3D High-Resolution Chemical Characterization of Sputtered Li-Rich NMC811 Thin Films Using TOF-SIMS.

Massive demand for Li-ion batteries stimulates the research of new materials such as high-capacity cathodes, metal anodes, and solid electrolytes, which should ultimately lead to new generations of batteries such as all-solid-state batteries. Such material discovery often requires knowledge on lithium's content and local distribution in complex Li-containing systems, which is a challenging analytical task. The state-of-the-art time-of-flight secondary-ion mass spectrometry (TOF-SIMS) is one of the few chemical analysis techniques allowing for parallel detection of all sample components and representing their distributions in 3D with nanoscale resolution. In this work, we explore the outstanding potential of TOF-SIMS for comprehensive chemical and nano-/micro-structural characterization of novel Li-rich nickel manganese cobalt oxide thin films, which are potential cathode materials for the future generation batteries. Off-stoichiometric thin films of Li- and Ni-rich layered oxide with the composition of LixNi0.8Mn0.1Co0.1O2 (LR-NMC811, x > 1) were deposited using reactive magnetron sputtering. Such thin films do not contain any conductive additives or binders and therefore serve as model 2D systems to investigate compositional fluctuations, surface and interface phenomena, and their aging. TOF-SIMS revealed the presence of 400 ± 100 nm overlithiated grains and 100 ± 30 nm nanoparticles with an increased 7Li16O+ ion content in the buried part of LR-NMC811. The Li-rich agglomerates could potentially serve as Li reservoirs for compensating Li losses during cathode fabrication and cell operation. Interestingly, these sub-micron structures decomposed in time upon exposure to ambient conditions for 30 days.

Draw-spun, photonically annealed Ag fibers as alternative electrodes for flexible CIGS solar cells.

We explore the feasibility of Ag fiber meshes as electron transport layer for high-efficiency flexible Cu(In,Ga)Se2 (CIGS) solar cells. Woven meshes of Ag fibers after UV illumination and millisecond flash-lamp treatment results in a sheet resistance of 17 Ω/sq and a visible transmittance above 85%. Conductive Ag meshes are integrated into flexible CIGS cells as transparent conductive electrode (TCE) alone or together with layers of Al-doped ZnO (AZO) with various thickness of 0…900 nm. The Ag mesh alone is not able to function as a current collector. If used together with a thin AZO layer (50 nm), the Ag mesh markedly improves the fill factor and cell efficiency, in spite of the adverse mesh shadowing. When Ag mesh is combined with thicker (200 nm or 900 nm) AZO layers, no improvements in photovoltaic parameters are obtained. When comparing a hybrid TCE consisting of 50 nm AZO and Ag fiber mesh with a thick 900 nm reference AZO device, an improved charge carrier collection in the near-infrared range is observed. Regardless of the AZO thickness, the presence of Ag mesh slows down cell degradation upon mechanical tensile stress, which could be interesting for implementation into flexible thin film CIGS modules.

Electrochemical Activation of Fe-LiF Conversion Cathodes in Thin-Film Solid-State Batteries.

Transition metal fluoride (TMF) conversion-type cathodes promise up to 4 times higher gravimetric energy densities compared to those of common intercalation-type cathodes. However, TMF cathodes demonstrate sluggish kinetics, poor efficiencies, and incompatibility with many liquid electrolytes. In this work, coevaporated heterostructured iron and lithium fluoride (Fe-LiF) cathodes are investigated in thin-film solid-state batteries with a LiPON electrolyte and a lithium metal anode. The cells were cycled 2000 times at a cycling rate of 6C. They show a gradual improvement in voltaic efficiency (37-53%) and specific capacity (146-216 mAh/g) during cycling. After 2000 cycles, the cathode capacity reaches 480 mAh/g at a cycling rate of C/3.6, close to its theoretical capacity of 498 mAh/g, at room temperature conditions. This capacity gain is correlated with an observed electrochemically activated nanorestructuring of the cathode, characterized by cycling-induced coarsening (from 2.8 to 4.2 nm) of the metallic iron phase and its accumulation near the current collector interface, as well as lithium fluoride phase accumulation near the LiPON interface.

Influence of Au, Pt, and C Seed Layers on Lithium Nucleation Dynamics for Anode-Free Solid-State Batteries.

In the concept of anode-free lithium-ion batteries, cells are manufactured with a bare anode current collector where the lithium metal anode is electrochemically formed from the lithium-containing cathode during the first charge cycle. While this concept has many attractive aspects from a manufacturing and energy density standpoint, stable plating and stripping remain challenging. We have investigated gold, platinum, and amorphous carbon as seed layers placed between the copper current collector and the lithium phosphorus oxynitride thin-film solid electrolyte. These layers guide lithium nucleation and improve the plating and stripping dynamics. All seed layers facilitate reversible lithium plating and stripping even at high current densities up to 8 mA cm-2. Of particular note is the amorphous carbon seed layer, which allowed a significant reduction in plating potential from 300 mV to as low as 50 mV. These results underscore the critical role of seed layers in improving the efficiency of anode-free solid-state batteries and open the door to simplified manufacturing of anode-free battery designs.

Monolithically-stacked thin-film solid-state batteries.

The power capability of Li-ion batteries has become increasingly limiting for the electrification of transport on land and in the air. The specific power of Li-ion batteries is restricted to a few thousand W kg-1 due to the required cathode thickness of a few tens of micrometers. We present a design of monolithically-stacked thin-film cells that has the potential to increase the power ten-fold. We demonstrate an experimental proof-of-concept consisting of two monolithically stacked thin-film cells. Each cell consists of a silicon anode, a solid-oxide electrolyte, and a lithium cobalt oxide cathode. The battery can be cycled for more than 300 cycles between 6 and 8 V. Using a thermo-electric model, we predict that stacked thin-film batteries can achieve specific energies >250 Wh kg-1 at C-rates above 60, resulting in a specific power of tens of kW kg-1 needed for high-end applications such as drones, robots, and electric vertical take-off and landing aircrafts.

Highly efficient Cu(In,Ga)Se2 solar cells grown on flexible polymer films.

Solar cells based on polycrystalline Cu(In,Ga)Se(2) absorber layers have yielded the highest conversion efficiency among all thin-film technologies, and the use of flexible polymer films as substrates offers several advantages in lowering manufacturing costs. However, given that conversion efficiency is crucial for cost-competitiveness, it is necessary to develop devices on flexible substrates that perform as well as those obtained on rigid substrates. Such comparable performance has not previously been achieved, primarily because polymer films require much lower substrate temperatures during absorber deposition, generally resulting in much lower efficiencies. Here we identify a strong composition gradient in the absorber layer as the main reason for inferior performance and show that, by adjusting it appropriately, very high efficiencies can be obtained. This implies that future manufacturing of highly efficient flexible solar cells could lower the cost of solar electricity and thus become a significant branch of the photovoltaic industry.

Aerosol Jet Printing of 3D Pillar Arrays from Photopolymer Ink.

An aerosol jet printing (AJP) printing head built on top of precise motion systems can provide positioning deviation down to 3 µm, printing areas as large as 20 cm × 20 cm × 30 cm, and five-axis freedom of movement. Typical uses of AJP are 2D printing on complex or flexible substrates, primarily for applications in printed electronics. Nearly all commercially available AJP inks for 2D printing are designed and optimized to reach desired electronic properties. In this work, we explore AJP for the 3D printing of free-standing pillar arrays. We utilize aryl epoxy photopolymer as ink coupled with a cross-linking "on the fly" technique. Pillar structures 550 µm in height and with a diameter of 50 µm were 3D printed. Pillar structures were characterized via scanning electron microscopy, where the morphology, number of printed layers and side effects of the AJP technique were investigated. Satellite droplets and over-spray seem to be unavoidable for structures smaller than 70 µm. Nevertheless, reactive ion etching (RIE) as a post-processing step can mitigate AJP side effects. AJP-RIE together with photopolymer-based ink can be promising for the 3D printing of microstructures, offering fast and maskless manufacturing without wet chemistry development and heat treatment post-processing.

Influence of amorphous carbon interlayers on nucleation and early growth of lithium metal at the current collector-solid electrolyte interface.

Nucleation and early growth of Li metal is critical to the performance of anode-free solid-state batteries. We report the use of amorphous carbon deposited by direct current magnetron sputtering as an intermediate layer between the Cu current collector and the Lipon solid electrolyte. The density, conductivity, and microstructure of the carbon interlayer are varied and their influence on the reversible formation and removal of the Li metal anode is investigated. It is shown that thin films of amorphous carbon act as seed layers, reducing the overpotential for Li plating and increasing the critical current density for Li plating and stripping from 2 up to 8 mA cm-2. It is further demonstrated that the ionic conductivity of the Li ions in the carbon interlayers determines their optimum thickness to be 100 nm or less, and that the initial Li loss due to interphase formation can be reduced to a few tens of nm by decreasing the density of the carbon films.

Detection of Au+ Ions During Fluorine Gas-Assisted Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS) for the Complete Elemental Characterization of Microbatteries.

Due to excellent electric conductivity and chemical inertness, Au can be used in new microdevices for energy applications, microelectronics, and biomedical solutions. However, the chemical analysis of Au-containing systems using time-of-flight secondary ion mass spectrometry (TOF-SIMS) can be difficult because of the negative ionization of Au, as most metals form positive ions, and therefore cannot be detected from the same analytical volume. In this work, we present the potential of fluorine gas coinjection for altering the polarity, from the negative to positive, of Au secondary ions generated under Ga+ beam bombardment. The importance of detecting Au+ ions and representing their spatial distribution in nanoscale was demonstrated using a novel solid electrolyte for Li-ion solid-state batteries, amorphous Li7La3Zr2O12 (aLLZO). This allowed for assessing the migration of mobile Li+ ions outside the aLLZO layer and alloying the Au layer with Li, which explained the presence of an internal electric field observed during the polarization measurements. Remarkably, during fluorine gas-assisted TOF-SIMS measurements, the trace amount of Au content (5 ppm) was detected in a Pt layer (unattainable under standard vacuum conditions). In conclusion, fluorine gas-assisted TOF-SIMS can help understanding operation mechanisms and potential degradation processes of microdevices and therefore help optimizing their functionality.

Millisecond photonic sintering of iron oxide doped alumina ceramic coatings.

The sintering of alumina (Al2O3) traditionally occurs at high temperatures (up to ca. 1700 °C) and in significantly long times (up to several hours), which are required for the consolidation of the material by diffusion processes. Here we investigate the photonic sintering of alumina particles using millisecond flash lamp irradiation with extreme heating rates up to 108 K/min. The limitation of the low visible light absorption of alumina is resolved by adding colored α-Fe2O3 nanoparticles, which initiated the grain growth during sintering. After the millisecond-long light pulses from a xenon flash lamp, a bimodal mixture of α-Al2O3 precursor particles was sintered and iron segregation at the grain boundaries was observed. The proposed photonic sintering approach based on doping with colored centers may be extended to other refractory ceramics with low absorption in the visible light range once appropriate high-absorbing dopants are identified.

Influence of the Rear Interface on Composition and Photoluminescence Yield of CZTSSe Absorbers: A Case for an Al2O3 Intermediate Layer.

The rear interface of kesterite absorbers with Mo back contact represents one of the possible sources of nonradiative voltage losses (ΔVoc,nrad) because of the reported decomposition reactions, an uncontrolled growth of MoSe2, or a nonoptimal electrical contact with high recombination. Several intermediate layers (IL), such as MoO3, TiN, and ZnO, have been tested to mitigate these issues, and efficiency improvements have been reported. However, the introduction of IL also triggers other effects such as changes in alkali diffusion, altered morphology, and modifications in the absorber composition, all factors that can also influence ΔVoc,nrad. In this study, the different effects are decoupled by designing a special sample that directly compares four rear structures (SLG, SLG/Mo, SLG/Al2O3, and SLG/Mo/Al2O3) with a Na-doped kesterite absorber optimized for a device efficiency >10%. The IL of choice is Al2O3 because of its reported beneficial effect to reduce the surface recombination velocity at the rear interface of solar cell absorbers. Identical annealing conditions and alkali distribution in the kesterite absorber are preserved, as measured by time-of-flight secondary ion mass spectrometry and energy-dispersive X-ray spectroscopy. The lowest ΔVoc,nrad of 290 mV is measured for kesterite grown on Mo, whereas the kesterite absorber on Al2O3 exhibits higher nonradiative losses up to 350 mV. The anticipated field-effect passivation from Al2O3 at the rear interface could not be observed for the kesterite absorbers prepared by the two-step process, further confirmed by an additional experiment with air annealing. Our results suggest that Mo with an in situ formed MoSe2 remains a suitable back contact for high-efficiency kesterite devices.

Radiative lifetime-encoded unicolour security tags using perovskite nanocrystals.

Traditional fluorescence-based tags, used for anticounterfeiting, rely on primitive pattern matching and visual identification; additional covert security features such as fluorescent lifetime or pattern masking are advantageous if fraud is to be deterred. Herein, we present an electrohydrodynamically printed unicolour multi-fluorescent-lifetime security tag system composed of lifetime-tunable lead-halide perovskite nanocrystals that can be deciphered with both existing time-correlated single-photon counting fluorescence-lifetime imaging microscopy and a novel time-of-flight prototype. We find that unicolour or matching emission wavelength materials can be prepared through cation-engineering with the partial substitution of formamidinium for ethylenediammonium to generate "hollow" formamidinium lead bromide perovskite nanocrystals; these materials can be successfully printed into fluorescence-lifetime-encoded-quick-read tags that are protected from conventional readers. Furthermore, we also demonstrate that a portable, cost-effective time-of-flight fluorescence-lifetime imaging prototype can also decipher these codes. A single comprehensive approach combining these innovations may be eventually deployed to protect both producers and consumers.

Fast Charge Transfer across the Li7La3Zr2O12 Solid Electrolyte/LiCoO2 Cathode Interface Enabled by an Interphase-Engineered All-Thin-Film Architecture.

Lithium garnet Li7La3Zr2O12 (LLZO) is being investigated as a potential solid electrolyte for next-generation solid-state batteries owing to its high ionic conductivity and electrochemical stability against metallic lithium and high potential cathodes. While the LLZO/Li metal anode interface has been thoroughly investigated to achieve almost negligible interface resistances, the LLZO/cathode interface still suffers from high interfacial resistances mainly due to the high-temperature sintering required for proper ceramic bonding. In this work, the LLZO solid electrolyte/LiCoO2 (LCO) cathode interface is investigated in an all-thin-film model system. This architecture provides an easy access to the interface for in situ and ex situ characterization, allowing one to identify the degradation processes taking place under high-temperature cosintering and to test solutions such as interface modifications. Introducing an in situ-lithiated Nb2O5 diffusion barrier at the interface, we were able to lower the LLZO/LCO charge transfer resistance to about 50 Ω cm2, a 3-fold reduction with respect to previously reported values. The low interfacial resistance combined with the high conductance through the LLZO thin-film electrolyte allows one to investigate the charge transfer at high charge-discharge rates, unlike in bulk systems. At 1C, discharge capacities of about 140 mA h g-1 were measured, and at 10C, 60% of the theoretical capacity was retained with a cycle life over 100 cycles. Besides the role of this architecture in the interface investigation, this work also constitutes a milestone in the development of thin-film solid-state batteries with higher power densities.

Synaptic transistors with aluminum oxide dielectrics enabling full audio frequency range signal processing.

The rapid evolution of the neuromorphic computing stimulates the search for novel brain-inspired electronic devices. Synaptic transistors are three-terminal devices that can mimic the chemical synapses while consuming low power, whereby an insulating dielectric layer physically separates output and input signals from each other. Appropriate choice of the dielectric is crucial in achieving a wide range of operation frequencies in these devices. Here we report synaptic transistors with printed aluminum oxide dielectrics, improving the operation frequency of solution-processed synaptic transistors by almost two orders of magnitude to 50 kHz. Fabricated devices, yielding synaptic response for all audio frequencies (20 Hz to 20 kHz), are employed in an acoustic response system to show the potential for future research in neuro-acoustic signal processing with printed oxide electronics.

Analysis of the Voltage Losses in CZTSSe Solar Cells of Varying Sn Content.

The performance of kesterite (Cu2ZnSn(S,Se)4, CZTSSe) solar cells is hindered by low open circuit voltage ( Voc). The commonly used metric for Voc-deficit, namely, the difference between the absorber band gap and qVoc, is not well-defined for compositionally complex absorbers like kesterite where the bandgap is hard to determine. Here, nonradiative voltage losses are analyzed by measuring the radiative limit of Voc, using external quantum efficiency (EQE) and electroluminescence (EL) spectra, without relying on precise knowledge of the bandgap. The method is applied to a series of Cu2ZnSn(S,Se)4 devices with Sn content variation from 27.6 to 32.9 at. % and a corresponding Voc range from 423 to 465 mV. Surprisingly, the lowest nonradiative loss, and hence the highest external luminescence efficiency (QELED), were obtained for the device with the lowest Voc. The trend is assigned to better interface quality between absorber and CdS buffer layer at lower Sn content.

Effect of Magnesium Incorporation on Solution-Processed Kesterite Solar Cells.

The introduction of the alkaline-earth element Magnesium (Mg) into Cu2ZnSn(S,Se)4 (CTZSSe) is explored in view of potential photovoltaic applications. Cu2Zn1-xMgxSn(S,Se)4 absorber layers with variable Mg content x = 0…1 are deposited using the solution approach with dimethyl sulfoxide solvent followed by annealing in selenium atmosphere. For heavy Mg alloying with x = 0.55…1 the phase separation into Cu2SnSe3, MgSe2, MgSe and SnSe2 occurs in agreement with literature predictions. A lower Mg content of x = 0.04 results in the kesterite phase as confirmed by XRD and Raman spectroscopy. A photoluminescence maximum is red-shifted by 0.02 eV as compared to the band-gap and a carrier concentration NCV of 1 × 1016 cm-3 is measured for a Mg-containing kesterite solar cell device. Raman spectroscopy indicates that structural defects can be reduced in Mg-containing absorbers as compared to the Mg-free reference samples, however the best device efficiency of 7.2% for a Mg-containing cell measured in this study is lower than those frequently reported for the conventional Na doping.

ALD-Zn xTi yO as Window Layer in Cu(In,Ga)Se2 Solar Cells.

We report on the application of Zn xTi yO deposited by atomic layer deposition (ALD) as buffer layer in thin film Cu(In,Ga)Se2 (CIGS) solar cells to improve the photovoltaic device performance. State-of-the-art CIGS devices employ a CdS/ZnO layer stack sandwiched between the absorber layer and the front contact. Replacing the sputter deposited ZnO with ALD-Zn xTi yO allowed a reduction of the CdS layer thickness without adversely affecting open-circuit voltage ( VOC). This leads to an increased photocurrent density with a device efficiency of up to 20.8% by minimizing the parasitic absorption losses commonly observed for CdS. ALD was chosen as method to deposit homogeneous layers of Zn xTi yO with varying Ti content with a [Ti]/([Ti] + [Zn]) atomic fraction up to ∼0.35 at a relatively low temperature of 373 K. The Ti content influenced the absorption behavior of the Zn xTi yO layer by increasing the optical bandgap >3.5 eV in the investigated range. Temperature-dependent current-voltage ( I- V) measurements of solar cells were performed to investigate the photocurrent blocking behavior observed for high Ti content. Possible conduction band discontinuities introduced by Zn xTi yO are discussed based on X-ray photoelectron spectroscopy (XPS) measurements.

Enhanced Carrier Collection from CdS Passivated Grains in Solution-Processed Cu2ZnSn(S,Se)4 Solar Cells.

Solution processing of Cu2ZnSn(S,Se)4 (CZTSSe)-kesterite solar cells is attractive because of easy manufacturing using readily available metal salts. The solution-processed CZTSSe absorbers, however, often suffer from poor morphology with a bilayer structure, exhibiting a dense top crust and a porous bottom layer, albeit yielding efficiencies of over 10%. To understand whether the cell performance is limited by this porous layer, a systematic compositional study using (scanning) transmission electron microscopy ((S)TEM) and energy-dispersive X-ray spectroscopy of the dimethyl sulfoxide processed CZTSSe absorbers is presented. TEM investigation revealed a thin layer of CdS that is formed around the small CZTSSe grains in the porous bottom layer during the chemical bath deposition step. This CdS passivation is found to be beneficial for the cell performance as it increases the carrier collection and facilitates the electron transport. Electron-beam-induced current measurements reveal an enhanced carrier collection for this buried region as compared to reference cells with evaporated CdS.

Transparent, conducting ATO thin films by epoxide-initiated sol-gel chemistry: a highly versatile route to mixed-metal oxide films.

A robust synthesis approach to transparent conducting oxide (TCO) materials using epoxide assisted sol-gel chemistry is reported. The new route utilizes simple tin and antimony chloride precursors in aqueous solution, thus eliminating the need for organometallic precursors. Propylene oxide acts as a proton scavenger and drives metal hydroxide formation and subsequent polycondensation reactions. Thin films of antimony-doped tin oxide (ATO) were prepared by dip-coating of mixed metal oxide sols. After annealing at 600 °C in air, structural, electrical and optical properties of undoped and Sb-doped tin oxide films were characterized. Single layer films with 5 mol % Sb doping exhibited an optical transparency which was virtually identical to that of the plain glass substrate and an electrical resistivity of 2.8 × 10(-2) Ω cm. SEM and AFM analysis confirmed the presence of surface defects and cracks which increased with increasing Sb dopant concentration. Multiple depositions of identical ATO films showed a roughly 1 order of magnitude decrease in the film resistivity after the third layer, with typical values below 5 × 10(-3) Ω cm. This suggests that a second and third deposition fill up residual cracks and defects in the first layer and thus brings out the full performance of the ATO material. The epoxide-assisted sol chemistry is a promising technique for the preparation of mixed oxide thin film materials. Its superiority over conventional alkoxide and metal salt-based methods is explained in the context of a general description of the reaction mechanism.

Nanoscale infrared absorption spectroscopy of individual nanoparticles enabled by scattering-type near-field microscopy.

Infrared absorption spectroscopy is a powerful and widely used tool for analyzing the chemical composition and structure of materials. Because of the diffraction limit, however, it cannot be applied for studying individual nanostructures. Here we demonstrate that the phase contrast in substrate-enhanced scattering-type scanning near-field optical microscopy (s-SNOM) provides a map of the infrared absorption spectrum of individual nanoparticles with nanometer-scale spatial resolution. We succeeded in the chemical identification of silicon nitride nanoislands with heights well below 10 nm, by infrared near-field fingerprint spectroscopy of the Si-N stretching bond. Employing a novel theoretical model, we show that the near-field phase spectra of small particles correlate well with their far-field absorption spectra. On the other hand, the spectral near-field contrast does not scale with the volume of the particles. We find a nearly linear scaling law, which we can attribute to the near-field coupling between the near-field probe and the substrate. Our results provide fundamental insights into the spectral near-field contrast of nanoparticles and clearly demonstrate the capability of s-SNOM for nanoscale chemical mapping based on local infrared absorption.