Single-step fabrication of hybrid germanium-gold/silver nanoentities by femtosecond laser ablation and applications in SERS-based sensing

Abstract

Abstract We present a simple, fast, and single-step approach for fabricating hybrid semiconductor-metal nanoentities through liquid-assisted ultrafast (∼50 fs, 1 kHz, 800 nm) laser ablation. Femtosecond (fs) ablation of Germanium (Ge) substrate was executed in (i) distilled water (ii) silver nitrate (AgNO3—3, 5, 10 mM) (iii) Chloroauric acid (HAuCl4—3, 5, 10 mM), yielding the formation of pure Ge, hybrid Ge-silver (Ag), Ge-gold (Au) nanostructures (NSs) and nanoparticles (NPs). The morphological features and corresponding elemental compositions of Ge, Ge-Ag, and Ge-Au NSs/NPs have been conscientiously studied using different characterization techniques. Most importantly, the deposition of Ag/Au NPs on the Ge substrate and their size variation were thoroughly investigated by changing the precursor concentration. By increasing the precursor concentration (from 3 mM to 10 mM), the deposited Au NPs and Ag NPs’ size on the Ge nanostructured surface was increased from ∼46 nm to ∼100 nm and from ∼43 nm to ∼70 nm, respectively. Subsequently, the as-fabricated hybrid (Ge-Au/Ge-Ag) NSs were effectively utilized to detect diverse hazardous molecules (e.g. picric acid and thiram) via the technique of surface-enhanced Raman scattering (SERS). Our findings revealed that the hybrid SERS substrates achieved at 5 mM precursor concentration of Ag (denoted as Ge-5Ag) and Au (denoted as Ge-5Au) had demonstrated superior sensitivity with the enhancement factors of ∼2.5 × 104, 1.38 × 104 (for PA), and ∼9.7 × 105 and 9.2 × 104 (for thiram), respectively. Interestingly, the Ge-5Ag substrate has exhibited ∼10.5 times higher SERS signals than the Ge-5Au substrate.