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Additive Manufacture of Three Dimensional Nanocomposite Based Objects Through Multiphoton Fabrication polymers Article Additive Manufacture of Three Dimensional Nanocomposite Based Objects through Multiphoton Fabrication Yaan Liu 1, Qin Hu 1, Fan Zhang 1, Christopher Tuck 1, Derek Irvine 1, Richard Hague 1, Yinfeng He 1, Marco Simonelli 1, Graham A. Rance 2, Emily F. Smith 2 and Ricky D. Wildman 1,* 1 Faculty of Engineering, The University of Nottingham, University Park, Nottingham NG7 2RD, UK; [email protected] (Y.L.); [email protected] (Q.H.); [email protected] (F.Z.); [email protected] (C.T.); [email protected] (D.I.); [email protected] (R.H.); [email protected] (Y.H.); [email protected] (M.S.) 2 Nanoscale and Microscale Research Centre, The University of Nottingham, University Park, Nottingham NG7 2RD, UK; [email protected] (G.A.R.); [email protected] (E.F.S.) * Correspondence: [email protected]; Tel.: +44-115-8466-893 Academic Editor: Georg von Freymann Received: 25 May 2016; Accepted: 4 August 2016; Published: 1 September 2016 Abstract: Three-dimensional structures prepared from a gold-polymer composite formulation have been fabricated using multiphoton lithography. In this process, gold nanoparticles were simultaneously formed through photoreduction whilst polymerisation of two possible monomers was promoted. The monomers, trimethylopropane triacrylate (TMPTA) and pentaerythritol triacrylate (PETA) were mixed with a gold salt, but it was found that the addition of a ruthenium(II) complex enhanced both the geometrical uniformity and integrity of the polymerised/reduced material, enabling the first production of 3D gold-polymer structures by single step multiphoton lithography. Keywords: multiphoton fabrication (MF); two-photon lithography (TPL); nanocomposite; gold nanoparticles; polymerisation; metal reduction; 3D printing; additive manufacturing 1. Introduction Additive Manufacturing (AM) is attractive due to its design freedoms, particularly with relation to increased levels of complexity [1]. An extension of AM is additive fabrication at the nanoscale, putting into reach length scales that are useful for manipulating, for example, electromagnetic radiation at optical wavelengths; this nano-scale AM is most commonly achieved using femtosecond laser induced multiphoton fabrication (MF) [2–5]. MF was first demonstrated for the fabrication of three-dimensional (3D) structures by Maruo in 1997 [6], resulting in features at subwavelength scales [7,8]. Since this first demonstration, MF has been used to create complexity for a range of applications, including photonic crystals, mechanical devices and microscopic models [9–11]. MF can be utilised with a wider range of photochemistries than simply for polymerisation. For example, Kaneko et al. [2] reported gold nanoparticle grating lines fabricated using metal ion-doped polyvinyl alcohol (PVA), and in 2006, a self-standing silver gate structure with electrical conductivity was obtained using a metal-ion aqueous solution by Tanaka et al. [12]. This process was further enhanced by the addition of a suitable dye that improved metallic reduction and enabled the use of reduced laser powers [13–18]. These advances offer the potential to produce periodic metallic nano/microstructures all in a single processing step [19]. Recent endeavours have been focused on extending the AM approach to multiple materials [20–24], and this has been complemented by efforts to process nanocomposites using Polymers 2016, 8, 325; doi:10.3390/polym8090325 www.mdpi.com/journal/polymers Polymers 2016, 8, 325 2 of 14 PolymersRecent2016, 8 , 325endeavours have been focused on extending the AM approach to multiple2 of 14 materials [20–24], and this has been complemented by efforts to process nanocomposites using MF. MF.Combined Combined metal metal reduction reduction and andpolymerisation polymerisation has been has been observed observed using using a range a range of methods, of methods, but buteach each requires requires multiple multiple processing processing stages stages [4,5,17,19,25,26]. [4,5,17,19,25 ,A26 ].significant A significant step stepforward, forward, however, however, is in isthe in single-step the single-step fabrication fabrication by MF of by nano-composites, MF of nano-composites, reducing the reducing need for the multiple need for washes multiple and washesfabrication and fabricationsteps. This steps. has Thisbeen has demonstra been demonstrated,ted, in two intwo dimensions, dimensions, by by simultaneoussimultaneous photopolymerisationphotopolymerisation and photoreductionphotoreduction [[25],25], and, in a similar fashion, by the creationcreation ofof threethree dimensional filigree-likefiligree-like conductiveconductive elementselements thatthat areare ‘glued’‘glued’ togethertogether withwith aa polymerpolymer resinresin [27[27].]. InIn thisthis paper, paper, however, however, a method a method for fabricatingfor fabricating truly three-dimensionaltruly three-dimensional nanocomposite nanocomposite objects willobjects be presented.will be presented. Following Following the lead ofthe Shukla lead of et Shukla al. [13], et it willal. [13], be shown it will that,be shown by suitable that, selectionby suitable of monomer,selection of initiator monomer, and initiator dye, a stableand dye, three-dimensional a stable three-dimensional object can beobject formed. can be In formed. this case, In athis radical case, polymerisationa radical polymerisation is utilised, is whilst utilised, taking whilst advantage taking advantage of previously of previously observed beneficialobserved effectsbeneficial of adding effects rutheniumof adding ruthenium complexes complexes on multiphoton on multiphoton reactivity [21 reactivity], leading [21], to the leading role of to the the initiator role of inthe overcoming initiator in theovercoming competition the betweencompetition polymerisation between polyme and reductionrisation and being reduction explored. being explored. 2. Materials Materials and and Methods Methods 2.1. General Approach Formulations ableable to realiseto realise three-dimensional three-dimensional multiphoton multiphoton fabricated fabricated structures structures were identified were inidentified the following in the following way. First, way. acrylate First, acrylate based based formulations formulations were were prepared prepared with with combinations combinations of monomer,of monomer, photoinitiator, photoinitiator, gold(III) gold(III) chloride chloride hydrate, hydrate, and and photosensitive photosensitive dye. dye. TheseThese formulationsformulations werewere systematicallysystematically varied;varied; andand thenthen trialstrials withwith a commercial MF system were performed to identify thethe fidelityfidelity ofof two-two- andand three-dimensionalthree-dimensional structures.structures. Structures successfully formed werewere thenthen characterisedcharacterised toto confirmconfirm thethe presencepresence ofof goldgold withinwithin thethe polymericpolymeric framework.framework. 2.2. Multiphoton Fabrication A commercialcommercial two-photontwo-photon lithographylithography facility (Nanoscribe GmbH PhotonicPhotonic Professional GT) waswas utilised for for the the MF. MF. The The system system is driven is driven by a byfibre a fibrelaser at laser a 780 at nm a 780 central nm wavelength, central wavelength, 80 MHz 80repetition MHz repetition rate and rate a and120-fs a 120-fspulse pulseduration. duration. The Thelaser laser beam beam was was focused focused using using an an oil oil immersion objective lens (1.4 NA, NA, 63×, 63× 190, 190 µmµm WD). WD). Structures Structures were were built built by bymoving moving the the sample sample position position in the in theXY XYplaneplane using using a galvo a galvo mirror mirror and and in inthe the ZZ directiondirection using using a a piezoelectric piezoelectric actuator actuator to move thethe objective. The laser power was varied betweenbetween 1010 andand 5050 mWmW andand thethe scanscan speedspeed waswas 10,00010,000 µµm/s.m/s. Two monomers,monomers, trimethylopropanetrimethylopropane triacrylatetriacrylate (TMPTA)(TMPTA) (as(as received,received, Sigma-Aldrich,Sigma-Aldrich, Dorset, UK) and pentaerythritolpentaerythritol triacrylate (PETA) (as(as received,received, Sigma-Aldrich,Sigma-Aldrich, Dorset, UK) were used as basebase 0 materials forfor thethe proposedproposed formulations.formulations. 2-benzyl-2-(dimethylamino)-42-benzyl-2-(dimethylamino)-4′-morpholinobutyrophenone-morpholinobutyrophenone 0 (DBMP)(DBMP) (as(as received, received, Sigma-Aldrich, Sigma-Aldrich, Dorset, Dorset UK) was, UK) used aswas the photoinitiatorused as the and photoinitiator tris(2,2 -bipyridyl) and dichlororuthenium(II)tris(2,2′-bipyridyl) dichlororuthenium(II) hexahydrate (bipy) hexahydrate (as received, (bipy) Sigma-Aldrich, (as received, Dorset, Sigma-Aldrich, UK) was used Dorset, as a dye.UK) was The used chemical as a dye. structures The chemical are shown structures in Figure are1 shown. Gold(III) in Figure chloride 1. Gold(III) hydrate, chloride HAuCl hydrate,4·3H2O (Sigma-Aldrich,HAuCl4·3H2O (Sigma-Aldrich, Dorset, UK) was Dorset, used UK) as the was metal used salt as the and metal ethanol salt was and employed ethanol was as aemployed solvent for as botha solvent the ruthenium(II) for both the ruthenium(II) and gold(III) chlorideand gold(III) hydrate. chloride hydrate. (a) (b)(c)(d) Figure 1. Chemical structures of (a) trimethylopropane triacrylate (TMPTA); (b) pentaerythritol Figure 1. Chemical structures
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