effect, a giant softness of nanospring, and the mechanical stability of rinsed two-photon written polymer nanowires.

© 2009 Optical Society of America

Full Article  |  PDF Article

References

  • View by:
  • |
  • |
  • |

  1. C. N. LaFratta, J. T. Fourkas, B. T. Baldacchini, and R. A. Farrer, Angew. Chem. 46, 6238 (2007).
    [CrossRef]
  2. J. J. Li and J. T. Fourkas, Mater. Today 10, 30 (2007).
    [CrossRef]
  3. H.-B. Sun, S. Matsuo, and H. Misawa, Appl. Phys. Lett. 74, 786 (1999).
    [CrossRef]
  4. M. Straub and M. Gu, Opt. Lett. 27, 1824 (2002).
    [CrossRef]
  5. Q.-D. Chen, D. Wu, L.-G. Niu, J. Wang, X.-F. Lin, H. Xia, and H.-B. Sun, Appl. Phys. Lett. 91, 171105 (2007).
    [CrossRef]
  6. S. Yokoyama, T. Nakahama, H. Miki, and S. Mashiko, Appl. Phys. Lett. 82, 3221 (2003).
    [CrossRef]
  7. P. Galajda and P. Ormos, Appl. Phys. Lett. 78, 249 (2001).
    [CrossRef]
  8. H.-B. Sun, K. Takada, and S. Kawata, Appl. Phys. Lett. 79, 3173 (2001).
    [CrossRef]
  9. S. Maruo and H. Inoue, Appl. Phys. Lett. 91, 084101 (2007).
    [CrossRef]
  10. S. R. Marder, J. L. Bredas, and J. W. Perry, MRS Bull. 32, 561 (2007).
    [CrossRef]
  11. A. Xie, T. Ito, and D. A. Higgins, Adv. Funct. Mater. 17, 1515 (2007).
    [CrossRef]
  12. J. Kato, N. Takeyasu, Y. Adachi, H.-B. Sun, and S. Kawata, Appl. Phys. Lett. 86, 044102 (2004).
    [CrossRef]
  13. S. Kawata, H.-B. Sun, T. Tanaka, and K. Takada, Nature 412, 697 (2001).
    [CrossRef] [PubMed]
  14. D. Y. Yang, S. H. Park, T. W. Lim, H. J. Kong, S. W. Yi, H. K. Yang, and K. S. Lee, Appl. Phys. Lett. 90, 013113 (2007).
    [CrossRef]
  15. D. F. Tan, Y. Li, F. J. Qi, H. Yang, Q. H. Gong, X. Z. Dong, and X. M. Duan, Appl. Phys. Lett. 90, 071106 (2007).
    [CrossRef]
  16. H.-B. Sun, T. Tanaka, and S. Kawata, Appl. Phys. Lett. 80, 3073 (2002).
  17. S. Nakanishi, S. Shoji, S. Kawata, and H.-B. Sun, Appl. Phys. Lett. 91, 063112 (2007).
    [CrossRef]

2007 (9)

Q.-D. Chen, D. Wu, L.-G. Niu, J. Wang, X.-F. Lin, H. Xia, and H.-B. Sun, Appl. Phys. Lett. 91, 171105 (2007).
[CrossRef]

S. Maruo and H. Inoue, Appl. Phys. Lett. 91, 084101 (2007).
[CrossRef]

S. R. Marder, J. L. Bredas, and J. W. Perry, MRS Bull. 32, 561 (2007).
[CrossRef]

A. Xie, T. Ito, and D. A. Higgins, Adv. Funct. Mater. 17, 1515 (2007).
[CrossRef]

S. Nakanishi, S. Shoji, S. Kawata, and H.-B. Sun, Appl. Phys. Lett. 91, 063112 (2007).
[CrossRef]

C. N. LaFratta, J. T. Fourkas, B. T. Baldacchini, and R. A. Farrer, Angew. Chem. 46, 6238 (2007).
[CrossRef]

J. J. Li and J. T. Fourkas, Mater. Today 10, 30 (2007).
[CrossRef]

D. Y. Yang, S. H. Park, T. W. Lim, H. J. Kong, S. W. Yi, H. K. Yang, and K. S. Lee, Appl. Phys. Lett. 90, 013113 (2007).
[CrossRef]

D. F. Tan, Y. Li, F. J. Qi, H. Yang, Q. H. Gong, X. Z. Dong, and X. M. Duan, Appl. Phys. Lett. 90, 071106 (2007).
[CrossRef]

2004 (1)

J. Kato, N. Takeyasu, Y. Adachi, H.-B. Sun, and S. Kawata, Appl. Phys. Lett. 86, 044102 (2004).
[CrossRef]

2003 (1)

S. Yokoyama, T. Nakahama, H. Miki, and S. Mashiko, Appl. Phys. Lett. 82, 3221 (2003).
[CrossRef]

2002 (2)

H.-B. Sun, T. Tanaka, and S. Kawata, Appl. Phys. Lett. 80, 3073 (2002).

M. Straub and M. Gu, Opt. Lett. 27, 1824 (2002).
[CrossRef]

2001 (3)

P. Galajda and P. Ormos, Appl. Phys. Lett. 78, 249 (2001).
[CrossRef]

H.-B. Sun, K. Takada, and S. Kawata, Appl. Phys. Lett. 79, 3173 (2001).
[CrossRef]

S. Kawata, H.-B. Sun, T. Tanaka, and K. Takada, Nature 412, 697 (2001).
[CrossRef] [PubMed]

1999 (1)

H.-B. Sun, S. Matsuo, and H. Misawa, Appl. Phys. Lett. 74, 786 (1999).
[CrossRef]

Adachi, Y.

J. Kato, N. Takeyasu, Y. Adachi, H.-B. Sun, and S. Kawata, Appl. Phys. Lett. 86, 044102 (2004).
[CrossRef]

Baldacchini, B. T.

C. N. LaFratta, J. T. Fourkas, B. T. Baldacchini, and R. A. Farrer, Angew. Chem. 46, 6238 (2007).
[CrossRef]

Bredas, J. L.

S. R. Marder, J. L. Bredas, and J. W. Perry, MRS Bull. 32, 561 (2007).
[CrossRef]

Chen, Q.-D.

Q.-D. Chen, D. Wu, L.-G. Niu, J. Wang, X.-F. Lin, H. Xia, and H.-B. Sun, Appl. Phys. Lett. 91, 171105 (2007).
[CrossRef]

Dong, X. Z.

D. F. Tan, Y. Li, F. J. Qi, H. Yang, Q. H. Gong, X. Z. Dong, and X. M. Duan, Appl. Phys. Lett. 90, 071106 (2007).
[CrossRef]

Duan, X. M.

D. F. Tan, Y. Li, F. J. Qi, H. Yang, Q. H. Gong, X. Z. Dong, and X. M. Duan, Appl. Phys. Lett. 90, 071106 (2007).
[CrossRef]

Farrer, R. A.

C. N. LaFratta, J. T. Fourkas, B. T. Baldacchini, and R. A. Farrer, Angew. Chem. 46, 6238 (2007).
[CrossRef]

Fourkas, J. T.

C. N. LaFratta, J. T. Fourkas, B. T. Baldacchini, and R. A. Farrer, Angew. Chem. 46, 6238 (2007).
[CrossRef]

J. J. Li and J. T. Fourkas, Mater. Today 10, 30 (2007).
[CrossRef]

Galajda, P.

P. Galajda and P. Ormos, Appl. Phys. Lett. 78, 249 (2001).
[CrossRef]

Gong, Q. H.

D. F. Tan, Y. Li, F. J. Qi, H. Yang, Q. H. Gong, X. Z. Dong, and X. M. Duan, Appl. Phys. Lett. 90, 071106 (2007).
[CrossRef]

Gu, M.

Higgins, D. A.

A. Xie, T. Ito, and D. A. Higgins, Adv. Funct. Mater. 17, 1515 (2007).
[CrossRef]

Inoue, H.

S. Maruo and H. Inoue, Appl. Phys. Lett. 91, 084101 (2007).
[CrossRef]

Ito, T.

A. Xie, T. Ito, and D. A. Higgins, Adv. Funct. Mater. 17, 1515 (2007).
[CrossRef]

Kato, J.

J. Kato, N. Takeyasu, Y. Adachi, H.-B. Sun, and S. Kawata, Appl. Phys. Lett. 86, 044102 (2004).
[CrossRef]

Kawata, S.

S. Nakanishi, S. Shoji, S. Kawata, and H.-B. Sun, Appl. Phys. Lett. 91, 063112 (2007).
[CrossRef]

J. Kato, N. Takeyasu, Y. Adachi, H.-B. Sun, and S. Kawata, Appl. Phys. Lett. 86, 044102 (2004).
[CrossRef]

H.-B. Sun, T. Tanaka, and S. Kawata, Appl. Phys. Lett. 80, 3073 (2002).

H.-B. Sun, K. Takada, and S. Kawata, Appl. Phys. Lett. 79, 3173 (2001).
[CrossRef]

S. Kawata, H.-B. Sun, T. Tanaka, and K. Takada, Nature 412, 697 (2001).
[CrossRef] [PubMed]

Kong, H. J.

D. Y. Yang, S. H. Park, T. W. Lim, H. J. Kong, S. W. Yi, H. K. Yang, and K. S. Lee, Appl. Phys. Lett. 90, 013113 (2007).
[CrossRef]

LaFratta, C. N.

C. N. LaFratta, J. T. Fourkas, B. T. Baldacchini, and R. A. Farrer, Angew. Chem. 46, 6238 (2007).
[CrossRef]

Lee, K. S.

D. Y. Yang, S. H. Park, T. W. Lim, H. J. Kong, S. W. Yi, H. K. Yang, and K. S. Lee, Appl. Phys. Lett. 90, 013113 (2007).
[CrossRef]

Li, J. J.

J. J. Li and J. T. Fourkas, Mater. Today 10, 30 (2007).
[CrossRef]

Li, Y.

D. F. Tan, Y. Li, F. J. Qi, H. Yang, Q. H. Gong, X. Z. Dong, and X. M. Duan, Appl. Phys. Lett. 90, 071106 (2007).
[CrossRef]

Lim, T. W.

D. Y. Yang, S. H. Park, T. W. Lim, H. J. Kong, S. W. Yi, H. K. Yang, and K. S. Lee, Appl. Phys. Lett. 90, 013113 (2007).
[CrossRef]

Lin, X.-F.

Q.-D. Chen, D. Wu, L.-G. Niu, J. Wang, X.-F. Lin, H. Xia, and H.-B. Sun, Appl. Phys. Lett. 91, 171105 (2007).
[CrossRef]

Marder, S. R.

S. R. Marder, J. L. Bredas, and J. W. Perry, MRS Bull. 32, 561 (2007).
[CrossRef]

Maruo, S.

S. Maruo and H. Inoue, Appl. Phys. Lett. 91, 084101 (2007).
[CrossRef]

Mashiko, S.

S. Yokoyama, T. Nakahama, H. Miki, and S. Mashiko, Appl. Phys. Lett. 82, 3221 (2003).
[CrossRef]

Matsuo, S.

H.-B. Sun, S. Matsuo, and H. Misawa, Appl. Phys. Lett. 74, 786 (1999).
[CrossRef]

Miki, H.

S. Yokoyama, T. Nakahama, H. Miki, and S. Mashiko, Appl. Phys. Lett. 82, 3221 (2003).
[CrossRef]

Misawa, H.

H.-B. Sun, S. Matsuo, and H. Misawa, Appl. Phys. Lett. 74, 786 (1999).
[CrossRef]

Nakahama, T.

S. Yokoyama, T. Nakahama, H. Miki, and S. Mashiko, Appl. Phys. Lett. 82, 3221 (2003).
[CrossRef]

Nakanishi, S.

S. Nakanishi, S. Shoji, S. Kawata, and H.-B. Sun, Appl. Phys. Lett. 91, 063112 (2007).
[CrossRef]

Niu, L.-G.

Q.-D. Chen, D. Wu, L.-G. Niu, J. Wang, X.-F. Lin, H. Xia, and H.-B. Sun, Appl. Phys. Lett. 91, 171105 (2007).
[CrossRef]

Ormos, P.

P. Galajda and P. Ormos, Appl. Phys. Lett. 78, 249 (2001).
[CrossRef]

Park, S. H.

D. Y. Yang, S. H. Park, T. W. Lim, H. J. Kong, S. W. Yi, H. K. Yang, and K. S. Lee, Appl. Phys. Lett. 90, 013113 (2007).
[CrossRef]

Perry, J. W.

S. R. Marder, J. L. Bredas, and J. W. Perry, MRS Bull. 32, 561 (2007).
[CrossRef]

Qi, F. J.

D. F. Tan, Y. Li, F. J. Qi, H. Yang, Q. H. Gong, X. Z. Dong, and X. M. Duan, Appl. Phys. Lett. 90, 071106 (2007).
[CrossRef]

Shoji, S.

S. Nakanishi, S. Shoji, S. Kawata, and H.-B. Sun, Appl. Phys. Lett. 91, 063112 (2007).
[CrossRef]

Straub, M.

Sun, H.-B.

Q.-D. Chen, D. Wu, L.-G. Niu, J. Wang, X.-F. Lin, H. Xia, and H.-B. Sun, Appl. Phys. Lett. 91, 171105 (2007).
[CrossRef]

S. Nakanishi, S. Shoji, S. Kawata, and H.-B. Sun, Appl. Phys. Lett. 91, 063112 (2007).
[CrossRef]

J. Kato, N. Takeyasu, Y. Adachi, H.-B. Sun, and S. Kawata, Appl. Phys. Lett. 86, 044102 (2004).
[CrossRef]

H.-B. Sun, T. Tanaka, and S. Kawata, Appl. Phys. Lett. 80, 3073 (2002).

H.-B. Sun, K. Takada, and S. Kawata, Appl. Phys. Lett. 79, 3173 (2001).
[CrossRef]

S. Kawata, H.-B. Sun, T. Tanaka, and K. Takada, Nature 412, 697 (2001).
[CrossRef] [PubMed]

H.-B. Sun, S. Matsuo, and H. Misawa, Appl. Phys. Lett. 74, 786 (1999).
[CrossRef]

Takada, K.

S. Kawata, H.-B. Sun, T. Tanaka, and K. Takada, Nature 412, 697 (2001).
[CrossRef] [PubMed]

H.-B. Sun, K. Takada, and S. Kawata, Appl. Phys. Lett. 79, 3173 (2001).
[CrossRef]

Takeyasu, N.

J. Kato, N. Takeyasu, Y. Adachi, H.-B. Sun, and S. Kawata, Appl. Phys. Lett. 86, 044102 (2004).
[CrossRef]

Tan, D. F.

D. F. Tan, Y. Li, F. J. Qi, H. Yang, Q. H. Gong, X. Z. Dong, and X. M. Duan, Appl. Phys. Lett. 90, 071106 (2007).
[CrossRef]

Tanaka, T.

H.-B. Sun, T. Tanaka, and S. Kawata, Appl. Phys. Lett. 80, 3073 (2002).

S. Kawata, H.-B. Sun, T. Tanaka, and K. Takada, Nature 412, 697 (2001).
[CrossRef] [PubMed]

Wang, J.

Q.-D. Chen, D. Wu, L.-G. Niu, J. Wang, X.-F. Lin, H. Xia, and H.-B. Sun, Appl. Phys. Lett. 91, 171105 (2007).
[CrossRef]

Wu, D.

Q.-D. Chen, D. Wu, L.-G. Niu, J. Wang, X.-F. Lin, H. Xia, and H.-B. Sun, Appl. Phys. Lett. 91, 171105 (2007).
[CrossRef]

Xia, H.

Q.-D. Chen, D. Wu, L.-G. Niu, J. Wang, X.-F. Lin, H. Xia, and H.-B. Sun, Appl. Phys. Lett. 91, 171105 (2007).
[CrossRef]

Xie, A.

A. Xie, T. Ito, and D. A. Higgins, Adv. Funct. Mater. 17, 1515 (2007).
[CrossRef]

Yang, D. Y.

D. Y. Yang, S. H. Park, T. W. Lim, H. J. Kong, S. W. Yi, H. K. Yang, and K. S. Lee, Appl. Phys. Lett. 90, 013113 (2007).
[CrossRef]

Yang, H.

D. F. Tan, Y. Li, F. J. Qi, H. Yang, Q. H. Gong, X. Z. Dong, and X. M. Duan, Appl. Phys. Lett. 90, 071106 (2007).
[CrossRef]

Yang, H. K.

D. Y. Yang, S. H. Park, T. W. Lim, H. J. Kong, S. W. Yi, H. K. Yang, and K. S. Lee, Appl. Phys. Lett. 90, 013113 (2007).
[CrossRef]

Yi, S. W.

D. Y. Yang, S. H. Park, T. W. Lim, H. J. Kong, S. W. Yi, H. K. Yang, and K. S. Lee, Appl. Phys. Lett. 90, 013113 (2007).
[CrossRef]

Yokoyama, S.

S. Yokoyama, T. Nakahama, H. Miki, and S. Mashiko, Appl. Phys. Lett. 82, 3221 (2003).
[CrossRef]

Adv. Funct. Mater. (1)

A. Xie, T. Ito, and D. A. Higgins, Adv. Funct. Mater. 17, 1515 (2007).
[CrossRef]

Angew. Chem. (1)

C. N. LaFratta, J. T. Fourkas, B. T. Baldacchini, and R. A. Farrer, Angew. Chem. 46, 6238 (2007).
[CrossRef]

Appl. Phys. Lett. (11)

J. Kato, N. Takeyasu, Y. Adachi, H.-B. Sun, and S. Kawata, Appl. Phys. Lett. 86, 044102 (2004).
[CrossRef]

H.-B. Sun, S. Matsuo, and H. Misawa, Appl. Phys. Lett. 74, 786 (1999).
[CrossRef]

Q.-D. Chen, D. Wu, L.-G. Niu, J. Wang, X.-F. Lin, H. Xia, and H.-B. Sun, Appl. Phys. Lett. 91, 171105 (2007).
[CrossRef]

S. Yokoyama, T. Nakahama, H. Miki, and S. Mashiko, Appl. Phys. Lett. 82, 3221 (2003).
[CrossRef]

P. Galajda and P. Ormos, Appl. Phys. Lett. 78, 249 (2001).
[CrossRef]

H.-B. Sun, K. Takada, and S. Kawata, Appl. Phys. Lett. 79, 3173 (2001).
[CrossRef]

S. Maruo and H. Inoue, Appl. Phys. Lett. 91, 084101 (2007).
[CrossRef]

D. Y. Yang, S. H. Park, T. W. Lim, H. J. Kong, S. W. Yi, H. K. Yang, and K. S. Lee, Appl. Phys. Lett. 90, 013113 (2007).
[CrossRef]

D. F. Tan, Y. Li, F. J. Qi, H. Yang, Q. H. Gong, X. Z. Dong, and X. M. Duan, Appl. Phys. Lett. 90, 071106 (2007).
[CrossRef]

H.-B. Sun, T. Tanaka, and S. Kawata, Appl. Phys. Lett. 80, 3073 (2002).

S. Nakanishi, S. Shoji, S. Kawata, and H.-B. Sun, Appl. Phys. Lett. 91, 063112 (2007).
[CrossRef]

Mater. Today (1)

J. J. Li and J. T. Fourkas, Mater. Today 10, 30 (2007).
[CrossRef]

MRS Bull. (1)

S. R. Marder, J. L. Bredas, and J. W. Perry, MRS Bull. 32, 561 (2007).
[CrossRef]

Nature (1)

S. Kawata, H.-B. Sun, T. Tanaka, and K. Takada, Nature 412, 697 (2001).
[CrossRef] [PubMed]

Opt. Lett. (1)

Cited By

OSA participates in CrossRef's Cited-By Linking service. Citing articles from OSA journals and other participating publishers are listed here.

Alert me when this article is cited.


Figures (4)

Fig. 1
Fig. 1

Suspended array of wires. (a) SEM images. The exposure duration of the ended and the central segments are, under a laser pulse energy of 75 pJ at the focal spot, 8 and 2 ms , respectively. The left inset illustrates the fiber dimensions related to the focused laser beam. (b) Tilted view of the entire construction. (c) Array of wires under weaker exposure, i.e., the exposure duration is 1 ms .

Fig. 2
Fig. 2

Size-dependent polymer shrinkage: (a) size of wires produced under conditions described in Fig. 1 versus rinsing time by different solvents; (b) SEM images of suspended wires of varied laterals size; (c) reference wires with the same sizes and shapes as in (b), which are affixed to a glass substrate; (d) shrinkage rate dependent on the lateral sizes of wires. The lateral axis is the size of the reference wires.

Fig. 3
Fig. 3

Axial shrinkage of polymer wires. (a) and (b) Optical microscopic image of the suspended and the reference bent wires, respectively, both before rinsing. The inset is an SEM image of the reference sample. (c) and (d) Top- and tilt-view SEM images of the same wires as those in (a) after rinsing and dried. (e) and (f) Bent wires with larger lateral sizes 0.95 and 1.3 μ m , respectively. The insets are the SEM images of the corresponding structures.

Fig. 4
Fig. 4

Shape-memory effect of the wires. (a) Optical microscopic images of the same structures as Fig. 3c after rinsing. (b) Same structure after immersing into the solvent of ethanol.

Metrics