Sub-nm Near-Surface Activation Profiling for Highly Doped Si and Ge Using Differential Hall Effect Metrology (DHEM)

Contact resistivity at the metal-semiconductor interface is a strong function of the carrier concentration in the near surface. For next generation 2D/3D MOSFET transistors, industry has been investigating very highly doped materials (>1x1021cm-3) approaching alloy concentrations in Silicon and various Silicon-Germanium materials. All the while, contact development in Ge NMOS has favored co-doping approaches. Regardless of the material system, it is very important to accurately measure near-surface dopant activation. In this paper, we use Differential Hall Effect Metrology (DHEM) implemented on the ALPro™ tool to characterize the activation profiles in both materials. The method employs electrochemical means of reducing the electrically active thickness of a semiconductor film and determining the sheet resistance and mobility of the thinned down layer using Van der Pauw/Hall effect type measurements. By repeating this process and using differential equations, depth profiles of mobility and carrier concentration are obtained [1] at sub-nm resolutions. It is difficult to achieve high n-type dopant activation in Ge. Point defects in Ge are known to behave as acceptor sites and reduce the overall free electron density, particularly near the surface. Minimization of these defects is essential to achieving high performance Ge NMOS. Accurate analysis of dopant activation within 5 nm of the surface is critical to understanding effectiveness of various process steps on improving contact resistance. We have previously published a study on the effect of Ge co-doping with Sb and P on near-surface dopant activation. In Ge with only P-doping it was found that only ~5x1018cm-3 or 5% of the total surface dopants (~1x1020cm-3) were electrically active. With Sb as a co-dopant, the active electron concentration increased to ~2x1019cm-3 with a similar P chemical concentration. Prior work has shown similar increases in activation with co-doping but did not capture the significant decrease in electron concentration by 4x within 10 nm of the surface. Here, we further study the effects of the implantation and annealing processes on near-surface dopant activation in n-type Ge. Samples were prepared by growing 3 µm thick epi-Ge layers on Si substrates. Sample 1 was capped with 20 nm SiO2 and Sample 2 was capped with 20 nm Al2O3 to minimize implant damage and control implant depth. Both samples were implanted first with Sb (dose: 6x1014cm-2, energy: 65 keV) followed by P (dose: 6x1014cm-2, energy: 90 keV). Post-implant anneal was done at 500°C for 10 s in N2 to activate the dopants. ALProTM and SIMS measurements were done to characterize active dopant concentration and total chemical dopant concentration, respectively. The Al2O3 capped sample (Sample 2) showed significantly lower carrier concentration than the SiO2 capped sample (Sample 1) throughout the depth of the profile (Figure 1). Carrier concentration at the surface was lower by nearly an order of magnitude, decreasing from ~2x1019cm-3 to ~2x1018cm-3. Additionally, the peak concentration decreased from 1x1020cm-3 to 5x1019cm-3 at a depth of ~30 nm in both cases. The variations in the carrier profile for the Al2O3 capped sample also indicate greater process variation. SIMS profiles show that there is significant diffusion of Al into the Ge matrix after implant and anneal. Al chemical concentration is 1x1020cm-3 at the Ge surface and steadily decays up to a depth of more than 300 nm. This indicates that there is significant damage caused during the implantation process and the activation anneal is not enough to remove these defects. Al atoms then diffuse from the Al2O3 capping layer into the highly defective Ge substrate. Al is a p-type dopant in Ge and counter-dopes the Sb and P implants to reduce overall electron concentration in Sample 2. It is important to note the high resolution DHEM technique was able to resolve this important phenomenon right near the surface of the material. Additionally, we present early data on very highly phosphorus-doped (~1x1021cm-3) epitaxial silicon thin films grown on Si substrates. In very highly doped Silicon materials, the effect of near-alloy levels of dopant in the matrix on dopant deactivation is not well-known. Samples were obtained with different levels of dopant concentration above ~1x1021cm-3and different anneal temperatures. It was found that near-surface activation in these un-capped samples led to a lowering of activation in the References: Abhijeet Joshi and Bulent Basol, “ALPro System: An Electrical Profiling Tool for Ultra-thin Film Characterization”, 2017 Frontiers of Characterization and Metrology for Nanoelectronics (FCMN), pgs.170-172. Figure 1