Abstract

We report on the micro-pattering of fluorescent gold nanoclusters embedded in polyvinyl alcohol film using a low-cost continuous-wave laser. We show that the formation of gold nanoclusters requires low-level laser irradiation (<100 W/cm2), corresponding to a sub-microwatt focused beam. This low-intensity requirement enables substantially higher speed and cost-effective light patterning process. As a result of using only small intensities during gold nanoclusters production, no microscopic topological changes were observed in the polymer film. This class of gold nanoclusters potentially finds application in high-speed authenticity marking and similar labeling applications.

© 2019 Optical Society of America under the terms of the OSA Open Access Publishing Agreement

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    [Crossref]

2019 (1)

2018 (1)

G. Ou, J. Zhao, P. Chen, C. Xiong, F. Dong, B. Li, and X. Feng, “Fabrication and application of noble metal nanoclusters as optical sensors for toxic metal ions,” Anal. Bioanal. Chem. 410(10), 2485–2498 (2018).
[Crossref]

2017 (1)

U. D. Madhuri and T. Radhakrishnan, “Gold nanoclusters with a wide range of fluorescence characteristics generated in situ in polymer thin films: potential gas sensing application,” Dalton Trans. 46(46), 16236–16243 (2017).
[Crossref]

2016 (4)

2015 (2)

A. Selimis, V. Mironov, and M. Farsari, “Direct laser writing: Principles and materials for scaffold 3d printing,” Microelectron. Eng. 132, 83–89 (2015).
[Crossref]

L.-Y. Chen, C.-W. Wang, Z. Yuan, and H.-T. Chang, “Fluorescent gold nanoclusters: recent advances in sensing and imaging,” Anal. Chem. 87(1), 216–229 (2015).
[Crossref]

2014 (4)

L. Zhang and E. Wang, “Metal nanoclusters: new fluorescent probes for sensors and bioimaging,” Nano Today 9(1), 132–157 (2014).
[Crossref]

J. Sun and Y. Jin, “Fluorescent au nanoclusters: recent progress and sensing applications,” J. Mater. Chem. C 2(38), 8000–8011 (2014).
[Crossref]

M. Azubel, J. Koivisto, S. Malola, D. Bushnell, G. L. Hura, A. L. Koh, H. Tsunoyama, T. Tsukuda, M. Pettersson, H. Häkkinen, and R. D. Kornberg, “Electron microscopy of gold nanoparticles at atomic resolution,” Science 345(6199), 909–912 (2014).
[Crossref]

P. Kunwar, J. Hassinen, G. Bautista, R. H. Ras, and J. Toivonen, “Direct laser writing of photostable fluorescent silver nanoclusters in polymer films,” ACS Nano 8(11), 11165–11171 (2014).
[Crossref]

2013 (1)

L. Li, Z. Li, H. Zhang, S. Zhang, I. Majeed, and B. Tan, “Effect of polymer ligand structures on fluorescence of gold clusters prepared by photoreduction,” Nanoscale 5(5), 1986–1992 (2013).
[Crossref]

2012 (3)

J. Zheng, C. Zhou, M. Yu, and J. Liu, “Different sized luminescent gold nanoparticles,” Nanoscale 4(14), 4073–4083 (2012).
[Crossref]

S. Han, H. J. Bae, J. Kim, S. Shin, S.-E. Choi, S. H. Lee, S. Kwon, and W. Park, “Lithographically encoded polymer microtaggant using high-capacity and error-correctable qr code for anti-counterfeiting of drugs,” Adv. Mater. 24(44), 5924–5929 (2012).
[Crossref]

J. M. Meruga, W. M. Cross, P. S. May, Q. Luu, G. A. Crawford, and J. J. Kellar, “Security printing of covert quick response codes using upconverting nanoparticle inks,” Nanotechnology 23(39), 395201 (2012).
[Crossref]

2011 (5)

H. Yabu, “One-pot synthesis of blue light-emitting au nanoclusters and formation of photo-patternable composite films,” Chem. Commun. 47(4), 1196–1197 (2011).
[Crossref]

L. Shang, S. Dong, and G. U. Nienhaus, “Ultra-small fluorescent metal nanoclusters: synthesis and biological applications,” Nano Today 6(4), 401–418 (2011).
[Crossref]

C. M. Cobley, J. Chen, E. C. Cho, L. V. Wang, and Y. Xia, “Gold nanostructures: a class of multifunctional materials for biomedical applications,” Chem. Soc. Rev. 40(1), 44–56 (2011).
[Crossref]

S. Shukla, X. Vidal, E. P. Furlani, M. T. Swihart, K.-T. Kim, Y.-K. Yoon, A. Urbas, and P. N. Prasad, “Subwavelength direct laser patterning of conductive gold nanostructures by simultaneous photopolymerization and photoreduction,” ACS Nano 5(3), 1947–1957 (2011).
[Crossref]

I. Díez and R. H. Ras, “Fluorescent silver nanoclusters,” Nanoscale 3(5), 1963–1970 (2011).
[Crossref]

2010 (3)

G. De Cremer, B. F. Sels, J.-i. Hotta, M. B. Roeffaers, E. Bartholomeeusen, E. Coutiño-Gonzalez, V. Valtchev, D. E. De Vos, T. Vosch, and J. Hofkens, “Optical encoding of silver zeolite microcarriers,” Adv. Mater. 22(9), 957–960 (2010).
[Crossref]

A. Royon, K. Bourhis, M. Bellec, G. Papon, B. Bousquet, Y. Deshayes, T. Cardinal, and L. Canioni, “Silver clusters embedded in glass as a perennial high capacity optical recording medium,” Adv. Mater. 22(46), 5282–5286 (2010).
[Crossref]

J. Marqués-Hueso, R. Abargues, J. Canet-Ferrer, S. Agouram, J. L. Valdés, and J. P. Martínez-Pastor, “Au-pva nanocomposite negative resist for one-step three-dimensional e-beam lithography,” Langmuir 26(4), 2825–2830 (2010).
[Crossref]

2009 (5)

R. Gradess, R. Abargues, A. Habbou, J. Canet-Ferrer, E. Pedrueza, A. Russell, J. L. Valdés, and J. P. Martínez-Pastor, “Localized surface plasmon resonance sensor based on ag-pva nanocomposite thin films,” J. Mater. Chem. 19(48), 9233–9240 (2009).
[Crossref]

R. Abargues, R. Gradess, J. Canet-Ferrer, K. Abderrafi, J. L. Valdés, and J. Martínez-Pastor, “Scalable heterogeneous synthesis of metallic nanoparticles and aggregates with polyvinyl alcohol,” New J. Chem. 33(4), 913–917 (2009).
[Crossref]

C. Maurel, T. Cardinal, M. Bellec, L. Canioni, B. Bousquet, M. Treguer, J.-J. Videau, J. Choi, and M. Richardson, “Luminescence properties of silver zinc phosphate glasses following different irradiations,” J. Lumin. 129(12), 1514–1518 (2009).
[Crossref]

M. Sakamoto, T. Tachikawa, M. Fujitsuka, and T. Majima, “Photochemical reactivity of gold clusters: dependence on size and spin multiplicity,” Langmuir 25(24), 13888–13893 (2009).
[Crossref]

C.-A. J. Lin, C.-H. Lee, J.-T. Hsieh, H.-H. Wang, J. K. Li, J.-L. Shen, W.-H. Chan, H.-I. Yeh, and W. H. Chang, “Synthesis of fluorescent metallic nanoclusters toward biomedical application: recent progress and present challenges,” J. Med. Biol. Eng. 29, 276–283 (2009).

2007 (2)

J. Zheng, P. R. Nicovich, and R. M. Dickson, “Highly fluorescent noble-metal quantum dots,” Annu. Rev. Phys. Chem. 58(1), 409–431 (2007).
[Crossref]

N. de Souza, “All that glitters but does not blink,” Nat. Methods 4(7), 540 (2007).
[Crossref]

2005 (2)

Y. Negishi, K. Nobusada, and T. Tsukuda, “Glutathione-protected gold clusters revisited: Bridging the gap between gold (i)- thiolate complexes and thiolate-protected gold nanocrystals,” J. Am. Chem. Soc. 127(14), 5261–5270 (2005).
[Crossref]

K. Esumi, T. Matsumoto, Y. Seto, and T. Yoshimura, “Preparation of gold–, gold/silver–dendrimer nanocomposites in the presence of benzoin in ethanol by uv irradiation,” J. Colloid Interface Sci. 284(1), 199–203 (2005).
[Crossref]

2003 (2)

R. C. Willson and A. V. Mordvinov, “Secular total solar irradiance trend during solar cycles 21–23,” Geophys. Res. Lett. 30(5), 1 (2003).
[Crossref]

K. Kaneko, H.-B. Sun, X.-M. Duan, and S. Kawata, “Two-photon photoreduction of metallic nanoparticle gratings in a polymer matrix,” Appl. Phys. Lett. 83(7), 1426–1428 (2003).
[Crossref]

2001 (1)

S. Kawata, H.-B. Sun, T. Tanaka, and K. Takada, “Finer features for functional microdevices,” Nature 412(6848), 697–698 (2001).
[Crossref]

1996 (1)

Abargues, R.

J. Marqués-Hueso, R. Abargues, J. Canet-Ferrer, S. Agouram, J. L. Valdés, and J. P. Martínez-Pastor, “Au-pva nanocomposite negative resist for one-step three-dimensional e-beam lithography,” Langmuir 26(4), 2825–2830 (2010).
[Crossref]

R. Gradess, R. Abargues, A. Habbou, J. Canet-Ferrer, E. Pedrueza, A. Russell, J. L. Valdés, and J. P. Martínez-Pastor, “Localized surface plasmon resonance sensor based on ag-pva nanocomposite thin films,” J. Mater. Chem. 19(48), 9233–9240 (2009).
[Crossref]

R. Abargues, R. Gradess, J. Canet-Ferrer, K. Abderrafi, J. L. Valdés, and J. Martínez-Pastor, “Scalable heterogeneous synthesis of metallic nanoparticles and aggregates with polyvinyl alcohol,” New J. Chem. 33(4), 913–917 (2009).
[Crossref]

Abderrafi, K.

R. Abargues, R. Gradess, J. Canet-Ferrer, K. Abderrafi, J. L. Valdés, and J. Martínez-Pastor, “Scalable heterogeneous synthesis of metallic nanoparticles and aggregates with polyvinyl alcohol,” New J. Chem. 33(4), 913–917 (2009).
[Crossref]

Agouram, S.

J. Marqués-Hueso, R. Abargues, J. Canet-Ferrer, S. Agouram, J. L. Valdés, and J. P. Martínez-Pastor, “Au-pva nanocomposite negative resist for one-step three-dimensional e-beam lithography,” Langmuir 26(4), 2825–2830 (2010).
[Crossref]

Azubel, M.

M. Azubel, J. Koivisto, S. Malola, D. Bushnell, G. L. Hura, A. L. Koh, H. Tsunoyama, T. Tsukuda, M. Pettersson, H. Häkkinen, and R. D. Kornberg, “Electron microscopy of gold nanoparticles at atomic resolution,” Science 345(6199), 909–912 (2014).
[Crossref]

Bae, H. J.

S. Han, H. J. Bae, J. Kim, S. Shin, S.-E. Choi, S. H. Lee, S. Kwon, and W. Park, “Lithographically encoded polymer microtaggant using high-capacity and error-correctable qr code for anti-counterfeiting of drugs,” Adv. Mater. 24(44), 5924–5929 (2012).
[Crossref]

Bartholomeeusen, E.

G. De Cremer, B. F. Sels, J.-i. Hotta, M. B. Roeffaers, E. Bartholomeeusen, E. Coutiño-Gonzalez, V. Valtchev, D. E. De Vos, T. Vosch, and J. Hofkens, “Optical encoding of silver zeolite microcarriers,” Adv. Mater. 22(9), 957–960 (2010).
[Crossref]

Bautista, G.

P. Kunwar, J. Hassinen, G. Bautista, R. H. Ras, and J. Toivonen, “Sub-micron scale patterning of fluorescent silver nanoclusters using low-power laser,” Sci. Rep. 6(1), 23998 (2016).
[Crossref]

P. Kunwar, L. Turquet, J. Hassinen, R. H. Ras, J. Toivonen, and G. Bautista, “Holographic patterning of fluorescent microstructures comprising silver nanoclusters,” Opt. Mater. Express 6(3), 946–951 (2016).
[Crossref]

P. Kunwar, J. Toivonen, M. Kauranen, and G. Bautista, “Third-harmonic generation imaging of three-dimensional microstructures fabricated by photopolymerization,” Opt. Express 24(9), 9353–9358 (2016).
[Crossref]

P. Kunwar, J. Hassinen, G. Bautista, R. H. Ras, and J. Toivonen, “Direct laser writing of photostable fluorescent silver nanoclusters in polymer films,” ACS Nano 8(11), 11165–11171 (2014).
[Crossref]

Bellec, M.

A. Royon, K. Bourhis, M. Bellec, G. Papon, B. Bousquet, Y. Deshayes, T. Cardinal, and L. Canioni, “Silver clusters embedded in glass as a perennial high capacity optical recording medium,” Adv. Mater. 22(46), 5282–5286 (2010).
[Crossref]

C. Maurel, T. Cardinal, M. Bellec, L. Canioni, B. Bousquet, M. Treguer, J.-J. Videau, J. Choi, and M. Richardson, “Luminescence properties of silver zinc phosphate glasses following different irradiations,” J. Lumin. 129(12), 1514–1518 (2009).
[Crossref]

Bourhis, K.

A. Royon, K. Bourhis, M. Bellec, G. Papon, B. Bousquet, Y. Deshayes, T. Cardinal, and L. Canioni, “Silver clusters embedded in glass as a perennial high capacity optical recording medium,” Adv. Mater. 22(46), 5282–5286 (2010).
[Crossref]

Bousquet, B.

A. Royon, K. Bourhis, M. Bellec, G. Papon, B. Bousquet, Y. Deshayes, T. Cardinal, and L. Canioni, “Silver clusters embedded in glass as a perennial high capacity optical recording medium,” Adv. Mater. 22(46), 5282–5286 (2010).
[Crossref]

C. Maurel, T. Cardinal, M. Bellec, L. Canioni, B. Bousquet, M. Treguer, J.-J. Videau, J. Choi, and M. Richardson, “Luminescence properties of silver zinc phosphate glasses following different irradiations,” J. Lumin. 129(12), 1514–1518 (2009).
[Crossref]

Bushnell, D.

M. Azubel, J. Koivisto, S. Malola, D. Bushnell, G. L. Hura, A. L. Koh, H. Tsunoyama, T. Tsukuda, M. Pettersson, H. Häkkinen, and R. D. Kornberg, “Electron microscopy of gold nanoparticles at atomic resolution,” Science 345(6199), 909–912 (2014).
[Crossref]

Callan, J. P.

Canet-Ferrer, J.

J. Marqués-Hueso, R. Abargues, J. Canet-Ferrer, S. Agouram, J. L. Valdés, and J. P. Martínez-Pastor, “Au-pva nanocomposite negative resist for one-step three-dimensional e-beam lithography,” Langmuir 26(4), 2825–2830 (2010).
[Crossref]

R. Gradess, R. Abargues, A. Habbou, J. Canet-Ferrer, E. Pedrueza, A. Russell, J. L. Valdés, and J. P. Martínez-Pastor, “Localized surface plasmon resonance sensor based on ag-pva nanocomposite thin films,” J. Mater. Chem. 19(48), 9233–9240 (2009).
[Crossref]

R. Abargues, R. Gradess, J. Canet-Ferrer, K. Abderrafi, J. L. Valdés, and J. Martínez-Pastor, “Scalable heterogeneous synthesis of metallic nanoparticles and aggregates with polyvinyl alcohol,” New J. Chem. 33(4), 913–917 (2009).
[Crossref]

Canioni, L.

A. Royon, K. Bourhis, M. Bellec, G. Papon, B. Bousquet, Y. Deshayes, T. Cardinal, and L. Canioni, “Silver clusters embedded in glass as a perennial high capacity optical recording medium,” Adv. Mater. 22(46), 5282–5286 (2010).
[Crossref]

C. Maurel, T. Cardinal, M. Bellec, L. Canioni, B. Bousquet, M. Treguer, J.-J. Videau, J. Choi, and M. Richardson, “Luminescence properties of silver zinc phosphate glasses following different irradiations,” J. Lumin. 129(12), 1514–1518 (2009).
[Crossref]

Cardinal, T.

A. Royon, K. Bourhis, M. Bellec, G. Papon, B. Bousquet, Y. Deshayes, T. Cardinal, and L. Canioni, “Silver clusters embedded in glass as a perennial high capacity optical recording medium,” Adv. Mater. 22(46), 5282–5286 (2010).
[Crossref]

C. Maurel, T. Cardinal, M. Bellec, L. Canioni, B. Bousquet, M. Treguer, J.-J. Videau, J. Choi, and M. Richardson, “Luminescence properties of silver zinc phosphate glasses following different irradiations,” J. Lumin. 129(12), 1514–1518 (2009).
[Crossref]

Chan, W.-H.

C.-A. J. Lin, C.-H. Lee, J.-T. Hsieh, H.-H. Wang, J. K. Li, J.-L. Shen, W.-H. Chan, H.-I. Yeh, and W. H. Chang, “Synthesis of fluorescent metallic nanoclusters toward biomedical application: recent progress and present challenges,” J. Med. Biol. Eng. 29, 276–283 (2009).

Chang, H.-T.

L.-Y. Chen, C.-W. Wang, Z. Yuan, and H.-T. Chang, “Fluorescent gold nanoclusters: recent advances in sensing and imaging,” Anal. Chem. 87(1), 216–229 (2015).
[Crossref]

Chang, W. H.

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A. Royon, K. Bourhis, M. Bellec, G. Papon, B. Bousquet, Y. Deshayes, T. Cardinal, and L. Canioni, “Silver clusters embedded in glass as a perennial high capacity optical recording medium,” Adv. Mater. 22(46), 5282–5286 (2010).
[Crossref]

Russell, A.

R. Gradess, R. Abargues, A. Habbou, J. Canet-Ferrer, E. Pedrueza, A. Russell, J. L. Valdés, and J. P. Martínez-Pastor, “Localized surface plasmon resonance sensor based on ag-pva nanocomposite thin films,” J. Mater. Chem. 19(48), 9233–9240 (2009).
[Crossref]

Sakamoto, M.

M. Sakamoto, T. Tachikawa, M. Fujitsuka, and T. Majima, “Photochemical reactivity of gold clusters: dependence on size and spin multiplicity,” Langmuir 25(24), 13888–13893 (2009).
[Crossref]

Selimis, A.

A. Selimis, V. Mironov, and M. Farsari, “Direct laser writing: Principles and materials for scaffold 3d printing,” Microelectron. Eng. 132, 83–89 (2015).
[Crossref]

Sels, B. F.

G. De Cremer, B. F. Sels, J.-i. Hotta, M. B. Roeffaers, E. Bartholomeeusen, E. Coutiño-Gonzalez, V. Valtchev, D. E. De Vos, T. Vosch, and J. Hofkens, “Optical encoding of silver zeolite microcarriers,” Adv. Mater. 22(9), 957–960 (2010).
[Crossref]

Seto, Y.

K. Esumi, T. Matsumoto, Y. Seto, and T. Yoshimura, “Preparation of gold–, gold/silver–dendrimer nanocomposites in the presence of benzoin in ethanol by uv irradiation,” J. Colloid Interface Sci. 284(1), 199–203 (2005).
[Crossref]

Shang, L.

L. Shang, S. Dong, and G. U. Nienhaus, “Ultra-small fluorescent metal nanoclusters: synthesis and biological applications,” Nano Today 6(4), 401–418 (2011).
[Crossref]

Shen, J.-L.

C.-A. J. Lin, C.-H. Lee, J.-T. Hsieh, H.-H. Wang, J. K. Li, J.-L. Shen, W.-H. Chan, H.-I. Yeh, and W. H. Chang, “Synthesis of fluorescent metallic nanoclusters toward biomedical application: recent progress and present challenges,” J. Med. Biol. Eng. 29, 276–283 (2009).

Shin, S.

S. Han, H. J. Bae, J. Kim, S. Shin, S.-E. Choi, S. H. Lee, S. Kwon, and W. Park, “Lithographically encoded polymer microtaggant using high-capacity and error-correctable qr code for anti-counterfeiting of drugs,” Adv. Mater. 24(44), 5924–5929 (2012).
[Crossref]

Shukla, S.

S. Shukla, X. Vidal, E. P. Furlani, M. T. Swihart, K.-T. Kim, Y.-K. Yoon, A. Urbas, and P. N. Prasad, “Subwavelength direct laser patterning of conductive gold nanostructures by simultaneous photopolymerization and photoreduction,” ACS Nano 5(3), 1947–1957 (2011).
[Crossref]

Sun, H.-B.

K. Kaneko, H.-B. Sun, X.-M. Duan, and S. Kawata, “Two-photon photoreduction of metallic nanoparticle gratings in a polymer matrix,” Appl. Phys. Lett. 83(7), 1426–1428 (2003).
[Crossref]

S. Kawata, H.-B. Sun, T. Tanaka, and K. Takada, “Finer features for functional microdevices,” Nature 412(6848), 697–698 (2001).
[Crossref]

Sun, J.

J. Sun and Y. Jin, “Fluorescent au nanoclusters: recent progress and sensing applications,” J. Mater. Chem. C 2(38), 8000–8011 (2014).
[Crossref]

Swihart, M. T.

S. Shukla, X. Vidal, E. P. Furlani, M. T. Swihart, K.-T. Kim, Y.-K. Yoon, A. Urbas, and P. N. Prasad, “Subwavelength direct laser patterning of conductive gold nanostructures by simultaneous photopolymerization and photoreduction,” ACS Nano 5(3), 1947–1957 (2011).
[Crossref]

Tachikawa, T.

M. Sakamoto, T. Tachikawa, M. Fujitsuka, and T. Majima, “Photochemical reactivity of gold clusters: dependence on size and spin multiplicity,” Langmuir 25(24), 13888–13893 (2009).
[Crossref]

Takada, K.

S. Kawata, H.-B. Sun, T. Tanaka, and K. Takada, “Finer features for functional microdevices,” Nature 412(6848), 697–698 (2001).
[Crossref]

Tan, B.

L. Li, Z. Li, H. Zhang, S. Zhang, I. Majeed, and B. Tan, “Effect of polymer ligand structures on fluorescence of gold clusters prepared by photoreduction,” Nanoscale 5(5), 1986–1992 (2013).
[Crossref]

Tanaka, T.

S. Kawata, H.-B. Sun, T. Tanaka, and K. Takada, “Finer features for functional microdevices,” Nature 412(6848), 697–698 (2001).
[Crossref]

Terakawa, M.

Toivonen, J.

Treguer, M.

C. Maurel, T. Cardinal, M. Bellec, L. Canioni, B. Bousquet, M. Treguer, J.-J. Videau, J. Choi, and M. Richardson, “Luminescence properties of silver zinc phosphate glasses following different irradiations,” J. Lumin. 129(12), 1514–1518 (2009).
[Crossref]

Tsukuda, T.

M. Azubel, J. Koivisto, S. Malola, D. Bushnell, G. L. Hura, A. L. Koh, H. Tsunoyama, T. Tsukuda, M. Pettersson, H. Häkkinen, and R. D. Kornberg, “Electron microscopy of gold nanoparticles at atomic resolution,” Science 345(6199), 909–912 (2014).
[Crossref]

Y. Negishi, K. Nobusada, and T. Tsukuda, “Glutathione-protected gold clusters revisited: Bridging the gap between gold (i)- thiolate complexes and thiolate-protected gold nanocrystals,” J. Am. Chem. Soc. 127(14), 5261–5270 (2005).
[Crossref]

Tsunoyama, H.

M. Azubel, J. Koivisto, S. Malola, D. Bushnell, G. L. Hura, A. L. Koh, H. Tsunoyama, T. Tsukuda, M. Pettersson, H. Häkkinen, and R. D. Kornberg, “Electron microscopy of gold nanoparticles at atomic resolution,” Science 345(6199), 909–912 (2014).
[Crossref]

Turquet, L.

Urbas, A.

S. Shukla, X. Vidal, E. P. Furlani, M. T. Swihart, K.-T. Kim, Y.-K. Yoon, A. Urbas, and P. N. Prasad, “Subwavelength direct laser patterning of conductive gold nanostructures by simultaneous photopolymerization and photoreduction,” ACS Nano 5(3), 1947–1957 (2011).
[Crossref]

Valdés, J. L.

J. Marqués-Hueso, R. Abargues, J. Canet-Ferrer, S. Agouram, J. L. Valdés, and J. P. Martínez-Pastor, “Au-pva nanocomposite negative resist for one-step three-dimensional e-beam lithography,” Langmuir 26(4), 2825–2830 (2010).
[Crossref]

R. Gradess, R. Abargues, A. Habbou, J. Canet-Ferrer, E. Pedrueza, A. Russell, J. L. Valdés, and J. P. Martínez-Pastor, “Localized surface plasmon resonance sensor based on ag-pva nanocomposite thin films,” J. Mater. Chem. 19(48), 9233–9240 (2009).
[Crossref]

R. Abargues, R. Gradess, J. Canet-Ferrer, K. Abderrafi, J. L. Valdés, and J. Martínez-Pastor, “Scalable heterogeneous synthesis of metallic nanoparticles and aggregates with polyvinyl alcohol,” New J. Chem. 33(4), 913–917 (2009).
[Crossref]

Valtchev, V.

G. De Cremer, B. F. Sels, J.-i. Hotta, M. B. Roeffaers, E. Bartholomeeusen, E. Coutiño-Gonzalez, V. Valtchev, D. E. De Vos, T. Vosch, and J. Hofkens, “Optical encoding of silver zeolite microcarriers,” Adv. Mater. 22(9), 957–960 (2010).
[Crossref]

Vidal, X.

S. Shukla, X. Vidal, E. P. Furlani, M. T. Swihart, K.-T. Kim, Y.-K. Yoon, A. Urbas, and P. N. Prasad, “Subwavelength direct laser patterning of conductive gold nanostructures by simultaneous photopolymerization and photoreduction,” ACS Nano 5(3), 1947–1957 (2011).
[Crossref]

Videau, J.-J.

C. Maurel, T. Cardinal, M. Bellec, L. Canioni, B. Bousquet, M. Treguer, J.-J. Videau, J. Choi, and M. Richardson, “Luminescence properties of silver zinc phosphate glasses following different irradiations,” J. Lumin. 129(12), 1514–1518 (2009).
[Crossref]

Vosch, T.

G. De Cremer, B. F. Sels, J.-i. Hotta, M. B. Roeffaers, E. Bartholomeeusen, E. Coutiño-Gonzalez, V. Valtchev, D. E. De Vos, T. Vosch, and J. Hofkens, “Optical encoding of silver zeolite microcarriers,” Adv. Mater. 22(9), 957–960 (2010).
[Crossref]

Wang, C.-W.

L.-Y. Chen, C.-W. Wang, Z. Yuan, and H.-T. Chang, “Fluorescent gold nanoclusters: recent advances in sensing and imaging,” Anal. Chem. 87(1), 216–229 (2015).
[Crossref]

Wang, E.

L. Zhang and E. Wang, “Metal nanoclusters: new fluorescent probes for sensors and bioimaging,” Nano Today 9(1), 132–157 (2014).
[Crossref]

Wang, H.-H.

C.-A. J. Lin, C.-H. Lee, J.-T. Hsieh, H.-H. Wang, J. K. Li, J.-L. Shen, W.-H. Chan, H.-I. Yeh, and W. H. Chang, “Synthesis of fluorescent metallic nanoclusters toward biomedical application: recent progress and present challenges,” J. Med. Biol. Eng. 29, 276–283 (2009).

Wang, L. V.

C. M. Cobley, J. Chen, E. C. Cho, L. V. Wang, and Y. Xia, “Gold nanostructures: a class of multifunctional materials for biomedical applications,” Chem. Soc. Rev. 40(1), 44–56 (2011).
[Crossref]

Willson, R. C.

R. C. Willson and A. V. Mordvinov, “Secular total solar irradiance trend during solar cycles 21–23,” Geophys. Res. Lett. 30(5), 1 (2003).
[Crossref]

Xia, Y.

C. M. Cobley, J. Chen, E. C. Cho, L. V. Wang, and Y. Xia, “Gold nanostructures: a class of multifunctional materials for biomedical applications,” Chem. Soc. Rev. 40(1), 44–56 (2011).
[Crossref]

Xiong, C.

G. Ou, J. Zhao, P. Chen, C. Xiong, F. Dong, B. Li, and X. Feng, “Fabrication and application of noble metal nanoclusters as optical sensors for toxic metal ions,” Anal. Bioanal. Chem. 410(10), 2485–2498 (2018).
[Crossref]

Yabu, H.

H. Yabu, “One-pot synthesis of blue light-emitting au nanoclusters and formation of photo-patternable composite films,” Chem. Commun. 47(4), 1196–1197 (2011).
[Crossref]

Yeh, H.-I.

C.-A. J. Lin, C.-H. Lee, J.-T. Hsieh, H.-H. Wang, J. K. Li, J.-L. Shen, W.-H. Chan, H.-I. Yeh, and W. H. Chang, “Synthesis of fluorescent metallic nanoclusters toward biomedical application: recent progress and present challenges,” J. Med. Biol. Eng. 29, 276–283 (2009).

Yoon, Y.-K.

S. Shukla, X. Vidal, E. P. Furlani, M. T. Swihart, K.-T. Kim, Y.-K. Yoon, A. Urbas, and P. N. Prasad, “Subwavelength direct laser patterning of conductive gold nanostructures by simultaneous photopolymerization and photoreduction,” ACS Nano 5(3), 1947–1957 (2011).
[Crossref]

Yoshimura, T.

K. Esumi, T. Matsumoto, Y. Seto, and T. Yoshimura, “Preparation of gold–, gold/silver–dendrimer nanocomposites in the presence of benzoin in ethanol by uv irradiation,” J. Colloid Interface Sci. 284(1), 199–203 (2005).
[Crossref]

Yu, M.

J. Zheng, C. Zhou, M. Yu, and J. Liu, “Different sized luminescent gold nanoparticles,” Nanoscale 4(14), 4073–4083 (2012).
[Crossref]

Yuan, Z.

L.-Y. Chen, C.-W. Wang, Z. Yuan, and H.-T. Chang, “Fluorescent gold nanoclusters: recent advances in sensing and imaging,” Anal. Chem. 87(1), 216–229 (2015).
[Crossref]

Zhang, H.

L. Li, Z. Li, H. Zhang, S. Zhang, I. Majeed, and B. Tan, “Effect of polymer ligand structures on fluorescence of gold clusters prepared by photoreduction,” Nanoscale 5(5), 1986–1992 (2013).
[Crossref]

Zhang, L.

L. Zhang and E. Wang, “Metal nanoclusters: new fluorescent probes for sensors and bioimaging,” Nano Today 9(1), 132–157 (2014).
[Crossref]

Zhang, S.

L. Li, Z. Li, H. Zhang, S. Zhang, I. Majeed, and B. Tan, “Effect of polymer ligand structures on fluorescence of gold clusters prepared by photoreduction,” Nanoscale 5(5), 1986–1992 (2013).
[Crossref]

Zhao, J.

G. Ou, J. Zhao, P. Chen, C. Xiong, F. Dong, B. Li, and X. Feng, “Fabrication and application of noble metal nanoclusters as optical sensors for toxic metal ions,” Anal. Bioanal. Chem. 410(10), 2485–2498 (2018).
[Crossref]

Zheng, J.

J. Zheng, C. Zhou, M. Yu, and J. Liu, “Different sized luminescent gold nanoparticles,” Nanoscale 4(14), 4073–4083 (2012).
[Crossref]

J. Zheng, P. R. Nicovich, and R. M. Dickson, “Highly fluorescent noble-metal quantum dots,” Annu. Rev. Phys. Chem. 58(1), 409–431 (2007).
[Crossref]

Zhou, C.

J. Zheng, C. Zhou, M. Yu, and J. Liu, “Different sized luminescent gold nanoparticles,” Nanoscale 4(14), 4073–4083 (2012).
[Crossref]

ACS Nano (2)

S. Shukla, X. Vidal, E. P. Furlani, M. T. Swihart, K.-T. Kim, Y.-K. Yoon, A. Urbas, and P. N. Prasad, “Subwavelength direct laser patterning of conductive gold nanostructures by simultaneous photopolymerization and photoreduction,” ACS Nano 5(3), 1947–1957 (2011).
[Crossref]

P. Kunwar, J. Hassinen, G. Bautista, R. H. Ras, and J. Toivonen, “Direct laser writing of photostable fluorescent silver nanoclusters in polymer films,” ACS Nano 8(11), 11165–11171 (2014).
[Crossref]

Adv. Mater. (3)

A. Royon, K. Bourhis, M. Bellec, G. Papon, B. Bousquet, Y. Deshayes, T. Cardinal, and L. Canioni, “Silver clusters embedded in glass as a perennial high capacity optical recording medium,” Adv. Mater. 22(46), 5282–5286 (2010).
[Crossref]

G. De Cremer, B. F. Sels, J.-i. Hotta, M. B. Roeffaers, E. Bartholomeeusen, E. Coutiño-Gonzalez, V. Valtchev, D. E. De Vos, T. Vosch, and J. Hofkens, “Optical encoding of silver zeolite microcarriers,” Adv. Mater. 22(9), 957–960 (2010).
[Crossref]

S. Han, H. J. Bae, J. Kim, S. Shin, S.-E. Choi, S. H. Lee, S. Kwon, and W. Park, “Lithographically encoded polymer microtaggant using high-capacity and error-correctable qr code for anti-counterfeiting of drugs,” Adv. Mater. 24(44), 5924–5929 (2012).
[Crossref]

Anal. Bioanal. Chem. (1)

G. Ou, J. Zhao, P. Chen, C. Xiong, F. Dong, B. Li, and X. Feng, “Fabrication and application of noble metal nanoclusters as optical sensors for toxic metal ions,” Anal. Bioanal. Chem. 410(10), 2485–2498 (2018).
[Crossref]

Anal. Chem. (1)

L.-Y. Chen, C.-W. Wang, Z. Yuan, and H.-T. Chang, “Fluorescent gold nanoclusters: recent advances in sensing and imaging,” Anal. Chem. 87(1), 216–229 (2015).
[Crossref]

Annu. Rev. Phys. Chem. (1)

J. Zheng, P. R. Nicovich, and R. M. Dickson, “Highly fluorescent noble-metal quantum dots,” Annu. Rev. Phys. Chem. 58(1), 409–431 (2007).
[Crossref]

Appl. Phys. Lett. (1)

K. Kaneko, H.-B. Sun, X.-M. Duan, and S. Kawata, “Two-photon photoreduction of metallic nanoparticle gratings in a polymer matrix,” Appl. Phys. Lett. 83(7), 1426–1428 (2003).
[Crossref]

Chem. Commun. (1)

H. Yabu, “One-pot synthesis of blue light-emitting au nanoclusters and formation of photo-patternable composite films,” Chem. Commun. 47(4), 1196–1197 (2011).
[Crossref]

Chem. Soc. Rev. (1)

C. M. Cobley, J. Chen, E. C. Cho, L. V. Wang, and Y. Xia, “Gold nanostructures: a class of multifunctional materials for biomedical applications,” Chem. Soc. Rev. 40(1), 44–56 (2011).
[Crossref]

Dalton Trans. (1)

U. D. Madhuri and T. Radhakrishnan, “Gold nanoclusters with a wide range of fluorescence characteristics generated in situ in polymer thin films: potential gas sensing application,” Dalton Trans. 46(46), 16236–16243 (2017).
[Crossref]

Geophys. Res. Lett. (1)

R. C. Willson and A. V. Mordvinov, “Secular total solar irradiance trend during solar cycles 21–23,” Geophys. Res. Lett. 30(5), 1 (2003).
[Crossref]

J. Am. Chem. Soc. (1)

Y. Negishi, K. Nobusada, and T. Tsukuda, “Glutathione-protected gold clusters revisited: Bridging the gap between gold (i)- thiolate complexes and thiolate-protected gold nanocrystals,” J. Am. Chem. Soc. 127(14), 5261–5270 (2005).
[Crossref]

J. Colloid Interface Sci. (1)

K. Esumi, T. Matsumoto, Y. Seto, and T. Yoshimura, “Preparation of gold–, gold/silver–dendrimer nanocomposites in the presence of benzoin in ethanol by uv irradiation,” J. Colloid Interface Sci. 284(1), 199–203 (2005).
[Crossref]

J. Lumin. (1)

C. Maurel, T. Cardinal, M. Bellec, L. Canioni, B. Bousquet, M. Treguer, J.-J. Videau, J. Choi, and M. Richardson, “Luminescence properties of silver zinc phosphate glasses following different irradiations,” J. Lumin. 129(12), 1514–1518 (2009).
[Crossref]

J. Mater. Chem. (1)

R. Gradess, R. Abargues, A. Habbou, J. Canet-Ferrer, E. Pedrueza, A. Russell, J. L. Valdés, and J. P. Martínez-Pastor, “Localized surface plasmon resonance sensor based on ag-pva nanocomposite thin films,” J. Mater. Chem. 19(48), 9233–9240 (2009).
[Crossref]

J. Mater. Chem. C (1)

J. Sun and Y. Jin, “Fluorescent au nanoclusters: recent progress and sensing applications,” J. Mater. Chem. C 2(38), 8000–8011 (2014).
[Crossref]

J. Med. Biol. Eng. (1)

C.-A. J. Lin, C.-H. Lee, J.-T. Hsieh, H.-H. Wang, J. K. Li, J.-L. Shen, W.-H. Chan, H.-I. Yeh, and W. H. Chang, “Synthesis of fluorescent metallic nanoclusters toward biomedical application: recent progress and present challenges,” J. Med. Biol. Eng. 29, 276–283 (2009).

Langmuir (2)

M. Sakamoto, T. Tachikawa, M. Fujitsuka, and T. Majima, “Photochemical reactivity of gold clusters: dependence on size and spin multiplicity,” Langmuir 25(24), 13888–13893 (2009).
[Crossref]

J. Marqués-Hueso, R. Abargues, J. Canet-Ferrer, S. Agouram, J. L. Valdés, and J. P. Martínez-Pastor, “Au-pva nanocomposite negative resist for one-step three-dimensional e-beam lithography,” Langmuir 26(4), 2825–2830 (2010).
[Crossref]

Microelectron. Eng. (1)

A. Selimis, V. Mironov, and M. Farsari, “Direct laser writing: Principles and materials for scaffold 3d printing,” Microelectron. Eng. 132, 83–89 (2015).
[Crossref]

Nano Today (2)

L. Shang, S. Dong, and G. U. Nienhaus, “Ultra-small fluorescent metal nanoclusters: synthesis and biological applications,” Nano Today 6(4), 401–418 (2011).
[Crossref]

L. Zhang and E. Wang, “Metal nanoclusters: new fluorescent probes for sensors and bioimaging,” Nano Today 9(1), 132–157 (2014).
[Crossref]

Nanoscale (3)

I. Díez and R. H. Ras, “Fluorescent silver nanoclusters,” Nanoscale 3(5), 1963–1970 (2011).
[Crossref]

J. Zheng, C. Zhou, M. Yu, and J. Liu, “Different sized luminescent gold nanoparticles,” Nanoscale 4(14), 4073–4083 (2012).
[Crossref]

L. Li, Z. Li, H. Zhang, S. Zhang, I. Majeed, and B. Tan, “Effect of polymer ligand structures on fluorescence of gold clusters prepared by photoreduction,” Nanoscale 5(5), 1986–1992 (2013).
[Crossref]

Nanotechnology (1)

J. M. Meruga, W. M. Cross, P. S. May, Q. Luu, G. A. Crawford, and J. J. Kellar, “Security printing of covert quick response codes using upconverting nanoparticle inks,” Nanotechnology 23(39), 395201 (2012).
[Crossref]

Nat. Methods (1)

N. de Souza, “All that glitters but does not blink,” Nat. Methods 4(7), 540 (2007).
[Crossref]

Nature (1)

S. Kawata, H.-B. Sun, T. Tanaka, and K. Takada, “Finer features for functional microdevices,” Nature 412(6848), 697–698 (2001).
[Crossref]

New J. Chem. (1)

R. Abargues, R. Gradess, J. Canet-Ferrer, K. Abderrafi, J. L. Valdés, and J. Martínez-Pastor, “Scalable heterogeneous synthesis of metallic nanoparticles and aggregates with polyvinyl alcohol,” New J. Chem. 33(4), 913–917 (2009).
[Crossref]

Opt. Express (2)

Opt. Lett. (2)

Opt. Mater. Express (1)

Sci. Rep. (1)

P. Kunwar, J. Hassinen, G. Bautista, R. H. Ras, and J. Toivonen, “Sub-micron scale patterning of fluorescent silver nanoclusters using low-power laser,” Sci. Rep. 6(1), 23998 (2016).
[Crossref]

Science (1)

M. Azubel, J. Koivisto, S. Malola, D. Bushnell, G. L. Hura, A. L. Koh, H. Tsunoyama, T. Tsukuda, M. Pettersson, H. Häkkinen, and R. D. Kornberg, “Electron microscopy of gold nanoparticles at atomic resolution,” Science 345(6199), 909–912 (2014).
[Crossref]

Other (1)

I. Díez and R. H. Ras, “Few-atom silver clusters as fluorescent reporters,” in Advanced Fluorescence Reporters in Chemistry and Biology II, (Springer, 2010), pp. 307–332.

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Figures (7)

Fig. 1.
Fig. 1. Schematic illustration of laser patterning process on Au-PVA thin films. The desired ratio of gold chloride and PVA sources was dissolved in water, and the resulting aqueous solution was spun cast on a glass coverslip and dried to find a thickness of 50 nm. A CW laser beam with a wavelength of 473 nm was focused on the film to activate localized fluorescent patterns of AuNCs. The components are lenses (L1, L2, L3, L4, and L5), polarizing beamsplitter cube (PBS), beamsplitter cube (BS), mirror (M), dichroic mirror (DM), and microscope objective lens (O).
Fig. 2.
Fig. 2. (a) False-color fluorescence images of an Au-PVA film with Au/OH ratio of 20$\%$, captured at different stages while the sample was exposed to a laser irradiation with 473 nm wavelength and maximum intensity of <100 W/cm$^2$. (b) Fluorescence intensity evolution of 1.28 µm × 1.28 µm square regions of Au-PVA film exposed to different laser intensities. The inset represents the dependence of the NCs formation rate (blue circles) and the fluorescence intensity decay rate (red triangles) with respect to the laser intensity.
Fig. 3.
Fig. 3. Normalized fluorescence intensity evolution pertaining to 1.28 µm x 1.28 µm square regions of an Au-PVA film with 20 % Au/OH ratio, exposed to light beams with different wavelengths. The light intensity was set to be around 30 W/cm2 for all wavelengths.
Fig. 4.
Fig. 4. Emission spectral (a) growth, and (b) decay of AuNCs embedded in PVA film with 20 % Au/OH ratio. The spectra were recorded at different stages when the film was irradiated with a laser beam of 60 µm diameter and maximum intensity of 700 W/cm$^2$.
Fig. 5.
Fig. 5. Emission spectrum (blue symbols) of AuNCs within an Au-PVA film with 30 % Au/OH concentration, excited by 473 nm laser with 60 µm spot diameter and maximum intensity of 1.7 kW/cm$^2$. The emission profile was fit using a two-Gaussian model (red line), where the dashed and dash-dotted lines are the constituent elements. Inset depicts the relation between fluorescence intensity of AuNCs against Au/OH ratio.
Fig. 6.
Fig. 6. (a) A STEM image of a gold-precursor-loaded PVA film with 10 % Au/OH ratio before exposure to laser light. (b) Relative size distribution of AuNCs corresponding to the image shown in (a). (c) A STEM image of an identical film as in (a) but after the exposure to the laser light. (d) Relative size distribution of AuNCs corresponding to several STEM images of exposed Au-PVA film with identical Au/PVA concentration, exposure time and intensity as in (c).
Fig. 7.
Fig. 7. False-color emission images of patterns generated by scanning Au-PVA films against a focused laser beam with 473 nm wavelength. Patterns were written within (a) a film of 10 % Au/OH ratio, with a laser power of 2 µW and a scanning speed of 5 µm/s, and (b) a film of 20 % Au/OH ratio, with a laser power of 0.5 µW and a scanning speed of 2 µm/s. A collimated beam of the same laser used for DLW was exploited to excite the patterns. The white dashed circles indicate the points where the film was aligned with the focal spot of the laser beam.

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