J. Semicond. > Volume 41 > Issue 3 > Article Number: 032303

Enhancement of photocatalytic activity by femtosecond-laser induced periodic surface structures of Si

P. Satapathy 1, , A. Pfuch 2, , R. Grunwald 3, and S. K. Das 1, ,

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Abstract: Laser induced periodic surface structures (LIPSS) represent a kind of top down approach to produce highly reproducible nano/microstructures without going for any sophisticated process of lithography. This method is much simpler and cost effective. In this work, LIPSS on Si surfaces were generated using femtosecond laser pulses of 800 nm wavelength. Photocatalytic substrates were prepared by depositing TiO2 thin films on top of the structured and unstructured Si wafer. The coatings were produced by sputtering from a Ti target in two different types of oxygen atmospheres. In first case, the oxygen pressure within the sputtering chamber was chosen to be high (3 × 10–2 mbar) whereas it was one order of magnitude lower in second case (2.1 × 10–3 mbar). In photocatalytic dye decomposition study of Methylene blue dye it was found that in the presence of LIPSS the activity can be enhanced by 2.1 and 3.3 times with high pressure and low pressure grown TiO2 thin films, respectively. The increase in photocatalytic activity is attributed to the enlargement of effective surface area. In comparative study, the dye decomposition rates of TiO2 thin films grown on LIPSS are found to be much higher than the value for standard reference thin film material Pilkington ActivTM.

Key words: laser induced periodic surface structuresnanoripplessiliconphotocatalytic dye decompositionTiO2 thin filmfemtosecond laser pulses

Abstract: Laser induced periodic surface structures (LIPSS) represent a kind of top down approach to produce highly reproducible nano/microstructures without going for any sophisticated process of lithography. This method is much simpler and cost effective. In this work, LIPSS on Si surfaces were generated using femtosecond laser pulses of 800 nm wavelength. Photocatalytic substrates were prepared by depositing TiO2 thin films on top of the structured and unstructured Si wafer. The coatings were produced by sputtering from a Ti target in two different types of oxygen atmospheres. In first case, the oxygen pressure within the sputtering chamber was chosen to be high (3 × 10–2 mbar) whereas it was one order of magnitude lower in second case (2.1 × 10–3 mbar). In photocatalytic dye decomposition study of Methylene blue dye it was found that in the presence of LIPSS the activity can be enhanced by 2.1 and 3.3 times with high pressure and low pressure grown TiO2 thin films, respectively. The increase in photocatalytic activity is attributed to the enlargement of effective surface area. In comparative study, the dye decomposition rates of TiO2 thin films grown on LIPSS are found to be much higher than the value for standard reference thin film material Pilkington ActivTM.

Key words: laser induced periodic surface structuresnanoripplessiliconphotocatalytic dye decompositionTiO2 thin filmfemtosecond laser pulses



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Chang H W, Tsai Y C, Cheng C W, et al. Nanostructured Ag surface fabricated by femtosecond laser for surface-enhanced Raman scattering. J Colloid Interface Sci, 2011, 360, 305

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Messaoudi H, Das S K, Lange J, et al. Femtosecond-laser induced periodic surface structures for surface enhanced Raman spectroscopy of biomolecules. In: Progress in Nonlinear Nano-Optics. Basel: Springer International Publishing, 2014, 207

[3]

Long J, Fan P, Zhong M, et al. Superhydrophobic and colorful copper surfaces fabricated by picosecond laser induced periodic nanostructures. Appl Surf Sci, 2014, 31, 461

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Wang Z, Zhao Q, Wang C. Reduction of friction of metals using laser-induced periodic surface nanostructures. Micromachines, 2015, 6, 1606

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Vorobyev A Y, Guo C. Colorizing metals with femtosecond laser pulses. Appl Phys Lett, 2008, 92, 041914

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Dusser B, Sagan Z, Soder H, et al. Controlled nanostructrures formation by ultra fast laser pulses for color marking. Opt Exp, 2010, 18, 2913

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Vorobyev A Y, Makin V S, Guo C. Brighter light sources from black metal: significant increase in emission efficiency of incandescent light sources. Phys Rev Lett, 2009, 102, 234301

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Hwang T Y, Vorobyev A Y, Guo C. Surface-plasmon-enhanced photoelectron emission from nanostructure-covered periodic grooves on metals. Phys Rev B, 2009, 79, 085425

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Itina R T E, Vervisch V, Halbwax M, et al. Study on laser induced periodic structures and photovoltaic application. AIP Conf Proc, 2010, 1278, 576

[10]

Chen J T, Lai W C, Kao Y J, et al. Laser-induced periodic structures for light extraction efficiency enhancement of GaN-based light emitting diodes. Opt Express, 2012, 20, 5689

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Das S K, Andreev A, Messaoudi H, et al. Highly periodic laser-induced nanostructures on thin Ti and Cu foils for potential application in laser ion acceleration. J Appl Phys, 2016, 119, 13101

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Baldacchini T, Carey J E, Zhou M, et al. Superhydrophobic surfaces prepared by microstructuring of silicon using a femtosecond laser. Langmuir, 2006, 22, 4917

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Shimotsuma Y, Sakakura M, Miura K, et al. Application of femtosecond-laser induced nanostructures in optical memory. J Nanosci Nanotech, 2007, 7, 94

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Yang C, Dong W, Cui G, et al. Highly-efficient photocatalytic degradation of methylene blue by PoPD-modified TiO2 nanocomposites due to photosensitization-synergetic effect of TiO2 with PoPD. Sci Rep, 2017, 7, 3973

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Julkapli N, Bagheri S, Hamid S B A. Recent advances in heterogeneous photocatalytic decolorization of synthetic dyes. Sci World J, 2014, 692307

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Tölke T, Heft A, Pfuch A. Photocatalytically active multi-layer systems with enhanced transmission. Thin Solid Films, 2008, 516, 4578

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Tölke T, Kriltz A, Rechtenbach A. The influence of pressure on the structure and the self-cleaning properties of sputter deposited TiO2 layers. Thin Solid Films, 2010, 518, 4242

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Granados E, Calderon M M, Krzywinski J, et al. Enhancement of surface area and wettability properties of boron doped diamond by femtosecond laser-induced periodic surface structuring. Opt Mat Exp, 2017, 7, 3389

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Kuladeep R, Sahoo C, Rao D N. Direct writing of continuous and discontinuous sub-wavelength periodic surface structures on single-crystalline silicon using femtosecond laser. Appl Phys Lett, 2014, 104, 222103

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Chen J, Wang W, Li W, et al. Roles of crystal surface in Pt-loaded titania for photocatalytic conversion of organic pollutants: a first-principle theoretical calculation. ACS Appl Mater Interfaces, 2015, 7, 12671

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Marelli M, Evangelisti C, Diamanti M V, et al. TiO2 nanotubes arrays loaded with ligand-free Au nanoparticles: enhancement in photocatalytic activity. ACS Appl Mater Interfaces, 2016, 8, 31051

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Wang H L, Liu X H. Preparation of silver nanoparticle loaded mesoporous TiO2 and its photocatalytic property. J Inorg Mater, 2016, 31, 555

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Cheng H, Hsu C, Chen Y. Substrate materials and deposition temperature dependent growth characteristics and photocatalytic properties of ALD TiO2 films. J Electrochem Soc, 2009, 156, 275

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Shih P, Huang C, Chen T, et al. Enhancement on photocatalytic activity of an amorphous titanium oxide film with nano-textured surface by selective-fluorination etching process. Mater Res Bull, 2014, 52, 177

[28]

Zheng S K, Wang T M, Hao W C, et al. Improvement of photocatalytic activity of TiO2 thin film by Sn ion implantation. Vacuum, 2002, 65, 155

[29]

Bayati M R, Alipour H M, Joshi S, et al. Thin-film epitaxy and enhancement of photocatalytic activity of anatase/zirconia heterostructures by nanosecond excimer laser treatment. J Phys Chem C, 2013, 117, 7138

[30]

Liu P, Li W Y, Zhang J B, et al. Photocatalytic activity enhancement of TiO2 porous thin film due to homogeneous surface modification of RuO2. J Mater Res, 2011, 26, 1532

[31]

Álvaro A, Ramírez S, Próspero A P, et al. Enhanced photocatalytic activity of TiO2 films by modification with polyethylene glycol. Quím Nova, 2012, 35, 1931

[32]

Liu J, Zhang J. Photocatalytic activity enhancement of TiO2 nanocrystalline thin film with surface modification of poly-3-hexylthiophene by in situ polymerization. J Mater Res, 2016, 31, 1448

[33]

Cámara R M, Crespo E, Portela R, et al. Enhanced photocatalytic activity of TiO2 thin films on plasma-pretreated organic polymers. Catal Today, 2014, 230, 145

[34]

Cheng H E, Hung C H, Yu I S, et al. Strongly enhancing photocatalytic activity of TiO2 thin films by multi-heterojunction technique. Catalysts, 2018, 8, 440

[1]

Chang H W, Tsai Y C, Cheng C W, et al. Nanostructured Ag surface fabricated by femtosecond laser for surface-enhanced Raman scattering. J Colloid Interface Sci, 2011, 360, 305

[2]

Messaoudi H, Das S K, Lange J, et al. Femtosecond-laser induced periodic surface structures for surface enhanced Raman spectroscopy of biomolecules. In: Progress in Nonlinear Nano-Optics. Basel: Springer International Publishing, 2014, 207

[3]

Long J, Fan P, Zhong M, et al. Superhydrophobic and colorful copper surfaces fabricated by picosecond laser induced periodic nanostructures. Appl Surf Sci, 2014, 31, 461

[4]

Wang Z, Zhao Q, Wang C. Reduction of friction of metals using laser-induced periodic surface nanostructures. Micromachines, 2015, 6, 1606

[5]

Vorobyev A Y, Guo C. Colorizing metals with femtosecond laser pulses. Appl Phys Lett, 2008, 92, 041914

[6]

Dusser B, Sagan Z, Soder H, et al. Controlled nanostructrures formation by ultra fast laser pulses for color marking. Opt Exp, 2010, 18, 2913

[7]

Vorobyev A Y, Makin V S, Guo C. Brighter light sources from black metal: significant increase in emission efficiency of incandescent light sources. Phys Rev Lett, 2009, 102, 234301

[8]

Hwang T Y, Vorobyev A Y, Guo C. Surface-plasmon-enhanced photoelectron emission from nanostructure-covered periodic grooves on metals. Phys Rev B, 2009, 79, 085425

[9]

Itina R T E, Vervisch V, Halbwax M, et al. Study on laser induced periodic structures and photovoltaic application. AIP Conf Proc, 2010, 1278, 576

[10]

Chen J T, Lai W C, Kao Y J, et al. Laser-induced periodic structures for light extraction efficiency enhancement of GaN-based light emitting diodes. Opt Express, 2012, 20, 5689

[11]

Das S K, Andreev A, Messaoudi H, et al. Highly periodic laser-induced nanostructures on thin Ti and Cu foils for potential application in laser ion acceleration. J Appl Phys, 2016, 119, 13101

[12]

Baldacchini T, Carey J E, Zhou M, et al. Superhydrophobic surfaces prepared by microstructuring of silicon using a femtosecond laser. Langmuir, 2006, 22, 4917

[13]

Shimotsuma Y, Sakakura M, Miura K, et al. Application of femtosecond-laser induced nanostructures in optical memory. J Nanosci Nanotech, 2007, 7, 94

[14]

Yang C, Dong W, Cui G, et al. Highly-efficient photocatalytic degradation of methylene blue by PoPD-modified TiO2 nanocomposites due to photosensitization-synergetic effect of TiO2 with PoPD. Sci Rep, 2017, 7, 3973

[15]

Julkapli N, Bagheri S, Hamid S B A. Recent advances in heterogeneous photocatalytic decolorization of synthetic dyes. Sci World J, 2014, 692307

[16]

Tölke T, Heft A, Pfuch A. Photocatalytically active multi-layer systems with enhanced transmission. Thin Solid Films, 2008, 516, 4578

[17]

Tölke T, Kriltz A, Rechtenbach A. The influence of pressure on the structure and the self-cleaning properties of sputter deposited TiO2 layers. Thin Solid Films, 2010, 518, 4242

[18]

Granados E, Calderon M M, Krzywinski J, et al. Enhancement of surface area and wettability properties of boron doped diamond by femtosecond laser-induced periodic surface structuring. Opt Mat Exp, 2017, 7, 3389

[19]

Kuladeep R, Sahoo C, Rao D N. Direct writing of continuous and discontinuous sub-wavelength periodic surface structures on single-crystalline silicon using femtosecond laser. Appl Phys Lett, 2014, 104, 222103

[20]

Diesen V, Dunnill C W, Parkin I P, et al. Silver enhanced TiO2 thin films: photocatalytic characterization using aqueous solutions of tris(hydroxymethyl)aminomethane. Dalton Trans, 2014, 43, 344

[21]

Shuang S, Lv R, Xie Z, et al. Surface plasmon enhanced photocatalysis of Au/Pt-decorated TiO2 nanopillar arrays. Sci Rep, 2016, 6, 26670

[22]

Cui W, Xue D, Yuan X, et al. Acid-treated TiO2 nanobelt supported platinum nanoparticles for the catalytic oxidation of formaldehyde at ambient conditions. Appl Surf Sci, 2017, 411, 105

[23]

Chen J, Wang W, Li W, et al. Roles of crystal surface in Pt-loaded titania for photocatalytic conversion of organic pollutants: a first-principle theoretical calculation. ACS Appl Mater Interfaces, 2015, 7, 12671

[24]

Marelli M, Evangelisti C, Diamanti M V, et al. TiO2 nanotubes arrays loaded with ligand-free Au nanoparticles: enhancement in photocatalytic activity. ACS Appl Mater Interfaces, 2016, 8, 31051

[25]

Wang H L, Liu X H. Preparation of silver nanoparticle loaded mesoporous TiO2 and its photocatalytic property. J Inorg Mater, 2016, 31, 555

[26]

Cheng H, Hsu C, Chen Y. Substrate materials and deposition temperature dependent growth characteristics and photocatalytic properties of ALD TiO2 films. J Electrochem Soc, 2009, 156, 275

[27]

Shih P, Huang C, Chen T, et al. Enhancement on photocatalytic activity of an amorphous titanium oxide film with nano-textured surface by selective-fluorination etching process. Mater Res Bull, 2014, 52, 177

[28]

Zheng S K, Wang T M, Hao W C, et al. Improvement of photocatalytic activity of TiO2 thin film by Sn ion implantation. Vacuum, 2002, 65, 155

[29]

Bayati M R, Alipour H M, Joshi S, et al. Thin-film epitaxy and enhancement of photocatalytic activity of anatase/zirconia heterostructures by nanosecond excimer laser treatment. J Phys Chem C, 2013, 117, 7138

[30]

Liu P, Li W Y, Zhang J B, et al. Photocatalytic activity enhancement of TiO2 porous thin film due to homogeneous surface modification of RuO2. J Mater Res, 2011, 26, 1532

[31]

Álvaro A, Ramírez S, Próspero A P, et al. Enhanced photocatalytic activity of TiO2 films by modification with polyethylene glycol. Quím Nova, 2012, 35, 1931

[32]

Liu J, Zhang J. Photocatalytic activity enhancement of TiO2 nanocrystalline thin film with surface modification of poly-3-hexylthiophene by in situ polymerization. J Mater Res, 2016, 31, 1448

[33]

Cámara R M, Crespo E, Portela R, et al. Enhanced photocatalytic activity of TiO2 thin films on plasma-pretreated organic polymers. Catal Today, 2014, 230, 145

[34]

Cheng H E, Hung C H, Yu I S, et al. Strongly enhancing photocatalytic activity of TiO2 thin films by multi-heterojunction technique. Catalysts, 2018, 8, 440

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P Satapathy, A Pfuch, R Grunwald, S K Das, Enhancement of photocatalytic activity by femtosecond-laser induced periodic surface structures of Si[J]. J. Semicond., 2020, 41(3): 032303. doi: 10.1088/1674-4926/41/3/032303.

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Manuscript received: 15 August 2019 Manuscript revised: 21 September 2019 Online: Accepted Manuscript: 18 October 2019 Uncorrected proof: 21 October 2019 Published: 01 March 2020

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