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A novel tri-layer approach for immobilizing metal nanoparticles in SiO2 supports is presented. In this work, we show that under rapid heating to temperatures of approximately 1, 000 ℃, metal nanoparticles less than 15 nm in size will entrench in the SiO2 layer on a silicon wafer to create pores as deep as 250 nm. We studied and characterized this entrenching behavior and subsequent nanopore formation for a wide variety of metal nanoparticles, including Au, Ag, Pt, Pd, and Cu. We also demonstrate that an Al2O3 layer acts as a barrier to such pore formation. Thus, by creating a tri-layer architecture consisting of SiO2 on Al2O3 on silicon wafers, we can control the depth to which nanoparticles entrench between 3-5 nm. This small range allows one to entrench particles for the purpose of immobilization but still present them above the surface. The two advances of moving into the sub-15 nm size regime and of controlled particle immobilization through entrenchment have important implications in studying site-isolated and stabilized metal nanoparticles for applications in sensing, separations, and catalysis.


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A tri-layer approach to controlling nanopore formation in oxide supports

Show Author's information Abha A. Gosavi1,2James L. Hedrick1,2Peng-Cheng Chen2,3Justin M. Notestein1( )Chad A. Mirkin1,2,3,4( )
Department of Chemical and Biological Engineering,Northwestern University, 2145 Sheridan Road, Evanston,Illinois,60208,USA;
International Institute for Nanotechnology,Northwestern University, 2145 Sheridan Road,Evanston, Illinois,60208,USA;
,,,,; Department of Materials Science and Engineering, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, USA
,,,,; Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, USA

Abstract

A novel tri-layer approach for immobilizing metal nanoparticles in SiO2 supports is presented. In this work, we show that under rapid heating to temperatures of approximately 1, 000 ℃, metal nanoparticles less than 15 nm in size will entrench in the SiO2 layer on a silicon wafer to create pores as deep as 250 nm. We studied and characterized this entrenching behavior and subsequent nanopore formation for a wide variety of metal nanoparticles, including Au, Ag, Pt, Pd, and Cu. We also demonstrate that an Al2O3 layer acts as a barrier to such pore formation. Thus, by creating a tri-layer architecture consisting of SiO2 on Al2O3 on silicon wafers, we can control the depth to which nanoparticles entrench between 3-5 nm. This small range allows one to entrench particles for the purpose of immobilization but still present them above the surface. The two advances of moving into the sub-15 nm size regime and of controlled particle immobilization through entrenchment have important implications in studying site-isolated and stabilized metal nanoparticles for applications in sensing, separations, and catalysis.

Keywords: atomic force microscopy, Au nanoparticles, nanopore formation, nanoparticle entrenchment, nanoparticle stabilization

References(53)

1

Ajayan, P. M.; Marks, L. D. Evidence for sinking of small particles into substrates and implications for heterogeneous catalysis. Nature 1989, 338, 139-141.

2

Bábor, P.; Duda, R.; Polčák, J.; Průša, S.; Potoček, M.; Varga, P.; Čechal, J.; Šikola, T. Real-time observation of self-limiting SiO2/Si decomposition catalysed by gold silicide droplets. RSC Adv. 2015, 5, 101726-101731.

3

Ghetta, V.; Chatain, D. Morphologies adopted by Al2O3 single-crystal surfaces in contact with Cu droplets. J. Am. Ceram. Soc. 2004, 85, 961-964.

4

Curiotto, S.; Chien, H.; Meltzman, H.; Labat, S.; Wynblatt, P.; Rohrer, G. S.; Kaplan, W. D.; Chatain, D. Copper crystals on the (1120) sapphire plane: Orientation relationships, triple line ridges and interface shape equilibrium. J. Mater. Sci. 2013, 48, 3013-3026.

5

de Vreede, L. J.; Schmidt Muniz, M.; Van Den Berg, A.; Eijkel, J. C. T. Nanopore fabrication in silicon oxynitride membranes by heating Au-particles. J. Micromech. Microeng. 2016, 26, 037001.

6

de Vreede, L. J.; Van Den Berg, A.; Eijkel, J. C. T. Nanopore fabrication by heating au particles on ceramic substrates. Nano Lett. 2015, 15, 727-731.

7

Ilkiv, I.; Kotlyar, K.; Amel'chuk, D.; Lebedev, S.; Cirlin, G.; Bouravleuv, A. Thermal penetration of gold nanoparticles into silicon dioxide. Acta Phys. Pol. A 2017, 132, 366-368.

8

Ono, L. K.; Behafarid, F.; Cuenya, B. R. Nano-gold diggers: Au-Assisted SiO2-decomposition and desorption in supported nanocatalysts. ACS Nano 2013, 7, 10327-10334.

9

Sui, M.; Pandey, P.; Li, M. Y.; Zhang, Q. Z.; Kunwar, S.; Lee, J. Au-assisted fabrication of nano-holes on c-plane sapphire via thermal treatment guided by Au nanoparticles as catalysts. Appl. Surf. Sci. 2017, 393, 23-29.

10

Spatz, J. P.; Mössmer, S.; Hartmann, C.; Möller, M.; Herzog, T.; Krieger, M.; Boyen, H. G.; Ziemann, P.; Kabius, B. Ordered deposition of inorganic clusters from micellar block copolymer films. Langmuir 2000, 16, 407-415.

11

McBrayer, J. D.; Swanson, R. M.; Sigmon, T. W. Diffusion of metals in silicon dioxide. J. Electrochem. Soc. 1986, 133, 1242-1246.

12

Tauster, S. J.; Fung, S. C.; Garten, R. L. Strong metal-support interactions. group 8 noble metals supported on titanium dioxide. J. Am. Chem. Soc. 1978, 100, 170-175.

13

Pesty, F.; Steinrück, H. P.; Madey, T. E. Thermal stability of Pt films on TiO2(110): Evidence for encapsulation. Surf. Sci. 1995, 339, 83-95.

14

Schleich, B.; Schmeisser, D.; Göpel, W. Structure and reactivity of the system Si/SiO2/Pd: A combined XPS, UPS and HREELS study. Surf. Sci. 1987, 191, 367-384.

15

Kunwar, S.; Pandey, P.; Sui, M.; Zhang, Q. Z.; Li, M. Y.; Lee, J. Effect of systematic control of Pd thickness and annealing temperature on the fabrication and evolution of palladium nanostructures on Si (111) via the solid state dewetting. Nanoscale Res. Lett. 2017, 12, 364.

16

Mei, Q. S.; Lu, K. Melting and superheating of crystalline solids: From bulk to nanocrystals. Prog. Mater. Sci. 2007, 52, 1175-1262.

17

Carnevali, P.; Ercolessi, F.; Tosatti, E. Melting and nonmelting behavior of the Au(111) surface. Phys. Rev. B 1987, 36, 6701-6704.

18

Chatain, D.; Curiotto, S.; Wynblatt, P.; Meltzman, H.; Kaplan, W. D.; Rohrer, G. S. Orientation relationships of copper crystals on sapphire (1010) m-plane and (1012) r-plane substrates. J. Cryst. Growth 2015, 418, 57-63.

19

Saiz, E.; Tomsia, A. P.; Cannon, R. M. Ridging effects on wetting and spreading of liquids on solids. Acta Mater. 1998, 46, 2349-2361.

20

Saiz, E.; Cannon, R. M.; Tomsia, A. P. Reactive spreading in ceramic/metal systems. Oil Gas Sci. Technol. 2001, 56, 89-96.

21

Pretorius, R.; Harris, J. M.; Nicolet, M. A. Reaction of thin metal films with SiO2 substrates. Solid-State Electron. 1978, 21, 667-675.

22

Karakouz, T.; Maoz, B. M.; Lando, G.; Vaskevich, A.; Rubinstein, I. Stabilization of gold nanoparticle films on glass by thermal embedding. ACS Appl. Mater. Interfaces 2011, 3, 978-987.

23

Karakouz, T.; Tesler, A. B.; Bendikov, T. A.; Vaskevich, A.; Rubinstein, I. Highly stable localized plasmon transducers obtained by thermal embedding of gold island films on glass. Adv. Mater. 2008, 20, 3893-3899.

24

Karakouz, T.; Tesler, A. B.; Sannomiya, T.; Feldman, Y.; Vaskevich, A.; Rubinstein, I. Mechanism of morphology transformation during annealing of nanostructured gold films on glass. Phys. Chem. Chem. Phys. 2013, 15, 4656-4665.

25

Malyi, O.; Rabkin, E. The effect of evaporation on size and shape evolution of faceted gold nanoparticles on sapphire. Acta Mater. 2012, 60, 261-268.

26

Meng, G.; Yanagida, T.; Kanai, M.; Suzuki, M.; Nagashima, K.; Xu, B.; Zhuge, F. W.; Klamchuen, A.; He, Y.; Rahong, S. et al. Pressure-induced evaporation dynamics of gold nanoparticles on oxide substrate. Phys. Rev. E 2013, 87, 012405.

27

Lee, J.; Pandey, P.; Sui, M.; Li, M. Y.; Zhang, Q. Z.; Kunwar, S. Evolution of self-assembled Au NPs by controlling annealing temperature and dwelling time on sapphire (0001). Nanoscale Res. Lett. 2015, 10, 494.

28

Johnson, L. E.; Sushko, P. V.; Tomota, Y.; Hosono, H. Electron anions and the glass transition temperature. Proc. Natl. Acad. Sci. USA 2016, 113, 10007-10012.

29

Nascimento M. L. F.; Zanotto, E. D. Diffusion processes in vitreous silica revisited. Phys. Chem. Glasses: Eur. J. Glass Sci. Technol. B 2007, 48, 201-217.

30

Ojovan, M. I. Configurons: Thermodynamic parameters and symmetry changes at glass transition. Entropy 2008, 10, 334-364.

31

Rouxel, T.; Sanglebœuf, J. C. The brittle to ductile transition in a soda-lime-silica glass. J. Non. Cryst. Solids 2000, 271, 224-235.

32

Perez, J.; Duperray, B.; Lefevre, D. Viscoelastic behaviour of an oxide glass near the glass transition temperature. J. Non. Cryst. Solids 1981, 44, 113-136.

33

Kiyonaga, T.; Jin, Q. L.; Kobayashi, H.; Tada, H. Size-dependence of catalytic activity of gold nanoparticles loaded on titanium (IV) dioxide for hydrogen peroxide decomposition. ChemPhysChem 2009, 10, 2935-2938.

34

Beck, I. E.; Bukhtiyarov, V. I.; Pakharukov, I. Y.; Zaikovsky, V. I.; Kriventsov, V. V.; Parmon, V. N. Platinum nanoparticles on Al2O3: Correlation between the particle size and activity in total methane oxidation. J. Catal. 2009, 268, 60-67.

35

Reske, R.; Mistry, H.; Behafarid, F.; Roldan Cuenya, B.; Strasser, P. Particle size effects in the catalytic electroreduction of CO2 on Cu nanoparticles. J. Am. Chem. Soc. 2014, 136, 6978-6986.

36

Overbury, S. H.; Schwartz, V.; Mullins, D. R.; Yan, W. F.; Dai, S. Evaluation of the Au size effect: CO oxidation catalyzed by Au/TiO2. J. Catal. 2006, 241, 56-65.

37

Chai, J. N.; Huo, F. W.; Zheng, Z. J.; Giam, L. R.; Shim, W.; Mirkin, C. A. Scanning probe block copolymer lithography. Proc. Natl. Acad. Sci. USA 2010, 107, 20202-20206.

38

Chen, P. C.; Liu, G. L.; Zhou, Y.; Brown, K. A.; Chernyak, N.; Hedrick, J. L.; He, S.; Xie, Z.; Lin, Q. Y.; Dravid, V. P. et al. Tip-directed synthesis of multimetallic nanoparticles. J. Am. Chem. Soc. 2015, 137, 9167-9173.

39

Chen, P. C.; Liu, X. L.; Hedrick, J. L.; Xie, Z.; Wang, S. Z.; Lin, Y. Q.; Hersam, M. C.; Dravid, V. P.; Mirkin, C. A. Polyelemental nanoparticle libraries. Science 2016, 352, 1565-1569.

40

Hedrick, J. L.; Brown, K. A.; Kluender, E. J.; Cabezas, M. D.; Chen, P. C.; Mirkin, C. A. Hard transparent arrays for polymer pen lithography. ACS Nano 2016, 10, 3144-3148.

41

Huo, F. W.; Zheng, Z. J.; Zheng, G. F.; Giam, L. R.; Zhang, H.; Mirkin, C. A. Polymer pen lithography. Science 2008, 321, 1658-1660.

42

Huang, N.; Xu, Y. H.; Jiang, D. L. High-performance heterogeneous catalysis with surface-exposed stable metal nanoparticles. Sci. Rep. 2014, 4, 7228.

43

Behafarid, F.; Roldan Cuenya, B. Towards the understanding of sintering phenomena at the nanoscale: Geometric and environmental effects. Top. Catal. 2013, 56, 1542-1559.

44

Liao, J. H.; Zhang, Y.; Yu, W.; Xu, L. N.; Ge, C. W.; Liu, J. H.; Gu, N. Linear aggregation of gold nanoparticles in ethanol. Colloids Surf A: Physicochem. Eng. Aspects 2003, 223, 177-183.

45

Jochem, A. R.; Ankah, G. N.; Meyer, L. A.; Elsenberg, S.; Johann, C.; Kraus, T. Colloidal mechanisms of gold nanoparticle loss in asymmetric flow field-flow fractionation. Anal. Chem. 2016, 88, 10065-10073.

46

Striemer, C. C.; Gaborski, T. R.; McGrath, J. L.; Fauchet, P. M. Charge- and size-based separation of macromolecules using ultrathin silicon membranes. Nature 2007, 445, 749-753.

47

Howorka, S.; Siwy, Z. Nanopore analytics: Sensing of single molecules. Chem. Soc. Rev. 2009, 38, 2360-2384.

48

Shendure, J.; Ji, H. Next-generation DNA sequencing. Nat. Biotechnol. 2008, 26, 1135-1145.

49

Li, Y. Q.; Bastakoti, B. P.; Imura, M.; Hwang, S. M.; Sun, Z. Q.; Kim, J. H.; Dou, S. X.; Yamauchi, Y. Synthesis of mesoporous TiO2/SiO2 hybrid films as an efficient photocatalyst by polymeric micelle assembly. Chem. —Eur. J. 2014, 20, 6027-6032.

50

Spinney, P. S.; Howitt, D. G.; Smith, R. L.; Collins, S. D. Nanopore formation by low-energy focused electron beam machining. Nanotechnology 2010, 21, 375301.

51

Tsujino, K.; Matsumura, M. Boring deep cylindrical nanoholes in silicon using silver nanoparticles as a catalyst. Adv. Mater. 2005, 17, 1045-1047.

52

Chartier, C.; Bastide, S.; Lévy-Clément, C. Metal-assisted chemical etching of silicon in HF-H2O2. Electrochim. Acta 2008, 53, 5509-5516.

53

Tsujino, K.; Matsumura, M. Morphology of nanoholes formed in silicon by wet etching in solutions containing HF and H2O2 at different concentrations using silver nanoparticles as catalysts. Electrochim. Acta 2007, 53, 28-34.

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Publication history
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Acknowledgements

Publication history

Received: 02 January 2019
Revised: 28 January 2019
Accepted: 02 February 2019
Published: 29 May 2019
Issue date: June 2019

Copyright

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2019

Acknowledgements

Acknowledgements

This material is based upon work supported by the Sherman Fairchild Foundation, Inc. and the Air Force Office of Scientific Research under Award number FA9550-16-1-0150. J. L. H. was supported by the Department of Defense (DoD) through the National Defense Science & Engineering Graduate Fellowship (NDSEG). P. C. C. acknowledges support from the Cabell Terminal Year Fellowship from Northwestern University. This work made use of the EPIC and SPID facilities of Northwestern University's NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205); the MRSEC program (NSF DMR-1121262) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN. This work utilized Northwestern University Micro/Nano Fabrication Facility (NUFAB), which is partially supported by Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the Materials Research Science and Engineering Center (DMR-1720139), the State of Illinois, and Northwestern University.

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