Single-crystal Membranes Research Articles

Electrochemical Reduction of Carbon Dioxide on Single-Crystal Copper Membrane

The selective electrochemical reduction of carbon dioxide (CO2) was demonstrated over single-crystal copper membranes. The crystalline copper membranes were deposited on specific support substrates that were c-plane sapphire for Cu(111), MgO(100) for Cu(100), and MgO(110) for Cu(110). Methane (CH4) and ethylene (C2H4) formation in CO2 electrochemical reduction was more favorable on Cu(111) membranes than that on polycrystalline copper plates. The electrolyte type that CO2 gas was effectively dissolved in, was important to significantly maintain electrochemical activity. The product selectivity for CO2 conversion was strongly dependent on the crystal structure of the copper surface.

Analysis of Interfacial Processes at the SOFC Electrodes by I n-Situ Raman Spectroscopy

Kinetics of redox reactions and the variations of real charge-carrier concentrations across the SOFC electrode / electrolyte interfaces have critical importance for the fuel cell performance. The microscopic mechanisms of electrochemical processes in the vicinity of triple-phase boundary (TPB) can be assessed employing impedance spectroscopy, current-voltage measurements and various pulse techniques. Except for the micro-electrode approaches, however, these methods are cumulative. Moreover, unambiguous interpretation of the electrochemical measurement results requires, as a rule, to introduce complimentary experimental methods and/or to use simplified models. The present work is centered on the developments of a new combined technique for in-situ Raman spectroscopy studies of local chemical and electrochemical reactions, phase transitions, strains and morphological alterations in the SOFC electrodes under working conditions. The Raman spectroscopy was already successfully used to investigate both cathodic [1,2] and anodic [3] processes in SOFC, but the resultant information was mainly related to outer boundaries of the model electrochemical cells, primarily electrode surface, due to low penetration depth of the excitation radiation. The most important zones of the electrode systems, where the electrochemical reactions occur and ionic charge carriers are generated, cannot be achieved viewing the surface and edge areas. In the present work, this problem was solved by employing optically transparent, single-crystal membranes made of 10 mol.% Sc2O3 and 1% mol.% Y2O3 stabilized zirconia (10Sc1YSZ). In order to provide simultaneous Raman and electrochemical measurements of the cell placed under an oxygen chemical potential gradient, such as air/H2, a special controlled-atmosphere chamber was elaborated and tested. An appropriate selection of the electrodes geometry makes it possible to directly collect Raman spectra from the TPB zone, passing the beam through single-crystal solid electrolyte onto the interface, as a function of temperature, atmosphere, current density and/or overpotential. The results of case studies focused on redox kinetics of Ni-containing cermet anodes, are presented. This work was supported by grant 14-29-04031 of Russian Foundation for Basic Research. References S. Loridant, L. Abello, E. Siebert, G. Lucazeau, Solid State Ion. 78 (1995) 249-258K. Blinn, H. Abernathy, M.Liu, Advances in Solid Oxide Fuel Cells V. (2010) 63-73W. Bessler, M.Vogler, H. Stoermer, D. Gerthsen, A. Utz, A. Weber, E. Ivers-Tiffee, Phys. Chem. Chem. Phys., 12 (2010) 13888-13903

Hetero-Epitaxial Single Crystal 3C-SiC Opto-Mechanical Pressure Sensor

The design, fabrication, early testing and material property assessment work related to the development of an opto-mechanical pressure sensor implemented with hetero-epitaxial 3C-SiC on silicon is described. The sensor is constituted by a single-crystal 3C-SiC membrane whose deflection upon pressure application is measured using a fiber-optic interferometric readout. The fabrication of sensor prototypes and micromachined 3C-SiC membranes for test purposes is described and the results of bulge tests on the membranes are reported. Functional characterization of the sensor prototypes in the pressure range 0-3 bar is also presented, showing good linearity and reproducibility of the sensor response, sensitivity of roughly 2 mV/bar and estimated pressure resolution around 0.5 bar on a 0-200 bar dynamic range.

Gas permeation in a molecular crystal and space expansion.

A novel single-crystal membrane [Cu(II)2(4-F-bza)4(2-mpyz)]n (4-F-bza = 4-fluorobenzoate; 2-mpyz = 2-methylpyrazine) was synthesized and its identical permeability in any crystal direction in the correction for tortuosity proved that gas diffuses inside the channels without detour. H2 permeated by 1.18 × 10(-12) mol m m(-2) s(-1) Pa(-1) with a high selectivity (Fα: 23.5 for H2/CO and 48.0 for H2/CH4) through its 2D-channels having a minimum diameter of 2.6 Å, which is narrower than the Lennard-Jones diameter of H2 (2.827 Å), CO (3.690 Å), and CH4 (3.758 Å). The high rate of permeation was well explained by a modified Knudsen diffusion model based on the space expansion effect, which agrees with the observed permselectivity enhanced for smaller gases in considering the expansion of a channel resulting from the collision of gas molecules or atoms onto the channel wall. An analysis of single-crystal X-ray data showed the expansion order to be H2 > Ar > CH4, which was expected from the permeation analysis. The permselectivity of a porous solid depends on the elasticity of the pores as well as on the diameter of the vacant channel and the size of the target gas.

A preferable molecular crystal membrane for H₂ gas separation.

A novel molecular crystal membrane [Cu(II)2(9-AC)4(pyz)]n (9-AC: 9-anthracenecarboxylate, pyz: pyrazine) shows high permselectivity for H2/CO (79.0), H2/CH4 (137), and H2/CO2 (12.1) due to the high rate of H2 permeation (3820 Barrer) while inhibiting the permeation of such a large gaseous particle even in its wider channel than the Lennard-Jones diameter of each gas.

Experimental Measurements of Ultra-Thin Bragg Crystals for LCLS Beam-Sharing Operation

The successful lasing and operation of the LCLS hard X-ray FEL has brought tremendous interest to the user community spanning a wide range of scientific disciplines including physics, chemistry, structural biology, and material science. It created demand on beam time that is often left unfulfilled. Here we report experimental measurements of ultra-thin silicon single-crystal membranes for potentially beam-sharing the LCLS beam. The samples included the (111), (220), and (400) orientations with thicknesses ranging from 5 to 20 μm. Both high-resolution rocking curves and topographic data were first obtained using synchrotron X-rays, demonstrating near ideal diffraction qualities. Subsequent tests using the full LCLS beam revealed lattice distortions from beam-induced membrane vibrations, which were shown to be effectively reduced by ambient air and smaller membrane dimensions. High diffraction quality thin-diamonds in the (111) orientation are also being pursued as a parallel effort. Both approaches are paving a way for a practical beam-sharing implementation at LCLS in the near future.

Three-dimensional photonic crystals by large-area membrane stacking

We designed and analyzed a "mesh-stack" three-dimensional photonic crystal of a 12.4% bandgap with a dielectric constant ratio of 12 : 1. The mesh-stack consists of four offset identical square-lattice air-hole patterned membranes in each vertical period that is equal to the in-plane period of the square lattice. This design is fully compatible with the membrane-stacking fabrication method, which is based on alignment and stacking of large-area single-crystal membranes containing engineered defects. A bandgap greater than 10% is preserved as long as the membranes are subjected to in-plane misalignment less than 3% of the square period. By introducing a linear defect with a nonsymmorphic symmetry into the mesh-stack, we achieved a single-mode waveguide over a wide bandwidth.

Surface Barriers of Hydrocarbon Transport Triggered by Ideal Zeolite Structures

Shedding light on the nature of surface barriers of nanoporous materials, molecular simulations (Monte Carlo, Reactive Flux) have been employed to investigate the tracer-exchange characteristics of hydrocarbons in defect-free single-crystal zeolite membranes. The concept of a critical membrane thickness as a quantitative measure of surface barriers is shown to be appropriate and advantageous. Nanopore smoothness, framework density, and thermodynamic state of the fluid phase have been identified as the most important influencing variables of surface barriers. Despite the ideal character of the adsorbent, our simulation results clearly support current experimental findings on MOF Zn(tbip) where a larger number of crystal defects caused exceptionally strong surface barriers. Most significantly, our study predicts that the ideal crystal structure without any such defects will already be a critical aspect of experimental analysis and process design in many cases of the upcoming class of extremely thin and high...

3D nanostructures by stacking pre-patterned fluid-supported single-crystal Si membranes

The fabrication of complex three-dimensional (3D) structures at sub-100 nm resolution presents a difficult challenge. 3D photonic crystals that contain waveguides, resonant cavities, filters or other devices, and require deep-sub-100 nm dimensional control, are a particular example of this challenge. Multilayer 3D structures can be formed by stacking and bonding thin membranes that have been patterned in advance. This approach enables the full panoply of 2D planar-fabrication techniques to be employed. Membranes containing patterns that are not perfectly regular will exhibit in-plane distortion unless their intrinsic stress is zero. To minimize the effects of intrinsic stress we float individual membranes on the surface of a liquid. Thin single-crystal Si membranes on an oxide substrate are first patterned and then removed by etching the oxide in hydrofluoric acid. The freed Si membranes readily float on the liquid surface, aided by the hydrophobic nature of H-terminated Si. The authors describe methods for cleaning, patterning, manipulating, bonding and stacking such freely floating membranes.

X-ray reflectivity theory for determining the density profile of a liquid under nanometre confinement

An X-ray reflectivity theory on the determination of the density profile of a molecular liquid under nanometre confinement is presented. The confinement geometry acts like an X-ray interferometer, which consists of two opposing atomically flat single-crystal mica membranes with an intervening thin liquid film of variable thickness. The X-rays reflected from the parallel crystal planes (of known structure) and the layered liquid in between them (of unknown structure) interfere with one another, making X-ray reflectivity highly sensitive to the liquid's density profile along the confinement direction. An expression for the reflected intensity as a function of momentum transfer is given. The total structure factor intensity for the liquid-filled confinement device is derived as a sum of contributions from the inner and outer crystal terminations. The method presented readily distinguishes the confined liquid from the liquid adsorbed on the outer mica surfaces. It is illustrated for the molecular liquid tetrakis(trimethyl)siloxysilane, confined by two mica surfaces at a distance of 8.6 nm.

Single-Crystal Membrane for Anisotropic and Efficient Gas Permeation

Development of gas separation materials has been one of the basic requirements of industry. Microporous materials have adequate pores for gas separation and have contributed to the advancement of gas purification techniques. Because the simplest and most economical method would be membrane separation, various microporous membranes have been prepared and explored for their separation properties. However, a key issue remains as to how to generate defect-free membranes with practical gas permeance. Here we report the preparation of a well-oriented single-crystal membrane with high permeance by using a flexible single crystal of [Cu(2)(bza)(4)(pyz)](n) possessing one-dimensional (1D) penetration channels; this membrane exhibits anisotropic gas permeation through the 1D channels with high permselectivity for H(2) and CO(2). Although the diameter of the neck of the narrow channels is smaller than the kinetic diameters of the sample gases, various gases pass through the 1D channels. This report provides a new way of developing gas permeation membranes as sophisticated crystal devices for gas purification techniques.

The fabrication and characterization of organic light-emitting diodes using transparentsingle-crystal Si membranes

For applications such as solar cells and displays, transparent single-crystal Si membranes werefabricated on a silicon-on-insulator (SOI) wafer. The SOI wafer included a buried layer ofSiO2 andSi3N4 as an etch-stop layer. The etch-stop layer enabled fabrication of transparentsingle-crystal Si membranes with various thicknesses, and the thinningtechnology is described. For membranes with thicknesses of 18, 72 and 5000 nm,the respective optical transparent were 96.9%, 93.7% and 9% for R (red,λ = 660 nm), 96.9%, 91.4%and 1% for G (green, λ = 525 nm), and 97.0%, 93.2% and 0% for B (blue,λ = 470 nm). Organic light-emitting diodes (OLEDs) were then fabricated on transparent single-crystalSi membranes with various top Si thicknesses. OLEDs fabricated on 18, 72 and 5000 nmthick membranes and operated at 6 V demonstrated a luminance of 1350, 443 and27 cd m−2 at the current densitiesof 148, 131 and 1.5 mA cm−2, respectively.

A Piezoelectric Microspeaker with a High-Quality PMN-PT Single-Crystal Membrane

We have designed and fabricated a piezoelectric microspeaker with a lead magnesium niobatelead titanate (PMN-PT) single-crystal membrane. The PMN-PT piezoelectric membranes were designed with inter-digitated electrodes (IDEs) to obtain a higher sound output from the speakers. The PMN-PT microspeakers were successfully fabricated using silicon-based microelectromechanical systems (MEMS) technology and had a thickness of just 0.5 mm and an area of just 1.5 1.5 cm2. The areas of the 10m-thick PMN-PT active regions were just 1.2 1.2 cm2. The measured output sound pressure levels (SPL) of the microspeakers were about 85 dB SPL between 800 Hz and 7 kHz with an input drive of 14 Vp k at a distance of 1 cm, which produces a competitive output compared to other commercial microspeakers. Also, the displacements at the center of the PMN-PT membrane (with an input voltage of 1 Vp k) were measured to be 2.5 m and 4.1 m at the 1st resonant frequency of 840 Hz and the 2nd resonant frequency of 2.3 kHz, respectively.

Flexible photodetectors on plastic substrates by use of printing transferred single-crystal germanium membranes

This letter presents studies of multiwavelength flexible photodetectors on a plastic substrate by use of printing transferred single-crystal germanium (Ge) membranes. Ge membranes of 250nm thickness with selectively ion-implantation doped regions were released from a germanium-on-insulator substrate and integrated with a 175-μm-thick polyethylene terephthalate substrate via a dry printing technique. Photodiodes configured in lateral p-i-n configuration using the flexible Ge membranes with an intrinsic region width of 10μm exhibit an external quantum efficiency that varies from 5% at 411nm to 42% at 633nm under −1V bias condition. These results demonstrate the potential of utilizing single-crystal Ge-membrane photodiodes for imaging applications and as solar cells on objects with arbitrary curvatures and shapes.

Control of the Casimir force by the modification of dielectric properties with light

The experimental demonstration of the modification of the Casimir force between a gold coated sphere and a single-crystal Si membrane by light pulses is performed. The specially designed and fabricated Si membrane was irradiated with 514 nm laser pulses of 5 ms width in high vacuum leading to a change of the charge-carrier density. The difference in the Casimir force in the presence and in the absence of laser radiation was measured by means of an atomic force microscope as a function of separation at different powers of the absorbed light. The total experimental error of the measured force differences at a separation of 100 nm varies from 10 to 20% in different measurements. The experimental results are compared with theoretical computations using the Lifshitz theory at both zero and laboratory temperatures. The total theoretical error determined mostly by the uncertainty in the concentration of charge carriers when the light is incident is found to be about 14% at separations less than 140 nm. The experimental data are consistent with the Lifshitz theory at laboratory temperature, if the static dielectric permittivity of high-resistivity Si in the absence of light is assumed to be finite. If the dc conductivity of high-resistivity Si in the absence of light is included into the model of dielectric response, the Lifshitz theory at nonzero temperature is shown to be experimentally inconsistent at 95% confidence. The demonstrated phenomenon of the modification of the Casimir force through a change of the charge-carrier density is topical for applications of the Lifshitz theory to real materials in fields ranging from nanotechnology and condensed matter physics to the theory of fundamental interactions.

Study of electrochemical etch-stop for high-precision thickness control of single-crystal Si in aqueous TMAH : IPA : pyrazine solutions

In this paper, we describe a method of controlling the thickness of single-crystal Si membranes, fabricated by wet anisotropic etching in aqueous tetramethyl ammonium hydroxide (TMAH) : isopropyl alcohol (IPA) : pyrazine solutions. The Si surface of the etch-stopped microdiaphragm is extremely flat with no noticeable taper or nonuniformity. The benefits of the electrochemical etch-stop method for the etching of n epilayer-embedded p-type single-crystal Si(0 0 1) wafers in aqueous TMAH became apparent when the reproducibility of the microdiaphragm’s thickness in mass production was realized. The results indicated that the use of the electrochemical etch-stop method for the etching of Si in aqueous TMAH provided a powerful and versatile alternative process for the fabrication of high-yield Si microdiaphragms (20 ± 0.26 μm s.d). With etch-stop, the pressure sensitivity of devices fabricated on the same wafer can be controlled to within ±2.3% s.d.

The structure of suspended graphene sheets

The recent discovery of graphene has sparked much interest, thus far focused on the peculiar electronic structure of this material, in which charge carriers mimic massless relativistic particles. However, the physical structure of graphene--a single layer of carbon atoms densely packed in a honeycomb crystal lattice--is also puzzling. On the one hand, graphene appears to be a strictly two-dimensional material, exhibiting such a high crystal quality that electrons can travel submicrometre distances without scattering. On the other hand, perfect two-dimensional crystals cannot exist in the free state, according to both theory and experiment. This incompatibility can be avoided by arguing that all the graphene structures studied so far were an integral part of larger three-dimensional structures, either supported by a bulk substrate or embedded in a three-dimensional matrix. Here we report on individual graphene sheets freely suspended on a microfabricated scaffold in vacuum or air. These membranes are only one atom thick, yet they still display long-range crystalline order. However, our studies by transmission electron microscopy also reveal that these suspended graphene sheets are not perfectly flat: they exhibit intrinsic microscopic roughening such that the surface normal varies by several degrees and out-of-plane deformations reach 1 nm. The atomically thin single-crystal membranes offer ample scope for fundamental research and new technologies, whereas the observed corrugations in the third dimension may provide subtle reasons for the stability of two-dimensional crystals.

High-speed strained-single-crystal-silicon thin-film transistors on flexible polymers

We fabricate thin-film transistors (TFTs) on both strained and unstrained single-crystal Si membranes transferred to flexible-polymer substrates. The active layer is transferred from the starting silicon on insulator (SOI) using a simple, fast, and reliable dry-printing method. When a multilayer Si∕SiGe∕Si structure is pseudomorphically grown on SOI and the buried oxide is selectively removed, strained Si with a negligible density of dislocations is achieved via elastic strain sharing between the SiGe alloy layer and the Si layers. Both the drain current and the transconductance of TFTs fabricated on this strained Si∕SiGe∕Si membrane after its transfer to the flexible polymer are much higher than of TFTs fabricated on the unstrained-Si counterpart.

The role of molecular interactions and interfaces in diffusion: Permeation through single-crystal and polycrystalline microporous membranes

In this second paper of a two part series, we investigate the implications of the interfacial phenomenon, caused by adsorbate-adsorbate interactions coupled with the difference in adsorbate density between the zeolite and the gas phase, upon benzene permeation through single-crystal and polycrystalline microporous NaX membranes. The high flux predicted for thin single-crystal membranes reveals that substantially enhanced flux should be expected in submicron films. Simulations also indicate that the standard local equilibrium assumption made for larger scale membranes is inapplicable at the submicron scale associated with nanometer size grains of thin and/or polycrystalline membranes. Apparent activation energies predicted for benzene permeation through NaX membranes via kinetic Monte Carlo (KMC) simulations are in good agreement with laboratory experiments. The simulations also uncover temperature-dependent flux pathways leading to non-Arrhenius behavior observed experimentally. The failure of the Darken approximation, especially in the presence of the interfacial phenomenon, leads to a substantial overprediction of the flux. Simulations of polycrystalline membranes suggest that this same interfacial phenomenon leads to resistance that can reduce flux by an order of a magnitude with only moderate polycrystallinity.

The role of molecular interactions and interfaces in diffusion: Transport diffusivity and evaluation of the Darken approximation

Kinetic Monte Carlo (KMC) simulations are carried out to directly study diffusion of benzene through thin (37-100 nm) NaX zeolite membranes under a gradient in chemical potential. Nonlinearities in adsorbate loading near the membrane boundaries are shown to arise from the difference in adsorbate density between the zeolite and adjacent fluid phase. Direct extraction of the transport diffusivity from gradient KMC simulations enables testing of the Darken approximation. This rigorous approach reveals limitations of the Darken approximation and, for the first time, the potentially complex nonunique functionality and multiplicity of the transport diffusivity for strongly interacting adsorbates. In the companion paper we explore these nonlinear interfacial effects in the context of permeation through both single-crystal and polycrystalline membranes.