Air-sensitive Materials Research Articles

Compact vacuum transfer devices for highly air-sensitive materials in scanning electron microscopy

Surface analysis experiments on air-sensitive substances are challenging to avoid their contact with air, leading to inaccurate results due to oxidation or hygroscopicity. To address this issue, we designed a compact vacuum transfer device (VTD) and applied it to scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS) experiments. Our VTD features a split structure that can be opened and separated in the SEM specimen exchange chamber via magnetic control. This design allows the SEM manufacturer's stub to be fed directly into the SEM specimen chamber, preventing damage to the instrument's internal components and avoiding restrictions on specimen height. Additionally, the compact design maximizes the utilization of sample accommodation space. Besides, it can be flexibly customized in different sizes and types of stubs to adapt electron microscopes from various manufacturers. To confirm the reliability of our device, we applied it to several highly air-sensitive samples for morphology and chemical composition analysis by SEM and EDS. The EDS results showed that the atomic percentage of Na reaches 94.55 % after 14 minutes and 93.44 % after 30 minutes of storage when transferring metallic sodium. Furthermore, our VTD enables airtight recycling and re-transfer of samples after the SEM (-EDS) experiments. These results demonstrate that our device has excellent practicality and airtightness, making it suitable for medium- and long-distance sample transfer between laboratories on the campus.

Synthesis and Characterization of Epitaxially-Fused Quantum Dot Superlattices at the Single Grain Limit

Epitaxially-fused superlattices of colloidal quantum dots (QD epi-SLs) may exhibit electronic minibands and high-mobility charge transport, but doing so requires epi-SLs with extremely high degrees of spatial and chemical (compositional) uniformity. In this talk, I will discuss both our efforts to understand and improve the epi-SL formation process, as well as recent charge transport studies on single epi-SL grains.Epi-SLs are synthesized from a parent SL structure, typically composed of QDs with long insulating ligands. Over the past several years, we have developed insight into the physical and chemical mechanisms by which this parent SL structure is converted into an epi-SL. I will present detailed, multi-model structural characterization of the SL structures, which unveils the astonishing choreographic process by which millions of QDs rotate and translate, in concert, to form the epi-SL.This structural transformation is initiated by chemical changes to the QD ligand layer, usually through manual introduction of liquids into the SL film. Mechanistic studies into this ligand-exchange process reveal a multi-step chemical sequence that initiates with a simple acid-base reaction. We exploit this insight to fabricate epi-SLs by means of photochemical triggering (using ultraviolet illumination) rather than alternative “hands-on” techniques which suffer from poor experimental control and pronounced chemical inhomogeneity and structural damage in the films. The use of light to trigger the SL conversion process enables much finer control in both the temporal and spatial domains, opening the door to much larger-area SL films and direct photopatterning of epi-SLs.In the latter portion of the talk, I will present recent work charge transport studies in individual, highly-ordered PbSe QD epi-SL grains. One technical challenge in making these devices is the inherent mismatch in using traditional microfabrication techniques to make single-grained devices of air-sensitive materials. Here, we demonstrate the air-free fabrication of microscale field-effect transistors (μ-FETs) with channels consisting of single PbSe QD epi-SL grains (~ 1 -10 µm grain sizes) and analyze charge transport phenomena in these samples. The devices exhibit p-channel or ambipolar transport with a hole mobility as high as 3.5 cm2 V–1 s–1 at 290 K and 6.5 cm2 V–1 s–1 at 170–220 K, one order of magnitude larger than that of previous QD solids.

Transferable Optical Enhancement Nanostructures by Gapless Stencil Lithography.

Optical spectroscopy techniques are central for the characterization of two-dimensional (2D) quantum materials. However, the reduced volume of atomically thin samples often results in a cross section that is far too low for conventional optical methods to produce measurable signals. In this work, we developed a scheme based on the stencil lithography technique to fabricate transferable optical enhancement nanostructures for Raman and photoluminescence spectroscopy. Equipped with this new nanofabrication technique, we designed and fabricated plasmonic nanostructures to tailor the interaction of few-layer materials with light. We demonstrate orders-of-magnitude increase in the Raman intensity of ultrathin flakes of 2D semiconductors and magnets as well as selective Purcell enhancement of quenched excitons in WSe2/MoS2 heterostructures. We provide evidence that the method is particularly effective for air-sensitive materials, as the transfer can be performed in situ. The fabrication technique can be generalized to enable a high degree of flexibility for functional photonic devices.

Advances in 2D Material Transfer Systems for van der Waals Heterostructure Assembly

The assembly of van der Waals (vdW) heterostructures using 2D material transfer systems has revolutionized the field of materials science, enabling the development of novel electronic and optoelectronic devices and the probing of emergent phenomena. The innovative vertical stacking methods enabled by these 2D material transfer systems are central to constructing complex devices, which are often challenging to achieve with traditional bottom-up nanofabrication techniques. Over the past decade, vdW heterostructures have unlocked numerous applications leading to the development of advanced devices, such as transistors, photodetectors, solar cells, and sensors. However, achieving consistent performance remains challenging due to variations in transfer processes, contamination, and the handling of air-sensitive materials, among other factors. Several of these challenges can be addressed through careful design considerations of transfer systems and through innovative modifications. This mini-review critically examines the current state of transfer systems, focusing on their design, cost-effectiveness, and operational efficiency. Special emphasis is placed on low-cost systems and glovebox integration essential for handling air-sensitive materials. We highlight recent advancements in transfer systems, including the integration of cleanroom environments within gloveboxes and the advent of robotic automation. Finally, we discuss ongoing challenges and the necessity for further innovations to achieve reliable, cleaner, and scalable vdW technologies for future applications.

Controlling surface chemistry in cold sintering to advance battery materials

Cold sintering is a recently introduced densification method that is of interest due to the lower energy used in the process, the ability to densify metastable materials, the ability to integrate materials to develop unique composites, and the ability to synthesis materials that can be more easily recycled. Collectively, these advantages make cold sintering a promising approach for processing of battery components, and co-sintering into all solid-state batteries. To obtain high electrochemical performance with cold sintering, detailed control of the surface chemistry of powders is needed, to avoid or minimize the impact of carbonate formation in grain boundaries, and to limit concentrations of secondary phases that are a result of incongruent dissolution processes. In this paper, we outline the importance of surface chemical reactions of powders in cold sintering, and the mitigating processes that can be adopted to control these reactions and obtain high performance and unique opportunities for Li and Na-oxide secondary batteries. We focus on a series of examples that demonstrate how the control of low temperature densification (cold sintering) can address the environmental sensitivity of many battery materials, and highlight the issues faced and open questions. These examples include cold sintering of air-sensitive solid electrolytes, re-processing of crushed solid electrolytes, surface passivation of air-sensitive active materials for processing in air, and fabrication of solid-solid macroscopic interfaces for solid-state batteries.

In situ via Contact to hBN-Encapsulated Air-Sensitive Atomically Thin Semiconductors.

Establishing reliable electrical contacts to atomically thin materials is a prerequisite for both fundamental studies and applications yet remains a challenge. In particular, the development of contact techniques for air-sensitive monolayers has lagged behind, despite their unique properties and significant potential for applications. Here, we present a robust method to create contacts to device layers encapsulated within hexagonal boron nitride (hBN). This method uses plasma etching and metal deposition to create 'vias' in the hBN with graphene forming an atomically thin etch-stop. The resulting partially fluorinated graphene (PFG) protects the underlying device layer from air-induced degradation and damage during metal deposition. PFG is resistive in-plane but maintains high out-of-plane conductivity. The work function of the PFG/metal contact is tunable through the degree of fluorination, offering opportunities for contact engineering. Using the in situ via technique, we achieve ambipolar contact to air-sensitive monolayer 2H-molybdenum ditelluride (MoTe2) with more than 1 order of magnitude improvement in on-current density compared to previous literature. The complete encapsulation provides high reproducibility and long-term stability. The technique can be extended to other air-sensitive materials as well as air-stable materials, offering highly competitive device performance.

Van der Waals Encapsulation by Ultrathin Oxide for Air-Sensitive 2D Materials.

The ambient stability is one of the focal points for applications of 2D materials, especially for those well-known air-sensitive ones, such as black phosphorus (BP) and transitional metal telluride. Traditional methods of encapsulation, such as atomic layer deposition of oxides and heterogeneous integration of hexagonal boron nitride, can hardly avoid removal of encapsulation layer when the 2D materials are encapsulated for further device fabrication, which causes complexity and damage during the procedure. Here, a van der Waals encapsulation method that allows direct device fabrication without removal of encapsulation layer is introduced using Ga2O3 from liquid gallium. Taking advantage of the robust isolation ability against ambient environment of the dense native oxide of gallium, hundreds of times longer retention time of (opto)electronic properties of encapsulated BP and MoTe2 devices is realized than unencapsulated devices. Due to the ultrathin high-κ properties of Ga2O3, top-gated devices are directly fabricated with the encapsulation layer, simultaneously as a dielectric layer. This direct device fabrication is realized by selective etching of Ga2O3, leaving the encapsulated materials intact. Encapsulated 1T' MoTe2 exhibits high conductivity even after 150 days in ambient environment. This method is, therefore, highlighted as a promising and distinctive one compared with traditional passivation approaches.

Augmentation of hot cell facility for pyro-process of irradiated metal fuels

Hot cells with an inert atmosphere are used for handling air-sensitive, hygroscopic, and radioactive materials like mixed carbide fuels and for pyro-processing metallic fuels. Pyro-processing of spent metal fuels was based on the electrochemical recovery of actinides in high-temperature molten salts (LiCl-KCl eutectic with 58.5 mol.% LiCl). To demonstrate the remote operation feasibility of the electro-refining process of irradiated U-6 wt% Zr inside hot cells and also to study the process parameters, a pilot scale (∼100 g) pyro-process facility was set up in one of our hot cells. For this purpose, the existing hot cell facility was augmented with necessary modifications and customized to the experimental needs. This paper discusses in detail the augmentation works carried out on the existing facility to facilitate the remote operation of electro-refining of irradiated metallic fuels.

Apparent color and Raman vibrational modes of the high-temperature superconductor Bi2Sr2CaCu2O 8+δ exfoliated flakes

Studying and controlling the properties of individual exfoliated materials is one of the first steps towards the fabrication of complex van der Waals systems. In this work, we present a systematic study of optical properties and micro-Raman spectroscopy on exfoliated flakes of the high-temperature superconductor Bi2Sr2CaCu2O 8+δ (BSCCO-2212). We demonstrate that these are quick and non-invasive techniques for studying air sensitive materials. The apparent color of BSCCO-2212 exfoliated flakes on SiO2/Si has allowed a rough and fast identification of the number of layers. By analyzing the optical contrast of different flakes we determined the complex refractive index in the visible range and found the optimal combination of illumination wavelength and substrate properties for the identification of flakes with different thickness. In addition, we report the hardening of the most characteristic Raman modes as flake thickness decreases, possibly caused by strain in the BiO and CuO2 planes. Moreover, the evolution of the Raman modes establishes a second approach to determine the thickness of BSCCO-2212 thin flakes. As BSCCO-2212 is a challenging material due to its sensitivity to ambient conditions, the present work provides a guide for the fabrication and characterization of complex van der Waals systems paving the way for studying heterostructures based on unconventional superconductors in the 2D limit.

N-Type PVP/SWCNT Composite Films with Improved Stability for Thermoelectric Power Generation.

Single-walled carbon nanotubes (SWCNTs) are one of the promising thermoelectric materials in applications of powering wearable electronics. However, the electrical performance of n-type SWCNTs quickly decreases in air, showing a low stability, and low-cost and effective solutions to improving its stability are also lacking, all of which limit practical applications. In this study, we studied the stability of PVP/SWCNT composite films, where oxygen and moisture from air should be responsible for the decreased stability due to oxidation and hydration. In this case, we found that coating with a 0.20 g mL-1 PVP/0.002 g mL-1 PVDF layer on the surface of PVP/SWCNTs can prevent the penetration of oxygen and moisture from air, improving film stability, where there is almost no reduction in thermoelectric performance after they are exposed to air for 60 days. Based on the stable n-type PVP/SWCNT films, a thermoelectric generator was fabricated, where poly(dimethylsiloxane) (PDMS) was used to coat the surface of the thermoelectric leg to further improve its stability. This generator showed high output performance, which achieved an open-circuit voltage of 10.6 mV and a power density of 312.2 μW cm-2 at a temperature difference of 50 K. Particularly, it exhibited high stability, where the output performance kept almost unchanged after exposure to high-humidity air for 30 days. This coating technology is also applicable to other air-sensitive materials and promotes the development and application of thermoelectric materials and devices.

Glovebox-assisted magnetic force microscope for studying air-sensitive samples in a cryogen-free magnet.

Most known two-dimensional magnets exhibit a high sensitivity to air, making direct characterization of their domain textures technically challenging. Herein, we report on the construction and performance of a glovebox-assisted magnetic force microscope (MFM) operating in a cryogen-free magnet, realizing imaging of the intrinsic magnetic structure of water and oxygen-sensitive materials. It features a compact tubular probe for a 50 mm-diameter variable temperature insert installed in a 12T cryogen-free magnet. A detachable sealing chamber can be electrically connected to the tail of the probe, and its pump port can be opened and closed by a vacuum manipulator located on the top of the probe. This sealing chamber enables sample loading and positioning in the glove box and MFM transfer to the magnet maintained in an inert gas atmosphere (in this case, argon and helium gas). The performance of the MFM is demonstrated by directly imaging the surface (using no buffer layer, such as h-BN) of very air-sensitive van der Waals magnetic material chromium triiodide (CrI3) samples at low temperatures as low as 5K and high magnetic fields up to 11.9T. The system's adaptability permits replacing the MFM unit with a scanning tunneling microscope unit, enabling high-resolution atomic imaging of air-sensitive surface samples.

Soft X-Ray Operando Characterization of Electrochemical Interfaces

HIPPIE is a high-flux, high-resolution soft x-ray beamline at MAX IV Laboratory (Sweden) with a new dedicated experimental setup for operando studies of electrochemical interfaces.[1] Such experiments utilize the dip-and-pull method to form a thin liquid meniscus on the surface of the working electrode in a three-electrode cell with a liquid electrolyte solution. Both the liquid film itself and the electrode-electrolyte interface can then be probed using X-ray photoelectron spectroscopy (PES) whilst maintaining full electrochemical control. The technique can be used to probe oxidation state changes, chemical shifts, electronic structure and electrochemical potentials in-situ.In this talk we will discuss status of spectroelectrochemical PES using soft X-rays, discussing the merits of the various different approaches to cell design. We will present three case studies on the topics of molecular redox reactions, battery interfaces and metal corrosion, all of which can be studied using dip-and-pull.[2-4] We will primarily aim to provide an introduction to the dip-and-pull method for those interested in this genre of advanced operando characterization. We will additionally outline the experimental realities and challenges that any potential new user of the dip-and-pull method should be aware of before applying for beamtime to conduct an experiment.The three case studies were all measured at HIPPIE, where the beamline operates in the 250-2000 eV range, providing access to the L absorption edges of many transition metals and the K edges of light elements. The dip-and-pull PES experiments are realized with an ambient-pressure hemispherical electron analyzer allowing measurements in vapor pressures up to 25 mbar. Electrochemical cells can therefore use aqueous electrolyte solutions as well as some organic solvents, including many of those common in batteries. An argon/nitrogen atmosphere glove box can be attached to the measurement chamber such that air sensitive materials can be studied. Typically foils or thin films are used for the working electrode. This apparatus therefore provides one of the most flexible platforms for electrochemical studies using soft-X-ray spectroscopy.

Robust Conveniently Sealable Container for High-Temperature Single-Crystal Growth Out of Reactive Melts with High Vapor Pressure

The high-temperature crystal growth of intermetallics often asks for sealing of the materials in a protective atmosphere. Here, we report on the development of a convenient sealing method for alkali-containing melts, with high vapor pressure and reactivity. Our newly designed container made of high-temperature resistant steel can be sealed manually and reliably without any air exposure of the containing material. The closed container may be heated in air up to at least 1150 °C. The containers were applied for the development and optimization of a high-temperature self-flux growth of KFe1−xAg1+yCh2 (Ch = Se, Te) single crystals. Their crystal structure and the low-temperature electrical resistance are presented. The successful growths of these air-sensitive materials out of a reactive self-flux confirm the reliability of the container.

Nanoscale paraffin layer fabricated using spin coating technique for on-demand removable passivation

Passivation is an essential process in the research and application of reactive and air-sensitive materials, and there has been an increasing demand to develop materials for stable but readily removable temporary passivation layers. Paraffin coating has been suggested as a possible candidate for such applications, which, however, further requires the demonstration of thin paraffin coating with complete surface coverage as well as effective depassivation performance. In this study, we demonstrate on-demand removable passivation using nanoscale paraffin layers fabricated using a spin-coating technique. Based on the Emslie Bonner and Peck's and Mark-Houwink-Sakurada (MHS) equations, eicosane and hexane were selected as the solute and solvent, respectively, to ensure low viscosity for the fabrication of nanoscale paraffin layers, facilitating depassivation process under a vacuum. Optimizing the solution concentration and spin speed generates nanoscale paraffin layers with complete surface coverage, which is confirmed through optical microscopic images and subsequent image processing using Python. The simple removal of the nanoscale paraffin layer through vacuum treatment allows us to revisit a passivated surface underneath, and subsequent contact resistance and x-ray photoelectron spectroscopy measurements evince the suppressed surface oxidation of paraffin-coated silicon samples. These results further attest to the applicability of paraffin coating as an on-demand removable passivation technique.

Transferred Polymer-Encapsulated Metal Electrodes for Electrical Transport Measurements on Ultrathin Air-Sensitive Crystals.

Owing to rapid property degradation after ambient exposure and incompatibility with conventional device fabrication process, electrical transport measurements on air-sensitive 2D materials have always been a big issue. Here, for the first time, a facile one-step polymer-encapsulated electrode transfer (PEET) method applicable for fragile 2D materials is developed, which showed great advantages of damage-free electrodes patterning and in situ polymer encapsulation preventing from H2 O/O2 exposure during the whole electrical measurements process. The ultrathin SmTe2 metals grown by chemical vapor deposition (CVD) are chosen as the prototypical air-sensitive 2D crystals for their poor air-stability, which will become highly insulating when fabricated by conventional lithographic techniques. Nevertheless, the intrinsic electrical properties of CVD-grown SmTe2 nanosheets can be readily investigated by the PEET method instead, showing ultralow contact resistance and high signal/noise ratio. The PEET method can be applicable to other fragile ultrathin magnetic materials, such as (Mn,Cr)Te, to investigate their intrinsic electrical/magnetic properties.

In Situ Exfoliation Method of Large-Area 2D Materials.

2D materials provide a rich platform to study novel physical phenomena arising from quantum confinement of charge carriers. Many of these phenomena are discovered by surface sensitive techniques, such as photoemission spectroscopy, that work in ultra-high vacuum (UHV). Success in experimental studies of 2D materials, however, inherently relies on producing adsorbate-free, large-area, high-quality samples. The method that yields 2D materials of highest quality is mechanical exfoliation from bulk-grown samples. However, as this technique is traditionally performed in a dedicated environment, the transfer of samples into vacuum requires surface cleaning that might diminish the quality of the samples. In this article, a simple method for in situ exfoliation directly in UHV is reported, which yields large-area, single-layered films. Multiple metallic and semiconducting transition metal dichalcogenides are exfoliated in situ onto Au, Ag, and Ge. The exfoliated flakes are found to be of sub-millimeter size with excellent crystallinity and purity, as supported by angle-resolved photoemission spectroscopy, atomic force microscopy, and low-energy electron diffraction. The approach is well-suited for air-sensitive 2D materials, enabling the study of a new suite of electronic properties. In addition, the exfoliation of surface alloys and the possibility of controlling the substrate-2D material twist angle is demonstrated.

Accounting for stray capacitances in impedance measuring cells — A mandatory step in the investigation of solid ion conductors

The determination of the dielectric response properties is essential to the investigation of solid ion conductors. The stray capacitance contributions of the measuring cell must be systematically determined and subtracted from the acquired data. Hereby, we report and discuss a general method that can be used for the accurate determination of stray capacitance in impedance measuring cells. Our method can be applied to all commercial or custom-made impedance cells or sample holders used for variable temperature conductivity measurements of fast ion conductors. After the description of the method, we present the experimental calibration done for a 2032-type coin cell sample holder. The 2032-type coin cell is a highly reliable sample holder for impedance measurements of air sensitive materials. We tested the method on a known sample and we validated it by comparing with the results obtained in a simple reference configuration. Our simple, efficient and robust method for the determination of parasitic capacitive contributions may serve as an example of good practice in the field of solid electrolytes, solid state batteries and dielectric materials investigations.

In-situ scanning tunneling microscopy observation of thickness-dependent air-sensitive layered materials and heterodevices

Quasi-two-dimensional (Quasi-2D) van der Waals (vdW) materials can be mechanically or chemically exfoliated down to monolayer because of their strong intralayer bonding and the weak interlayer vdW interaction. Thanks to this unique property, one can often find exotic thickness-dependent electronic properties from these quasi-2D vdW materials, which can lead to bandgap opening, emerging superconductivity, or enhanced charge density waves with decreasing thickness. Surface-sensitive scanning tunneling microscopy (STM) can provide direct observation of structural and electronic characteristics of such layered materials with atomic precision in real space. However, it is very challenging to preserve the intrinsic surfaces of air-sensitive quasi-2D materials between preparation and measurement. In addition, vdW 2D crystals after exfoliation are extremely hard to explore with a typical STM setup due to their small size (≤ 10 μm). Here, we present a straightforward method compatible with any STM setup having optical access: (1) exfoliating and/or stacking layered materials in a glove box, (2) transferring them to an ultra-high vacuum STM chamber using a suitcase without exposure to air, and (3) navigating surface to locate exfoliated vdW 2D flakes with different thicknesses. We successfully demonstrated that the clean surfaces of the air-sensitive $$\hbox {Fe}_3\hbox {GeTe}_2$$ can be effectively protected from unwanted oxidation during transfer. Furthermore, our method provides a simple but useful way to access a specific tiny stack of layered materials without any ex-situ fabrication processes for STM navigation. Our experimental improvement will open up a new way to investigate air-sensitive layered vdW materials with various thicknesses via surface-sensitive techniques including STM.

Molten salt dynamic sealing synthesis of MAX phases (Ti3AlC2, Ti3SiC2 et al.) powder in air

Since the synthesis of non-oxidized ceramic and alloy powders requires both high temperature and oxygen insulation conditions, here we demonstrate a cost-efficient molten salt sealing/shielded synthesis method with dynamic gas tightness. Compared to conventional synthesis method, it can prevent the loss of reaction materials at high temperature, cut off the connection between reacting material and outside air, and does not require long-time ball milling mixing treatment or provision of applied pressing before or during heating. Only low-cost salts (e.g., NaCl, KCl), a few minutes of raw material mixing, and regular heating molds are required to obtain high-purity (>96 wt%), micron-sized Ti 3 AlC 2 and Ti 3 SiC 2 powders with narrow size distribution, which significantly decreased the complexity and production costs in the synthesis process. The effect of temperature and raw material content on the products were investigated. The mechanism of diffusion reaction between reactants in molten salt environment was analyzed. The new method developed here was also applicable to Ti 2 AlC, V 2 AlC and Cr 2 AlC MAX phases, as well as provided new ideas for the preparation of other MXenes precursors with certain stoichiometric ratios, air-sensitive materials and nanopowders.

A laboratory X-ray emission spectrometer for phosphorus Kα and Kβ study of air-sensitive samples

We report a compact laboratory-based, high resolution X-ray emission spectrometer installed in a glovebox for simultaneous measurement of phosphorus Kα and Kβ spectra of air-sensitive materials.