Direct Observation of Grain-Boundary-Migration-Assisted Radiation Damage Healing in Ultrafine Grained Gold under Mechanical Stress.

Nanostructured metals are a promising class of radiation-tolerant materials. A large volume fraction of grain boundaries (GBs) can provide plenty of sinks for radiation damage, and understanding the underlying healing mechanisms is key to developing more effective radiation tolerant materials. Here, we observe radiation damage absorption by stress-assisted GB migration in ultrafine-grained Au thin films using a quantitative in situ transmission electron microscopy nanomechanical testing technique. We show that the GB migration rate is significantly higher in the unirradiated specimens. This behavior is attributed to the presence of smaller grains in the unirradiated specimens that are nearly absent in the irradiated specimens. Our experimental results also suggest that the GB mobility is decreased as a result of irradiation. This work implies that the deleterious effects of irradiation can be reduced by an evolving network of migrating GBs under stress.

Skin-like low-noise elastomeric organic photodiodes.

Stretchable optoelectronics made of elastomeric semiconductors could enable the integration of intelligent systems with soft materials, such as those of the biological world. Organic semiconductors and photodiodes have been engineered to be elastomeric; however, for photodetector applications, it remains a challenge to identify an elastomeric bulk heterojunction (e-BHJ) photoactive layer that combines a low Young's modulus and a high strain at break that yields organic photodiodes with low electronic noise values and high photodetector performance. Here, a blend of an elastomer, a donor-like polymer, and an acceptor-like molecule yields a skin-like e-BHJ with a Young's modulus of a few megapascals, comparable to values of human tissues, and a high strain at break of 189%. Elastomeric organic photodiodes based on e-BHJ photoactive layers maintain low electronic noise current values in the tens of femtoamperes range and noise equivalent power values in the tens of picowatts range under at least 60% strain.

Correction: In situ TEM measurement of activation volume in ultrafine grained gold.

Correction for 'In situ TEM measurement of activation volume in ultrafine grained gold' by Saurabh Gupta et al., Nanoscale, 2020, 12, 7146-7158, DOI: 10.1039/D0NR01874K.

In situ TEM measurement of activation volume in ultrafine grained gold.

A micro-electromechanical system (MEMS) based technique is demonstrated for in situ transmission electron microscopy (TEM) measurements of stress relaxation with simultaneous observation of the underlying plastic deformation processes. True activation volumes are determined from repeated stress relaxation transients and thus provide a signature parameter of the governing mechanisms of plastic deformation. The technique is demonstrated with 100 nm-thick ultrafine-grained gold microspecimens under uniaxial tension. True activation volumes of approximately 3-5b3 (where b is the Burgers vector length) are obtained for tensile stresses ranging from 200-450 MPa. Grain boundary-dislocation interactions are observed via in situ TEM during stress relaxation measurements. The miniaturization of stress relaxation tests inside the TEM provides unique opportunities to characterize the plastic kinetics and underlying mechanisms in ultrafine-grained and nanocrystalline materials.

Influence of Polymer Substrate Damage on the Time Dependent Cracking of SiNx Barrier Films.

This work is concerned with the long-term behavior of environmentally-assisted subcritical cracking of PECVD SiNx barrier films on polyethylene terephthalate (PET) and polyimide (PI) substrates. While environmentally-assisted channel cracking in SiNx has been previously demonstrated, with constant crack growth rates over short periods of time (<1 hour) during which no substrate damage was observed, the present experiments over longer periods reveal a regime where cracking also develops in the polymer substrate. This time-dependent local cracking of the polymer underneath the channel crack is expected based on creep rupture or static fatigue. Our combined in-situ microscopy and finite-element modeling results highlight the combined effects of neighboring cracks and substrate cracking on the crack growth rate evolution in the film. In most cases, the subcritical crack growth rates decrease over time by up to two orders of magnitude until steady-state rates are reached. For SiNx on PI, crack growth rates were found to be more stable over time due to the lack of crack growth in the substrate as compared to SiNx on PET. These results provide a guideline to effectively improving the long-term reliability of flexible barriers by a substrate possessing high strength which limits substrate damage.

Quantitative in Situ SEM High Cycle Fatigue: The Critical Role of Oxygen on Nanoscale-Void-Controlled Nucleation and Propagation of Small Cracks in Ni Microbeams.

This Letter presents a quantitative in situ scanning electron microscope (SEM) nanoscale high and very high cycle fatigue (HCF/VHCF) investigation of Ni microbeams under bending, using a MEMS microresonator as an integrated testing machine. The novel technique highlights ultraslow fatigue crack growth (average values down to ∼10-14 m/cycle) that has heretofore not been reported and that indicates a discontinuous process; it also reveals strong environmental effects on fatigue lives that are 3 orders of magnitude longer in a vacuum than in air. This ultraslow fatigue regime does not follow the well documented fatigue mechanisms that rely on the common crack tip stress intensification, mediated by dislocation emission and associated with much larger crack growth rates. Instead, our study reveals fatigue nucleation and propagation mechanisms that mainly result from room temperature void formation based on vacancy condensation processes that are strongly affected by oxygen. This study therefore shows significant size effects governing the bending high/very high cycle fatigue behavior of metals at the micro- and nanoscales, whereby the stress concentration effect at the tip of a growing small fatigue crack is assumed to be greatly reduced by the effect of the bending-induced extreme stress gradients, which prevents any significant cyclic crack tip opening displacement. In this scenario, ultraslow processes relying on vacancy formation at the subsurface or in the vicinity of a crack tip and subsequent condensation into voids become the dominant fatigue mechanisms.

Environmentally Assisted Cracking in Silicon Nitride Barrier Films on Poly(ethylene terephthalate) Substrates.

A singular critical onset strain value has been used to characterize the strain limits of barrier films used in flexible electronics. However, such metrics do not account for time-dependent or environmentally assisted cracking, which can be critical in determining the overall reliability of these thin-film coatings. In this work, the time-dependent channel crack growth behavior of silicon nitride barrier films on poly(ethylene terephthalate) (PET) substrates is investigated in dry and humid environments by tensile tests with in situ optical microscopy and numerical models. The results reveal the occurrence of environmentally assisted crack growth at strains well below the critical onset crack strain and in the absence of polymer-relaxation-assisted, time-dependent crack growth. The crack growth rates in laboratory air are about 1 order of magnitude larger than those tested in dry environments (dry air or dry nitrogen). In laboratory air, crack growth rates increase from ∼200 nm/s to 60 µm/s for applied stress intensity factors, K, ranging from 1.0 to 1.4 MPa·m1/2, below the measured fracture toughness Kc of 1.8 MPa·m1/2. The crack growth rates in dry environments were also strongly dependent on the prior storage of the specimens, with larger rates for specimens exposed to laboratory air (and therefore moisture) prior to testing compared to specimens stored in a dry environment. This behavior is attributed to moisture-assisted cracking, with a measured power law exponent of ∼22 in laboratory air. This study also reveals that much larger densities of channel cracks develop in the humid environment, suggesting an easier initiation of channel cracks in the presence of water vapor. The results obtained in this work are critical to address the time-dependent and environmental reliability issues of thin brittle barriers on PET substrates for flexible electronics applications.

Quantifying and observing viscoplasticity at the nanoscale: highly localized deformation mechanisms in ultrathin nanocrystalline gold films.

This study unveils the stress relaxation transient deformation mechanisms in 100 nm-thick, nanocrystalline Au films thanks to a robust quantitative in situ TEM MEMS nanomechanical testing approach to quantify stress relaxation and to perform in situ observations of time-dependent deformation in ultrathin nanocrystalline films. The relaxation is characterized by a decrease in plastic strain rate of more than one order of magnitude over the first ∼30 minutes (from 10(-4) to less than 10(-5) s(-1)). For longer relaxation experiments, the plastic strain rate decreases down to 10(-7) s(-1) after several hours. The power-law exponent n, relating plastic strain rate and stress, continuously decreases from initial large values (n from 6 to 14 at t = 0) down to low values (n ∼ 1-2) after several hours. In situ TEM observations reveal that the relaxation behavior is initially accommodated by highly localized, sustained, intergranular and transgranular dislocation motion. Over time, the dislocation sources become less operative or exhausted, leading to a transition to grain-boundary-diffusion based mechanisms. The results also highlight a promising technique for nanoscale characterization of time-dependent deformation.

Comparison of the cohesive and delamination fatigue properties of atomic-layer-deposited alumina and titania ultrathin protective coatings deposited at 200 °C.

The fatigue properties of ultrathin protective coatings on silicon thin films were investigated. The cohesive and delamination fatigue properties of 22 nm-thick atomic-layered-deposited (ALD) titania were characterized and compared to that of 25 nm-thick alumina. Both coatings were deposited at 200 °C. The fatigue rates are comparable at 30 °C, 50% relative humidity (RH) while they are one order of magnitude larger for alumina compared to titania at 80 °C, 90% RH. The improved fatigue performance is believed to be related to the improved stability of the ALD titania coating with water compared to ALD alumina, which may in part be related to the fact that ALD titania is crystalline, while ALD alumina is amorphous. Static fatigue crack nucleation and propagation was not observed. The underlying fatigue mechanism is different from previously documented mechanisms, such as stress corrosion cracking, and appears to result from the presence of compressive stresses and a rough coating-substrate interface.

Quantitative in situ TEM tensile fatigue testing on nanocrystalline metallic ultrathin films.

A unique technique to perform quantitative in situ transmission electron microscopy (TEM) fatigue testing on ultrathin films and nanomaterials is demonstrated. The technique relies on a microelectromechanical system (MEMS) device to actuate a nanospecimen and measure its mechanical response. Compared to previously demonstrated MEMS-based in situ TEM techniques, the technique takes advantage of two identical capacitive sensors on each side of the specimen to measure electronically elongation (with nm resolution) and applied force (with µN resolution). Monotonic and fatigue tests were performed on nanocrystalline gold ultrathin film specimens that were manipulated and fixed onto the MEMS device without the use of a focused ion-beam microscope (and therefore, importantly, without any associated surface damage). The major advantage of the technique is its capability to use TEM imaging solely for high magnification microstructural observations while the MEMS device provides continuous tracking of the material's response, thereby expanding the capabilities of MEMS-based techniques towards more complex in situ TEM nanomechanical tests, such as fatigue tests.

Interfacial cyclic fatigue of atomic-layer-deposited alumina coatings on silicon thin films.

A microresonator-based interfacial fatigue testing technique was used to investigate the subcritical delamination of atomic-layer-deposited alumina coatings along the sidewalls of deep-reactive-ion-etched monocrystalline silicon thin films. This technique ensures loading conditions relevant to microelectromechanical system devices, including kHz testing frequency and fully reversed cyclic stresses. Four different coating thicknesses (4.2, 12.6, 25, and 50 nm) were investigated in two environments (30 °C, 50% relative humidity (RH) and 80 °C, 90% RH). Fatigue damage, in the form of channel cracks and delamination of the alumina coating, was found to accumulate slowly over more than 1 × 10(8) cycles. The average delamination rates increase with increasing energy release rate amplitude for delamination, modeled with a power law relationship. In the harsher environment, the rates are roughly 1 order of magnitude higher. Additionally, a few tests under static load were conducted for which no delamination (or crack growth) occurred, demonstrating that the governing interfacial fatigue mechanism is cycle-dependent.