SiNx Membrane Research Articles

A strategy to fabricate nanostructures with sub-nanometer line edge roughness

Line edge roughness (LER) has been an important issue in the nanofabrication research, especially in integrated circuits. Despite numerous research studies has made efforts on achieving smaller LER value, a strategy to achieve sub-nanometer level LER still remains challenging due to inability to deposit energy with a profile of sub-nanometer LER. In this work, we introduce a strategy to fabricate structures with sub-nanometer LER, specifically, we use scanning helium ion beam to expose hydrogen silsesquioxane (HSQ) resist on thin SiNx membrane (∼20 nm) and present the 0.16 nm spatial imaging resolution based on this suspended membrane geometric construction, which is characterized by scanning transmission electron microscope (STEM). The suspended membrane serves as an energy filter of helium ion beam and due to the elimination of backscattering induced secondary electrons, we can systematically study the factors that influences the LER of the fabricated nanostructures. Furthermore, we explore the parameters including step size, designed exposure linewidth (DEL), delivered dosage and resist thickness and choosing the high contrast developer, the process window allows to fabricate lines with 0.2 nm LER is determined. AFM measurement and simulation work further reveal that at specific beam step size and DEL, the nanostructures with minimum LER can only be fabricated at specific resist thickness and dosage.

In Situ Soft XAS Study of Electrocatalysts with an Ultrahigh Vacuum-Compatible Liquid Flow Cell

Synchrotron X-ray absorption spectroscopy offers a unique tool for investigating the element-specific electronic structure of materials in chemistry and quantum physics fields. In particular, in situ/operando X-ray absorption spectroscopy (XAS) has yielded valuable atomic-level insight into electrocatalysts in operation. While most studies have employed "hard" X-rays that are higher than ~5 keV in energy, "soft" X-rays with energies around or below 1-2 keV have the unique capability to probe core-level excitations of light elements such as oxygen or p→d excitations of 1st-row transition metals. The low-energy soft X-rays easily become absorbed and scattered by ambient air, however, requiring ultrahigh vacuum (UHV) environments. To acquire soft XAS spectra of electrocatalysts in action within a UHV chamber, we employ home-fabricated SiNx membranes and a sealed electrochemical liquid flow cell. We demonstrate the use of our technique with canonical water oxidation catalysts RuO2 and MnOx.

Highly sensitive electron-beam-induced X-ray detection from liquid using SiNx membrane ultra-thinned by gas cluster ion beams

We aimed to improve the detection sensitivity for liquid measurement by developing an ultrathin photoelectron transmission window (SiNx membrane) for liquid cells via X-ray photoelectron spectroscopy or X-ray photoelectron emission microscopy at an ultrahigh vacuum. The membrane using gas-cluster ion beams (GCIB) was thinned, and its burst pressure was compared with those of membranes thinned with atomic 400 eV Ar+ ions. The SiNx membranes thinned by GCIB had approximately 2.5 times higher burst pressure than Ar+ ions. In addition, the improved sensitivity of the characteristic X-ray from liquid water induced by low-energy electrons was investigated. With the use of the 4.5 nm-thick SiNx membrane etched by GCIB, the X-ray intensity became 1.6 times higher than those of the 11 nm-thick pristine membrane at the electron beam (EB) energy of 1.5 keV. This result showed a good agreement with Monte Carlo simulation results of the EB-induced X-ray emission from liquid water beneath the SiNx membrane.

Thermal characterization of thin films: A chip-based approach for in-plane property analysis

Accurate measurement of thermal properties in thin films is crucial for optimizing devices and deepening our understanding of heat transfer at nano and micro scales. This study presents a combined experimental and computational investigation on a chip-integrated technique for the assessment of in-plane thermal properties of thin films. This method stands out by incorporating inherent error cancelation to lessen the impact of radiative heat loss and allows simultaneous, independent determination of both thermal conductivity and diffusivity through straightforward linear fittings from the same dataset, reducing error propagation. We examine an 84 nm thick SiNx membrane over a temperature range from 100 K to nearly 500 K, aligning with previous studies. Further investigations into a conducting polymer film post-doping demonstrate a notable increase in both thermal conductivity and diffusivity, corroborating scanning thermal microscopy observations, confirming the technique's efficacy and reliability.

Microheater Chips with Carbon Nanotube Resistors.

The specific and excellent properties of the low-dimensional nanomaterials have made them promising building blocks to be integrated into microelectromechanical systems with high performances. Here, we present a new microheater chip for in situ TEM, in which a cross-stacked superaligned carbon nanotube (CNT) film resistor is located on a suspended SiNx membrane via van der Waals (vdW) interactions. The CNT microheater has a fast high-temperature response and low power consumption, thanks to the micro/nanostructure of the CNT materials. Moreover, the membrane bulging amplitude is significantly reduced to only ∼100 nm at 800 °C for the vdW interaction between the CNTs and the SiNx membrane. An in situ observation of the Sn melting process is successfully conducted with the assistance of a customized flexible temperature control system. The uniform wafer-scaled CNT films enable a high level of consistency and cost-effective mass production of such chips. The as-developed in situ chips, as well as the related techniques, hold great promise in nanoscience, materials science, and electrochemistry.

Fast Fabrication Nanopores on a PMMA Membrane by a Local High Electric Field Controlled Breakdown.

The sensitivity and accuracy of nanopore sensors are severely hindered by the high noise associated with solid-state nanopores. To mitigate this issue, the deposition of organic polymer materials onto silicon nitride (SiNx) membranes has been effective in obtaining low-noise measurements. Nonetheless, the fabrication of nanopores sub-10 nm on thin polymer membranes remains a significant challenge. This work proposes a method for fabricating nanopores on polymethyl methacrylate (PMMA) membrane by the local high electrical field controlled breakdown, exploring the impact of voltage and current on the breakdown of PMMA membranes and discussing the mechanism underlying the breakdown voltage and current during the formation of nanopores. By improving the electric field application method, transient high electric fields that are one-seven times higher than the breakdown electric field can be utilized to fabricate nanopores. A comparative analysis was performed on the current noise levels of nanopores in PMMA-SiNx composite membranes and SiNx nanopores with a 5 nm diameter. The results demonstrated that the fast fabrication of nanopores on PMMA-SiNx membranes exhibited reduced current noise compared to SiNx nanopores. This finding provides evidence supporting the feasibility of utilizing this technology for efficiently fabricating low-noise nanopores on polymer composite membranes.

In Situ X-ray Absorption Spectroscopy of LaFeO3 and LaFeO3/LaNiO3 Thin Films in the Electrocatalytic Oxygen Evolution Reaction.

We study the electrocatalytic oxygen evolution reaction using in situ X-ray absorption spectroscopy (XAS) to track the dynamics of the valence state and the covalence of the metal ions of LaFeO3 and LaFeO3/LaNiO3 thin films. The active materials are 8 unit cells grown epitaxially on 100 nm conductive La0.67Sr0.33MnO3 layers using pulsed laser deposition (PLD). The perovskite layers are supported on monolayer Ca2Nb3O10 nanosheet-buffered 100 nm SiNx membranes. The in situ Fe and Ni K-edges XAS spectra were measured from the backside of the SiNx membrane using fluorescence yield detection under electrocatalytic reaction conditions. The XAS spectra show significant spectral changes, which indicate that (1) the metal (co)valencies increase, and (2) the number of 3d electrons remains constant with applied potential. We find that the whole 8 unit cells react to the potential changes, including the buried LaNiO3 film.

Pressure resistance evaluation of an ultrathin SiNx membrane etched by a gas cluster ion beam

In this study, reactive etching of a SiNx free-standing membrane with a thickness of a few nanometers was performed using a gas cluster ion beam (GCIB) and the pressure resistance of the membrane with respect to its thickness was evaluated. The low-damage irradiation effect of a 7 keV GCIB in an acetylacetone (Hacac) atmosphere enabled the etching to retain its pressure resistance compared with that of 400 eV Ar+ beam irradiation. In a previous study, it was shown that irradiation of SiNx films with Ar plasma of several hundred eV causes defects in the bonding network of the Si–N bond and the network is easily oxidized. XPS measurements on SiNx films after GCIB etching with Hacac and Ar+ beam irradiation showed that the composition of the Si–O bond was smaller with GCIB irradiation compared to Ar+ beam irradiation. This indicates that GCIB etching with Hacac can suppress the formation of defects in the Si–N network, which reduces the degradation of the pressure resistance.

Ultrathin metasurface on a 100 nm-thick dielectric membrane absorbs infrared rays.

Flat optics based on metasurfaces produce unprecedented two-dimensional planar optical elements that cannot be developed with naturally occurring materials. However, it remains to be shown whether metasurfaces on ultrathin dielectric membranes can be adopted in a broad range of optical elements as flat optics. Here we demonstrate that a fabricated ultrathin metasurface composed of double-sided metal structures on a 100 nm-thick SiNx membrane absorbs infrared rays with a high absorptance of 97.1% at 50.1 THz. This ultrathin metasurface and its fabrication method would be a welcome contribution to a wide range of trailblazing applications, including ultrathin absorbers for imaging and light detection and ranging (LIDAR), directivity control of thermal radiation, and polarization control of vacuum ultraviolet light.

Differential pressure sensors based on transfer-free piezoresistive layered PdSe2 thin films

Piezoresistive layered two-dimensional (2D) crystals offer intriguing promise as pressure sensors for microelectromechanical systems (MEMS) due to their remarkable strain-induced conductivity modulation. However, integration of the conventional chemical vapor deposition grown 2D thin films onto a micromachined silicon platform requires a complex transfer process, which degrades their strain-sensing performance. In this study, we present a differential pressure sensor built on a transfer-free piezoresistive PdSe2 polycrystalline film deposited on a SiN x membrane by plasma-enhanced selenization of a metal film at a temperature as low as 200 °C. Based on the resistance change and finite element strain analysis of the film under membrane deflection, we show that a 7.9 nm thick PdSe2 film has a gauge factor (GF) of −43.3, which is ten times larger than that of polycrystalline silicon. The large GF enables the development of a diaphragm pressure sensor with a high sensitivity of 3.9 × 10−4 kPa−1 within the differential pressure range of 0–60 kPa. In addition, the sensor with a Wheatstone bridge circuit achieves a high voltage sensitivity of 1.04 mV·kPa−1, a rapid response time of less than 97 ms, and small output voltage variation of 8.1 mV in the temperature range of 25 °C to 55 °C. This transfer-free and low-temperature grown PdSe2 piezoresistive thin film is promising for MEMS transducer devices.

Mitigating challenges in aberration-corrected electron-beam lithography on electron-opaque substrates

Aberration-corrected electron-beam lithography (AC-EBL) using ultra-thin electron transparent membranes has achieved single-digit nanometer resolution in two widely used electron-beam resists: poly (methyl methacrylate) (PMMA) and hydrogen silsesquioxane. On the other hand, AC-EBL implementation on thick, electron-opaque substrates is appealing for conventional top-down fabrication of quantum devices with nanometer-scale features. To investigate the performance of AC-EBL on thick substrates, we measured the lithographic point spread function of a 200 keV aberration-corrected scanning transmission electron microscope by defining both positive and negative patterns in PMMA thin films, spin-cast on thick SiO2/Si substrates. We present the problems encountered during pre-exposure beam focusing and discuss methods to overcome them. In addition, applying some of these methods using commercial 50 nm thick SiN X membranes with thick Si support frames, we printed arrays of holes in PMMA with pitches around 26 nm on SiN X /Si substrates with increasing Si thickness. Our results show that proximity effects from even 50 nm thick SiN X membranes limit hole arrays to 20 nm pitch; however, down to this limit, the effect of the substrate thickness on the pattern quality is minimal. These results highlight the need for novel resists less susceptible to proximity effects, or resists which can be used directly, after development, as the dielectric material in periodic gates in 2D quantum devices.

Lock-in photothermal method for in-plane thermal diffusivity measurements using arrayed temperature sensors on suspended SiNx membranes.

A device consisting of a line- or spiral-shaped temperature sensor array on a two-dimensional (2D) silicon nitride (SiNx) membrane of thickness 50 or 150nm is developed for use in the lock-in photothermal method to determine the in-plane thermal diffusivity of SiNx membranes in air and in vacuum. The results of 2D heat diffusion are analyzed by the quadrupole method, and the system is approximated to the one-dimensional (1D) fin standing in a surrounding media (the fin approximation). The results show that 2D thermal diffusion on the membrane is affected not only by heat exchange with the surrounding environment but also by parallel thermal diffusion caused by heat conduction in the air along the membrane surface. The measurement using photothermal heating and contact detection of the temperature response enables the phenomenon to be detected consistently at a wide frequency range of temperature waves (50-1000Hz). The measured thermal diffusivity values of the SiNx membrane are much smaller than those of bulk material, which can be reasonably considered an effect of the confined state of the phonon in the nanoscale geometry of the membrane.

Isolation of Bovine Milk Exosome Using Electrophoretic Oscillation Assisted Tangential Flow Filtration with Antifouling of Micro-ultrafiltration Membrane Filters

Tangent flow-driven ultrafiltration (TF-UF) is an efficient isolation process of milk exosomes without morphological deformation. However, the TF-UF approach with micro-ultrafiltration SiNx membrane filters suffers from the clogging and fouling of micro-ultrafiltration membrane filter pores with large bioparticles. Thus, it is limited in the long term, continuous isolation of large quantities of exosomes. In this work, we introduced electrophoretic oscillation (EPO) in the TF-UF approach to remove pore clogging and fouling of with micro-ultrafiltration SiNx membrane filters by large bioparticles. As a result, the combined EPO-assisted TF (EPOTF) filtration can isolate large quantities of bovine milk exosomes without deformation. Furthermore, several morphological and biological analyses confirmed that the EPOTF filtration approach could isolate the milk exosomes in high concentrations with high purity and intact morphology. In addition, the uptake test of fluorescent-labeled exosomes by the keratinocyte cells visualized the biological function of purified exosomes. Hence, compared to the TF-UF process, the EPOTF filtration produced a higher yield of bovine milk exosomes without stopping the filtering process for over 200 h. Therefore, this isolation process enables scalable and continuous production of morphologically intact exosomes from bovine milk, suggesting that high-quality exosome purification is possible for future applications such as drug nanocarriers, diagnosis, and treatments.

Considerations of Liquid-Phase Transmission Electron Microscopy Applied to Heterogeneous Electrocatalysis

Liquid-phase transmission electron microscopy (LPTEM) is an essential tool for studying the dynamics of materials interactions at the nanoscale, in and/or with their operational environment. Microfabricated SiNx membrane cells further allow the integration of thin-film electrodes that opens the technique to studies of heterogeneous electrocatalysts under relevant electrochemical conditions. However, experiments remain challenging and the characteristics of the dedicated electrochemical cells and of the interactions of the electron beam with the liquid electrolyte demand careful interpretation of the results. Herein, we discuss important aspects that concern the implementation of electrochemical LPTEM (ec-LPTEM). We first consider the range of information that can be accessible with the technique for electrocatalytic applications and we detail the influence of the thickness and flow of liquid electrolytes using membrane-based microcells. Further, we provide guidelines pertinent to the electrochemical configuration of the substrate working, reference, and counter electrodes. We validate these considerations by experimentally demonstrating the application of ec-LPTEM for the CO2 reduction reaction (CO2RR), the oxygen reduction reaction (ORR), and the oxygen evolution reaction (OER). The probed effects in metallic and oxide catalysts are directly related to the applied electrochemical stimuli and corroborate the representativity of the processes under investigation following the considerations described herein.

A universal metasurface transfer technique for heterogeneous integration.

Metasurfaces offer a versatile platform for engineering the wavefront of light using nanostructures with subwavelength dimensions and hold great promise for dramatically miniaturizing conventional optical elements due to their small footprint and broad functionality. However, metasurfaces so far have been mainly demonstrated on bulky and planar substrates that are often orders of magnitude thicker than the metasurface itself. Conventional substrates not only nullify the reduced footprint advantage of metasurfaces, but also limit their application scenarios. The bulk substrate also determines the metasurface dielectric environment, with potentially undesired optical effects that undermine the optical performance. Here we develop a universal polymer-assisted transfer technique to tackle this challenge by decoupling the substrate employed on the fabrication of metasurfaces from that used for the target application. As an example, Huygens' metasurfaces with 120 nm thickness in the visible range (532 nm) are demonstrated to be transferred onto a 100 nm thick freestanding SiNx membrane while maintaining excellent structural integrity and optical performance of diffraction-limited focusing. This transfer method not only enables the thinnest dielectric metalens to the best of our knowledge, but also opens up new opportunities in integrating cascaded and multilayer metasurfaces, as well as the heterogeneous integration with nonconventional substrates and various electronic/photonic devices.

Graphene Microheater Chips for In Situ TEM.

Low-dimensional materials are bringing significant innovations to in situ TEM characterization. Here a new graphene microheater chip for TEM was developed by stacking graphene on a suspended SiNx membrane as the Joule heating element. It could be heated up to 800 °C within 26.31 ms with a low power consumption of 0.025 mW/1000 μm2. The bulging was only ∼50 nm at 650 °C, which is 2 orders of magnitude smaller than those of conventional MEMS heaters at similar temperatures. The performances benefit from the employment of graphene, since its monolayer structure greatly reduces the heat capacity, and the vdW contact significantly reduces the interfacial interaction. The TEM observation on the Sn melting process verifies its great potential in resolving thermodynamic processes. Moreover, more multifunctional in situ chips could be developed by integrating other stimuli to such chips. This work opens a new frontier for both graphene and in situ characterization techniques.

Improved Responsivity of an a-Si-based Micro-bolometer Focal Plane Array with a SiNx Membrane Layer

Improved Responsivity of an a-Si-based Micro-bolometer Focal Plane Array with a SiNx Membrane Layer

A one-step pattern transferring process for freestanding diffractive spiral photon sieves in extreme ultraviolet

Spiral zone plates in the form of photon sieves are one of the important phase modulation devices, being well developed in both visible lights and X-rays for mode conversion from Gaussian beam to vortex one. However, in extreme ultraviolet (EUV) region as a diffractive focusing lens, spiral photon sieves in freestanding SiNx membrane with through-holes to avoid significant absorptions of EUV light by the membrane material, still remain a big challenge in manufacturing. In this work, a simplified nanofabrication process using electron beam lithography directly followed by reactive ion etch, was developed. The fabricated spiral photon sieves involve two layers of SiNx/ZEP520A with the focusing efficiency estimated to be 23%. Optical characterization of the converted vortex beam by using a typical imprint technique was carried out using a 46.9 nm EUV laser. Donut-shaped ablation pattern by EUV laser was observed on the exposed PMMA (polymethyl methacrylate), indirectly proving the phase modulation functionality of the fabricated freestanding spiral photon sieves. The developed fabrication process greatly simplifies the manufacturing of freestanding zone plates/photon sieves as well as other freestanding nanometer structures, and should be applicable in the production in large volume.

Low-Area Four-Channel Controlled Dielectric Breakdown System Design for Point-of-Care Applications.

In this study, we propose a low-area multi-channel controlled dielectric breakdown (CDB) system that simultaneously produces several nanopore sensors. Conventionally, solid-state nanopores are prepared by etching or drilling openings in a silicon nitride (SiNx) substrate, which is expensive and requires a long processing time. To address these challenges, a CDB technique was introduced and used to fabricate nanopore channels in SiNx membranes. However, the nanopore sensors produced by the CDB result in a severe pore-to-pore diameter variation as a result of different fabrication conditions and processing times. Accordingly, it is indispensable to simultaneously fabricate nanopore sensors in the same environment to reduce the deleterious effects of pore-to-pore variation. In this study, we propose a four-channel CDB system that comprises an amplifier that boosts the command voltage, a 1-to-4 multiplexer, a level shifter, a low-noise transimpedance amplifier and a data acquisition device. To prove our design concept, we used the CDB system to fabricate four nanopore sensors with diameters of <10 nm, and its in vitro performance was verified using λ-DNA samples.

Inhibition of vacuum sublimation artefacts for (Scanning) Transmission Electron Microscopy ((S)TEM) of sulphur samples via encapsulation

Lithium-sulfur battery is one of promising candidates for next-generation energy storage device due to the sulfur cathode material with low cost and nontoxicity, and super high theoretical energy density (nearly 2600Wh kg−1) and specific energy (2567Wh kg−1). Sulphur, however, poses a few interesting challenges before it can gain widespread utilisation. The biggest issue is known as the polysulphide shuttling effect which contributes to rapid capacity loss after cycling. Accurate characterisation of sulphur cathodic materials becomes critical to our understanding polysulphide shuttling effect in the quest of finding mitigating solutions. Electron microscopy is playing a crucial role in battery research in determining structure–property–function relations. However, sulphur undergoes sublimation at a point above the typical pressures found in the column of a transmission electron microscope (TEM) at room temperature. This makes the imaging and characterisation of any sort of nanostructured sulphur samples challenging, as the material will be modified or even disappear rapidly as soon as it is inserted into the TEM vacuum. As a result, materials characterised by such methods are prone to deviation from normal conditions to a great extent. To prevent this, a novel method of encapsulating sulphur particles between silicon nitride (SiNx) membranes is demonstrated in this work.