High mobility channel materials like SiGe, Ge and IIIV receive lots of interest in order to enable the continuation of Moore’s path during the upcoming technology nodes. Recently Si-cap-free SiGe passivation with the number of interface states (N_IT) down to 2 10¹¹ cm^-2 have been demonstrated. [1-3] A clear correlation was established between Ge-content in the SiGe-oxide and N_IT. Unfortunately no process information has been provided on how the Ge-oxide-free interlayers were obtained. In a separate study the impact of HF, HCl and SC1 cleaning solution on the SiGe surface and oxide composition was reported. [4]

A comparison of SiGe Gate-All-Around (GAA) and FinFET devices using a Si-cap-free SiGe 25% passivation scheme in a replacement metal gate (RMG) integration indicate the device performance is improved by a TMAH (aq) treatment prior to SiGe interlayer formation and high-k deposition. [5] Here the formation of a SiGe wet chemical oxide will be presented. The impact of dummy gate processing on the interlayer composition is reported. Also the impact of a TMAH (aq) treatment prior to chemical oxide formation has been analyzed and will be reported.

Blanket strained SiGe 25% and 45% were grown by epitaxy. The SiGe-substrate and -oxide composition were measured by angle-resolved XPS using the Si2p and Ge3d peaks. The Ge3d peak is fitted with three different compounds: elemental Ge, GeO₂ and Ge-suboxide. The angle dependence lets us estimate the distribution of the different components with respect to the sample top surface. An concentration increase with increasing angle (relative to the surface normal) indicates the compound is located closer to the sample surface. And reversely a concentration increase with increasing angle indicates the compound is located deeper into the sample.

A native oxide was grown on SiGe 25 and 45% by exposing the wafers to the cleanroom air for approx. 1 week. The native oxide was found to be stoichiometric or nearly stoichiometric with a uniform Ge content throughout the oxide for SiGe 25 and 45% respectively. A wet chemical oxide was grown using an ‘imec clean’ [6] having a final O₃/HCl (aq) rinse. The wet chemical oxide is Ge-poor compared to the SiGe substrate. No or only a small variation in Ge content of the SiGe-oxide is seen with ARXPS. However the fraction Ge-suboxide decreases with increasing angle, indicating the Ge-suboxide are located deeper within the sample, so closer to the SiGe-oxide/SiGe-substrate interface. The Ge-content of the SiGe-substrate after wet chemical oxidation shows a weak incident-angle-dependence, indicative a limited Ge enrichment of the SiGe substrate towards the SiGe-oxide/-substrate interface. The low Ge content of the SiGe-oxide is attributed to the water solubility of GeO2. The increase in Ge-content towards the SiGe-oxide/-substrate can be (at least partially) attributed to the poor water solubility of Ge-suboxide. The small increase in Ge content of the SiGe substrate can be attributed to the thermodynamically preferred oxidation of Si over Ge.

The combined impact of dummy gate deposition, spike anneal and dummy gate removal prior to SiGe interlayer formation was investigated by AR-XPS and SIMS. The temperature used during spike anneal was found to have a significant impact on the Ge-content of the SiGe-oxide formed during an O₃-last imec clean. The results will be reported in detail at the conference. The impact of TMAH (aq) on the chemical oxide composition and surface roughness will also be reported. TMAH (aq) was found to improve SiGe device performance. [5] Also the interaction with the subsequent HfO₂ deposition will be reported.

In summary SiGe is found to behave as a non-linear combination of Si and Ge. In HF-free aqueous solutions, the SiGe oxide composition is a combination of (1) thermodynamically preferred oxidation of Si versus Ge; (2) poor water-solubility of SiO₂ and/or its low solubilization rate; and (3) fast dissolution of GeO₂ but slow dissolution of Ge-suboxides.

[1] CH Lee et al. VLSI 2016.

[2] S. Siddiqui et al. presented MRS Spring Meeting 2016.

[3] CH Lee et al. IEDM 2016.

[4] S.L. Heslop et al. ECS Trans 69 (2015) 287.

[5] H. Mertens et al VLSI 2015.

[6] M. Meuris et al. Solid State Phenom, July 1995, p. 109.