Measuring Surface Energies of GaAs (100) and Si (100) by Three Liquid Contact Angle Analysis (3LCAA) for Heterogeneous Nano-BondingTM

Abstract

Analysis of the total surface energy γTand its three components as established by the van Oss-Chaudhury-Good Theory (vOCG) is conducted via Three Liquid Contact Angle Analysis (3LCAA). γTis correlated with the composition of the top monolayers (ML) obtained from High-Resolution Ion Beam Analysis (HR-IBA). Control of γTenables surface engineering for wafer bonding (Nano-BondingTM) and/or epitaxial growth. Native oxides on boron-doped p-Si(100) are found to average γTof 53 ± 1.4 mJ/m2) and are always hydrophilic. An HF in methanol or aqueous HF etch for 60 s always renders Si(100) hydrophobic. Its γTdecreases by 20% to 44 ± 3 mJ/m2in HF in methanol etch and by 10% to 48 ± 3 mJ/m2in aqueous HF. On the contrary, GaAs(100) native oxides are found to always be hydrophobic. Tellurium n+-doped GaAs(100) yields an average of γTof 37 ± 2 mJ/m2, 96% of which is due to the Lifshitz-Van der Waals molecular interactions (γLW= 36 ± 1 mJ/m2). However, hydrophobic GaAs(100) can be made highly hydrophilic. After etching, γTincreases by almost 50% to 66 ± 1.4 mJ/m2. 3LCAA shows that the γTincrease is due to electron acceptor and donor interactions, while the Lifshitz-van der Waals energy γLWremains constant. IBA combining the 3.039 ± 0.01 MeV oxygen nuclear resonance with <111> channeling, shows that oxygen on Si(100) decreases by 10% after aqueous HF etching, from 13.3 ± 0.3 monolayers (ML) to 11.8 ± 0.4 ML 1 hour after etch.Te-doped GaAs(100) exhibits consistent oxygen coverage of 7.2 ± 1.4 ML, decreasing by 50% after etching to a highly hydrophilic surface with 3.6 ± 0.2 oxygen ML. IBA shows that etching does not modify the GaAs surface stoichiometry to within 1% . Combining 3LCAA with HR-IBA provides a quantitative metrology to measure how GaAs and Si surfaces can be altered to a different hydroaffinity and surface termination.

GaAs to Si Direct Wafer Bonding at T ≤ 220°C in Ambient Air via Nano-BondingTM and Surface Energy Engineering (SEE)

“…Thus, HR-IBA shows that SEE decreases oxygen coverage on GaAs by 50%. Critically, the Ga:As ratio does not change after etching[23,29]. The 50% decrease in O detected by HR-IBA affects primarily the oxidation states of Arsenic.…”