Identification of nanoindentation-induced phase changes in silicon by in situ electrical characterization

In situ electrical measurements during nanoindentation of Czochralski grown p-type crystalline silicon (100) have been performed using a conducting diamond Berkovich indenter tip. Through-tip current monitoring with a sensitivity of ∼10pA and extraction of current-voltage curves at various points on the complete load-unload cycle have been used to track the phase transformations of silicon during the loading and unloading cycle. Postindent current-voltage curves prove to be extremely sensitive to phase changes during indentation, as well as to the final phase composition within the indented volume. For example, differences in the final structure are detected by current-voltage measurements even in an unloading regime in which only amorphous silicon is expected to form. The electrical measurements are interpreted with the aid of previously reported transmission electron microscopy and Raman microspectroscopy measurements.This work was funded by the Australian Research Council and WRiota Pty Ltd

Phase transformations induced by spherical indentation in ion-implanted amorphous silicon

The deformation behavior of ion-implanted (unrelaxed) and annealed ion-implanted (relaxed) amorphous silicon(a-Si) under spherical indentation at room temperature has been investigated. It has been found that the mode of deformation depends critically on both the preparation of the amorphous film and the scale of the mechanical deformation.Ex situmeasurements, such as Raman microspectroscopy and cross-sectional transmission electron microscopy, as well as in situ electrical measurements reveal the occurrence of phase transformations in all relaxed a-Si films. The preferred deformation mode of unrelaxed a-Si is plastic flow, only under certain high load conditions can this state of a-Si be forced to transform. In situ electrical measurements have revealed more detail of the transformation process during both loading and unloading. We have used ELASTICA simulations to obtain estimates of the depth of the metallic phase as a function of load, and good agreement is found with the experiment. On unloading, a clear change in electrical conductivity is observed to correlate with a “pop-out” event on load versus penetration curves

Effect of oxygen concentration on nanoindentation-induced phase transformations in ion-implanted amorphous silicon

The effect of the local oxygen concentration in ion-implanted amorphous Si (a-Si) on nanoindentation-inducedphase transformations has been investigated. Implantation of oxygen into the a-Sifilms has been used to controllably introduce an approximately constant concentration of oxygen, ranging from ∼10¹⁸ to ∼10²¹ cm⁻³, over the depth range of the phase transformed zones. Nanoindentation was performed under conditions that ensure a phase transformed zone composed completely of Si-III/XII in the nominally oxygen-free a-Si. The effect of the local oxygen concentration has been investigated by analysis of the unloading curves, Raman microspectroscopy, and cross-sectional transmission electron microscopy (XTEM). The formation of Si-III/XII is suppressed with increasing oxygen concentration, favoring a greater volume of a-Si within the zones. The Raman microspectroscopy and XTEM verify that the volume of Si-III/XII decreases with increasing O concentration. With the smaller volumes of Si-III/XII, the pop-out normally observed on load versus penetration depth curves during unloading decreases in magnitude, becoming more kinklike and is barely discernable at high concentrations of oxygen. The probability of forming any high pressure phases is reduced from 1 to ∼0.1 for a concentration of 10²¹ cm⁻³. We suggest that the bonding of O with Si reduces the formation of Si-III/XII during unloading through a similar mechanism to that of oxygen-retarded solid phase crystallization of a-Si.This project is funded by the Australian Research Council and WRiota Pty Ltd

Nanoindentation-induced deformation of Ge

The deformation mechanisms of crystalline (100) Ge were studied using nanoindentation, cross sectional transmission electron microscopy (XTEM) and Raman microspectroscopy. For a wide range of indentation conditions using both spherical and pointed indenters, multiple discontinuities were found in the force–displacement curves on loading, but no discontinuities were found on unloading. Raman microspectroscopy, measured from samples which had plastically deformed on loading, showed a spectrum shift from that in pristine Ge, suggesting only residual strain. No evidence (such as extra Raman bands) was found to suggest that any pressure-induced phase transformations had occurred, despite the fact that the material had undergone severe plastic deformation.Selected area diffraction pattern studies of the mechanically damaged regions also confirmed the absence of additional phases. Moreover, XTEM showed that, at low loads, plastic deformation occurs by twinning and dislocation motion. This indicates that the hardness of Gemeasured by indentation is not primarily dominated by phase transformation, rather by the nucleation and propagation of twin bands and/or dislocations

High pressure crystalline phase formation during nanoindentation: Amorphous versus crystalline silicon

Phase transformations induced by indentation at different unloading rates have been studied in crystalline and amorphous silicon via Raman microspectroscopy and transmission electron microscopy. Unloading was performed at a “slow” rate of ∼0.9mN∕s which is known to create volumes of high pressure phases (Si-III and Si-XII) in crystalline silicon as well as “rapid” unloading (∼1000mN∕s), where amorphous phases are expected. Stark differences between the resulting structures are observed depending on whether the starting material is amorphous or crystalline silicon. Interestingly, amorphous silicon transforms to high pressure phases much more readily than crystalline silicon even after rapid unloading.This work was funded by the Australian Research Council and WRiota Pty Ltd

Giant pop-ins and amorphization in germanium during indentation

Sudden excursions of unusually large magnitude (>1 μm), “giant pop-ins,” have been observed in the force-displacement curve for high load indentation of crystalline germanium(Ge). A range of techniques including Raman microspectroscopy, focused ion-beam cross sectioning, and transmission electron microscopy, are applied to study this phenomenon. Amorphous material is observed in residual indents following the giant pop-in. The giant pop-in is shown to be a material removal event, triggered by the development of shallow lateral cracks adjacent to the indent. Enhanced depth recovery, or “elbowing,” observed in the force-displacement curve following the giant pop-in is explained in terms of a compliant response of plates of material around the indent detached by lateral cracking. The possible causes of amorphization are discussed, and the implications in light of earlier indentation studies of Ge are considered

Effect of hydrogen on nanoindentation-induced phase transformations in amorphous silicon

The effect of local hydrogen concentration on nanoindentation-inducedphase transformations has been investigated in ion-implanted amorphous silicon(a-Si). Elevated concentrations of H ranging from 5×10¹⁸ to 5×10²⁰ cm⁻³, over the depth of indentation-induced phase transformed zones have been formed in the a-Si by H ion-implantation. Indentation has been performed under conditions that result in phase transformed zones composed totally of Si-III/Si-XII in the “H-free” samples. Deformation during indentation and determination of phase transformation behavior has been examined by analysis of load/unload curves, Raman microspectroscopy, and cross-sectional transmission electron microscopy (XTEM). With increasing H content, the probability of forming Si-III/Si-XII and the volume fraction of Si-III/Si-XII decrease. XTEM shows that these reduced volumes are randomly distributed within the phase transformed zone and are surrounded by indentation-induced a-Si. For a H concentration of 5×10²⁰ cm⁻³, the probability of forming Si-III/Si-XII is reduced to 0.5 compared to 1 in “H-free” material and for those indents that exhibit the Si-III/Si-XII end phase the volume fraction is approximately 60 %. We suggest that the monohydride bonding configuration of Si and H in a-Si reduces the formation of the high pressure crystalline phases by retarding growth of the crystallites through a similar mechanism to that of hydrogen-retarded solid phase crystallization of a-Si to diamond cubic crystalline Si-I phase.The authors are grateful to funding from the Australian Research Council

Patterning of silicon by indentation and chemical etching

An array of features on Si 100 is fabricated by a new maskless pattering process involving a combination of indentation and anisotropic wet chemical etching. Indentation is carried out in order to induce transformation to the high-pressure phases, Si III and Si XII, before etching in a KOH solution. The pressure-induced phases are found to be highly resistant to etching in the KOH solution, with an etch rate more than an order of magnitude slower than that of Si 100. The possibility of exploiting this mechanism for a maskless nanoscale patterning process in Si using indentation is discussed.The authors would like to acknowledge the Australian Research Council and the WRiota Pty Ltd. for funding

Segregation and precipitation of Er in Ge

Although Er-doped Genanomaterials are attractive for photonic applications, very little is known about the basic properties of Er in Ge. Here, the authors study the annealing behavior of Geimplanted with keV Er ions to doses resulting in ≲1at.% of Er. Large redistribution of Er, with segregation at the amorphous/crystalline interface, starts at ≳500°C, while lower temperatures are required for material recrystallization. However, even at 400°C, Er forms precipitates. The concentration of Er trapped in the bulk after recrystallization decreases with increasing temperature but is independent of the initial bulk Er concentration for the range of ion doses studied here.Work at the ANU was supported by the ARC

Experimental evidence of new tetragonal polymorphs of silicon formed through ultrafast laser-induced confined microexplosion

Ordinary materials can transform into novel phases at extraordinary high pressure and temperature. The recently developed method of ultrashort laser-induced confined microexplosions initiates a non-equilibrium disordered plasma state. Ultra-high quenching rates overcome kinetic barriers to the formation of new metastable phases, which are preserved in the surrounding pristine crystal for subsequent exploitation. Here we demonstrate that confined microexplosions in silicon produce several metastable end phases. Comparison with an ab initio random structure search reveals six energetically competitive potential phases, four tetragonal and two monoclinic structures. We show the presence of bt8 and st12, which have been predicted theoretically previously, but have not been observed in nature or in laboratory experiments. In addition, the presence of the as yet unidentified silicon phase, Si-VIII and two of our other predicted tetragonal phases are highly likely within laser-affected zones. These findings may pave the way for new materials with novel and exotic properties