000150644 001__ 150644
000150644 005__ 20250214153849.0
000150644 0247_ $$2doi$$a10.1016/j.addma.2025.104645
000150644 0248_ $$2sideral$$a142752
000150644 037__ $$aART-2025-142752
000150644 041__ $$aeng
000150644 100__ $$aChang, Bingdong
000150644 245__ $$a3D ice lithography and post-processing using gold organometallic precursor
000150644 260__ $$c2025
000150644 5060_ $$aAccess copy available to the general public$$fUnrestricted
000150644 5203_ $$a3D ice lithography (3DIL) is an emerging method for fabricating polymeric 3D objects with submicrometer patterns. However, there are no studies on 3DIL using metal-containing precursors. In addition, unlike numerous post-processing studies of two-photon polymerization (2PP) and focused electron beam-induced deposition (FEBID), there are no 3DIL post-processing investigations. Here, we present a 3DIL process using an organometallic precursor (gold dimethyl acetylacetonate, Au(acac)Me2), and its first post-processing study. We investigated 3D processing parameters and post-processing using Ar-, air annealing, and O2 plasma. X-ray photoelectron spectroscopy (XPS), atomic force microscopy, energy-dispersive X-ray spectroscopy, and transmission electron microscopy were used for materials analysis. Our results show (i) 3DIL processed materials exhibit thermoset properties, as they decompose rather than melt at elevated temperatures; (ii) free metal atoms diffuse and form clusters, here, gold nanoparticles with a diameter of around 10 nm were formed; (iii) oxygen treatments remove carbon-based ligands while leaving noble metals behind. Also, Ar annealing leads to less material loss than air annealing, while O2 plasma generates oxidized Au states and efficiently removes carbon ligands. Ar annealing at 600 °C reduces the carbon XPS signals significantly and increases the gold XPS signal by ten times, giving a good purification effect but with a high material removal of around 95 %. We printed large Au metalorganic 3D structures (>1000 times larger volume than FEBID), which suggests 3DIL bridges the gap between the capabilities of 2PP and FEBID. The unique capabilities of organometallic compounds to detect environmental changes can position 3DIL for sensing applications, and 3DIL is a safe and non-toxic technique to manufacture nanoparticle-containing 3D structures, which may have applications in many fields such as nanophotonics, drug delivery, and catalysis.
000150644 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E13-23R$$9info:eu-repo/grantAgreement/ES/MICINN-AEI/PID2020-112914RB-100/AEI/10.13039/501100011033
000150644 540__ $$9info:eu-repo/semantics/openAccess$$aby$$uhttp://creativecommons.org/licenses/by/3.0/es/
000150644 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000150644 700__ $$aAnand, Gwendoline A.E.
000150644 700__ $$aLe, Hoa Thanh
000150644 700__ $$aLiu, Xiyuan
000150644 700__ $$aHansen, Thomas W.
000150644 700__ $$0(orcid)0000-0001-9566-0738$$ade Teresa, Jose María
000150644 700__ $$aHan, Anpan
000150644 773__ $$g98 (2025), 104645 [10 pp.]$$tAdditive Manufacturing$$x2214-8604
000150644 8564_ $$s612985$$uhttps://zaguan.unizar.es/record/150644/files/texto_completo.pdf$$yVersión publicada
000150644 8564_ $$s2435888$$uhttps://zaguan.unizar.es/record/150644/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
000150644 909CO $$ooai:zaguan.unizar.es:150644$$particulos$$pdriver
000150644 951__ $$a2025-02-14-14:01:47
000150644 980__ $$aARTICLE