R. Milazzo

N-type doping of Ge by As implantation and excimer laser annealing

The diffusion and activation of arsenic implanted into germanium at 40 keV with maximum concentrations below and above the solid solubility (8 × 1019 cm−3) have been studied, both experimentally and theoretically, after excimer laser annealing (λ = 308 nm) in the melting regime with different laser energy densities and single or multiple pulses. Arsenic is observed to diffuse similarly for different fluences with no out-diffusion and no formation of pile-up at the maximum melt depth. The diffusion profiles have been satisfactorily simulated by assuming two diffusivity states of As in the molten Ge and a non-equilibrium segregation at the maximum melt depth. The electrical activation is partial and decreases with increasing the chemical concentration with a saturation of the active concentration at 1 × 1020 cm−3, which represents a new record for the As-doped Ge system.

B-doping in Ge by excimer laser annealing

An experimental and theoretical study of the effect of excimer laser annealing (ELA) on B redistribution and electrical activation in Ge is reported. We performed detailed structural, chemical, and electrical characterizations of Ge samples implanted with B (20 keV, 1 × 1015, or 1 × 1016 B/cm2) and processed by ELA (λ = 308 nm) with multiple pulses (1, 3, or 10). We also developed a diffusion model, in order to simulate the B redistribution induced by the ELA process. We found an anomalous impurity redistribution in the molten phase, which causes a dopant incorporation during the melt-growth at the maximum melt depth. The investigated samples showed a partial electrical activation of the B dopant. The inactivation of B in the samples implanted with 1 × 1015 B/cm2 was correlated to an oxygen contamination, while the poor electrical activation of B in the samples implanted with 1 × 1016 B/cm2 was related to the precipitation of the dopant, in good agreement with the experimental and theoretical results.

Impurity and defect interactions during laser thermal annealing in Ge

The microscopic mechanisms involving dopants, contaminants, and defects in Ge during pulsed melting laser thermal annealing (LTA) are investigated in detail. Samples both un-implanted and implanted with As or B are processed by LTA as well as characterized in terms of chemical (1D and 3D), electrical, and strain profiling. The clustering of As is directly measured by 3D chemical profiling and correlated with its partial electrical activation along with a reduction of the lattice strain induced by As atoms. A semi-quantitative microscopic model involving the interaction with mobile As-vacancy (AsV) complexes is proposed to describe the clustering mechanism. Boron is shown to follow different clustering behavior that changes with depth and marked by completely different strain levels. Oxygen penetrates from the surface into all the samples as a result of LTA and, only in un-implanted Ge, it occupies an interstitial position inducing also positive strain in the lattice. On the contrary, data suggest that the presence of As or B forces O to assume different configurations with negligible strain, through O-V or O-B interactions for the two dopant species, respectively. These data suggest that LTA does not inject a significant amount of vacancies in Ge, at variance with Si, unless As atoms or possibly other n-type dopants are present. These results have to be carefully considered for modeling the LTA process in Ge and its implementation in technology

Low temperature deactivation of Ge heavily n-type doped by ion implantation and laser thermal annealing

Heavy doping of Ge is crucial for several advanced micro- and optoelectronic applications, but, at the same time, it still remains extremely challenging. Ge heavily n-type doped at a concentration of 1 × 1020 cm−3 by As ion implantation and melting laser thermal annealing (LTA) is shown here to be highly metastable. Upon post-LTA conventional thermal annealing As electrically deactivates already at 350 °C reaching an active concentration of ∼4 × 1019 cm−3. No significant As diffusion is detected up to 450 °C, where the As activation decreases further to ∼3 × 1019 cm−3. The reason for the observed detrimental deactivation was investigated by Atom Probe Tomography and in situ High Resolution X-Ray Diffraction measurements. In general, the thermal stability of heavily doped Ge layers needs to be carefully evaluated because, as shown here, deactivation might occur at very low temperatures, close to those required for low resistivity Ohmic contacting of n-type Ge.

Switching Between Giant Positive and Negative Thermal Expansions of a YFe(CN)6-Based Prussian Blue Analogue Induced by Guest Species

The control of thermal expansion of solid compounds is intriguing but remains challenging. The effect of guests on the thermal expansion of open-framework structures was investigated. Notably, the presence of guest ions (K+ ) and molecules (H2 O) can substantially switch thermal expansion of YFe(CN)6 from negative (αv =-33.67×10-6  K-1 ) to positive (αv =+42.72×10-6  K-1 )-a range that covers the thermal expansion of most inorganic compounds. The mechanism of such substantial thermal expansion switching is revealed by joint studies with synchrotron X-ray diffraction, X-ray absorption fine structure, neutron powder diffraction, and density functional theory calculations. The presence of guest ions or molecules plays a critical damping effect on transverse vibrations, thus inhibiting negative thermal expansion. An effective method is demonstrated to control the thermal expansion in open-framework materials by adjusting the presence of guests.

High level active n+ doping of strained germanium through co-implantation and nanosecond pulsed laser melting

Obtaining high level active n+ carrier concentrations in germanium (Ge) has been a significant challenge for further development of Ge devices. By ion implanting phosphorus (P) and fluorine (F) into Ge and restoring crystallinity using Nd:YAG nanosecond pulsed laser melting (PLM), we demonstrate 1020 cm−3 n+ carrier concentration in tensile-strained epitaxial germanium-on-silicon. Scanning electron microscopy shows that after laser treatment, samples implanted with P have an ablated surface, whereas P + F co-implanted samples have good crystallinity and a smooth surface topography. We characterize P and F concentration depth profiles using secondary ion mass spectrometry and spreading resistance profiling. The peak carrier concentration, 1020 cm−3 at 80 nm below the surface, coincides with the peak F concentration, illustrating the key role of F in increasing donor activation. Cross-sectional transmission electron microscopy of the co-implanted sample shows that the Ge epilayer region damaged during impla...

Nanoscale measurements of phosphorous-induced lattice expansion in nanosecond laser annealed germanium

Laser Thermal Annealing (LTA) at various energy densities was used to recrystallize and activate amorphized germanium doped with phosphorous by ion implantation. The structural modifications induced during the recrystallization and the related dopant diffusion were first investigated. After LTA at low energy densities, the P electrical activation was poor while the dopant distribution was mainly localized in the polycrystalline Ge resulting from the anneal. Conversely, full dopant activation (up to 1 × 1020 cm−3) in a perfectly recrystallized material was observed after annealing at higher energy densities. Measurements of lattice parameters performed on the fully activated structures show that P doping results in a lattice expansion, with a perpendicular lattice strain per atom βPs = +0.7 ± 0.1 A3. This clearly indicates that, despite the small atomic radius of P compared to Ge, the “electronic contribution” to the lattice parameter modification (due to the increased hydrostatic deformation potential in the conduction band of P doped Ge) is larger than the “size mismatch contribution” associated with the atomic radii. Such behavior, predicted by theory, is observed experimentally for the first time, thanks to the high sensitivity of the measurement techniques used in this work.Laser Thermal Annealing (LTA) at various energy densities was used to recrystallize and activate amorphized germanium doped with phosphorous by ion implantation. The structural modifications induced during the recrystallization and the related dopant diffusion were first investigated. After LTA at low energy densities, the P electrical activation was poor while the dopant distribution was mainly localized in the polycrystalline Ge resulting from the anneal. Conversely, full dopant activation (up to 1 × 1020 cm−3) in a perfectly recrystallized material was observed after annealing at higher energy densities. Measurements of lattice parameters performed on the fully activated structures show that P doping results in a lattice expansion, with a perpendicular lattice strain per atom βPs = +0.7 ± 0.1 A3. This clearly indicates that, despite the small atomic radius of P compared to Ge, the “electronic contribution” to the lattice parameter modification (due to the increased hydrostatic deformation potential in ...

Characterization and modeling of thermally-induced doping contaminants in high-purity Germanium

High purity germanium (HPGe) is the key material for gamma ray detectors production. Its high purity level (≤2 10−4 ppb of doping impurity) has to be preserved in the bulk during the processes needed to form the detector junctions. With the goal of improving the device performance and expanding the application fields, in this paper many alternative doping processes are evaluated, in order to verify their effect on the purity of the material. In more detail, we investigated the electrical activation of contaminating doping defects or impurities inside the bulk HPGe, induced by both conventional and non-conventional surface doping processes, such as boron ion implantation, phosphorus and gallium diffusion from spin-on doping sources, antimony equilibrium diffusion from a remote sputtered source and laser thermal annealing (LTA) of sputtered antimony. Doping defects, thermally-activated during high temperature annealing, were characterized through electrical measurements. A phenomenological model describing the contamination process was developed and used to analyze the diffusion parameters and possible process thermal windows. It resulted that out-of-equilibrium doping processes confined to the HPGe surface have higher possibilities to be successfully employed for the formation of thin contacts, maintaining the pristine purity of the bulk material. Among them, LTA turned out to be the most promising.

Heavily-doped germanium on silicon with activated doping exceeding 10 20 cm −3 as an alternative to gold for mid-infrared plasmonics

Ge-on-Si has been demonstrated as a platform for Si foundry compatible plasmonics. We use laser thermal annealing to demonstrate activated doping levels >10²⁰ cm⁻³ which allows most of the 3 to 20 μm mid-infrared sensing window to be covered with enhancements comparable to gold plasmonics.