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At least 163 records · Page 9

Pulsed-laser epitaxy of metallic delafossite PdCrO 2 films

Alternate stacking of a highly conducting metallic layer with a magnetic triangular layer found in delafossite PdCrO 2 provides an excellent platform for discovering intriguing correlated quantum phenomena. Thin film growth of delafossites may enable not only the tuning of the basic physical properties beyond what bulk materials can exhibit, but also the development of novel hybrid materials by interfacing with dissimilar materials, yet this has proven to be extremely challenging. Here, we report the epitaxial growth of metallic delafossite PdCrO 2 films by pulsed laser epitaxy (PLE). The fundamental role of the PLE growth conditions, epitaxial strain, and chemical and structural characteristics of the substrate is investigated by growing under various growth conditions and on various types of substrates. While strain plays a large role in improving the crystallinity, the direct growth of epitaxial PdCrO 2 films without impurity phases was not successful. We attribute this difficulty to both the chemical and structural dissimilarities with the substrate and volatile nature of the PdO sublayer, which make nucleation of the right phase difficult. This difficulty was overcome by growing CuCrO 2 buffer layers before PdCrO 2 films were grown. Unlike PdCrO 2 , CuCrO 2 films were readily grown with a relatively wide growth window. Only a monolayer thick buffer layer was sufficient to grow the correct PdCrO 2 phase. This result indicates that the epitaxy of Pd-based delafossites is extremely sensitive to the chemistry and structure of the interface, necessitating near perfect substrate materials. The resulting films are commensurately strained and show an antiferromagnetic transition at 40 K that persists down to as thin as 3.6 nm in thickness. This work provides key insights into advancing the epitaxial growth of the broader class of metallic delafossites for both studying the basic physical properties and developing new spintronic and computing devices.

36 MATERIALS SCIENCE↗

High-performance 2D electronic devices enabled by strong and tough two-dimensional polymer with ultra-low dielectric constant

As the feature size of microelectronic circuits is scaling down to nanometer order, the increasing interconnect crosstalk, resistance-capacitance (RC) delay and power consumption can limit the chip performance and reliability. To address these challenges, new low-k dielectric (k < 2) materials need to be developed to replace current silicon dioxide (k = 3.9) or SiCOH, etc. However, existing low-k dielectric materials, such as organosilicate glass or polymeric dielectrics, suffer from poor thermal and mechanical properties. Two-dimensional polymers (2DPs) are considered promising low-k dielectric materials because of their good thermal and mechanical properties, high porosity and designability. Here, we report a chemical-vapor-deposition (CVD) method for growing fluoride rich 2DP-F films on arbitrary substrates. We show that the grown 2DP-F thin films exhibit ultra-low dielectric constant (in plane k = 1.85 and out-of-plane k = 1.82) and remarkable mechanical properties (Young’s modulus > 15 GPa). We also demonstrated the improved performance of monolayer MoS 2 field-effect-transistors when utilizing 2DP-F thin films as dielectric substrates.

36 MATERIALS SCIENCE↗

Elucidating CO Oxidation Pathways on Rh Atoms and Clusters on the “29” Cu 2 O/Cu(111) Surface

We report single-atom catalysts have attracted a great deal of attention due to their distinct reactivity and potential for cost savings. However, despite the wealth of literature in recent years, identifying the exact nature of the active sites and associated reaction mechanisms remains challenging in many cases. Herein, we take a surface science approach to understand how Rh single atoms and small clusters behave on the thin film “29” Cu 2 O grown on Cu(111). We find that in contrast to Pt, which is present solely as single atoms on the “29” Cu 2 O surface, Rh atoms and clusters coexist and each enable low-temperature CO oxidation, but via different pathways. Specifically, the single Rh atoms produce CO 2 at 444 K via a Mars van Krevelen mechanism whereas the Rh clusters can also dissociate CO, as demonstrated via isotope labeling, and liberate CO 2 at 313 K. Density functional theory (DFT) calculations quantify the energetics of these different pathways and demonstrate that only extended Rh is capable of CO dissociation. Low-temperature scanning tunneling microscopy (STM) reveals that unlike Pt atoms on the same surface, which stay atomically dispersed, the distribution of Rh structures is dependent on pretreatment conditions. DFT calculations reveal the greater tendency of Rh atoms to cluster than Pt, and STM image simulations confirm the active sites. Ambient pressure X-ray photoelectron spectroscopy studies on the same single crystal model systems demonstrate that 1% of a monolayer of Rh on the “29” Cu 2 O thin film significantly accelerates its reduction by CO at 400 K, thus confirming the ultrahigh vacuum surface science findings. Together, these results illustrate how well-defined single crystal experiments are useful in building structure–function relationships that elucidate the reactivity of different ensemble sizes with a level of detail beyond what is possible with high surface area catalysis.

36 MATERIALS SCIENCE↗

Effects of growth substrate on the nucleation of monolayer MoTe 2

The discovery and characterization of two-dimensional (2D) materials beyond graphene has increased dramatically over the past decade with increasingly fine control over the growth dynamics of these materials. MoTe 2 represents a model material for studying phase change properties of 2D materials due to small energy differences between its 2H semiconducting phase and 1T' semimetallic phase. Although some substrates are demonstrated to be better than others for the wafer-scale growth of high quality MoTe 2 films, substrate effects on the nucleation and growth of MoTe 2 are still not well understood. Here, we grow monolayer MoTe 2 by converting MoO x thin films deposited on three different substrates: sapphire Al 2 O 3 (0001), amorphous SiO 2 , and amorphous AlO x , and examine the early stages of the conversion reaction to elucidate the substrate effects on the nucleation of MoTe 2 . We observe that the chemical composition of the substrate is more important than the surface topography and crystallinity of the substrate, with high quality monolayer 2H MoTe 2 formed on both Al 2 O 3 (0001) and AlO x in contrast to mixed phase 2H/1T' MoTe 2 formed on SiO 2 , as determined by Raman spectroscopy, X-ray photoelectron spectroscopy, and atomic force microscopy.

36 MATERIALS SCIENCE↗

A type-I van der Waals heterostructure formed by monolayer WS 2 and trilayer PdSe 2

Two-dimensional (2D) heterostructures, formed by stacking 2D semiconductors through the van der Waals force, have been extensively studied recently. However, the majority of the heterostructures discovered so far possess type-II interfaces that facilitate interlayer charge separation. Type-I interfaces, on the other hand, confine both electrons and holes in one layer, which is beneficial for optical applications that utilize electron–hole radiative recombination. So far, only a few type-I 2D heterostructures have been achieved, which has limited the construction of multilayer heterostructures with sophisticated band landscapes. Here, we report experimental evidence of a type-I interface between monolayer WS 2 and trilayer PdSe 2 . Two-dimensional PdSe 2 has emerged as a promising material for infrared optoelectronic and other applications. We fabricated the heterostructure by stacking an exfoliated monolayer WS 2 flake on top of a trilayer PdSe 2 film, synthesized by chemical vapor deposition. Photoluminescence spectroscopy measurements revealed that the WS 2 exciton peak is significantly quenched in the heterostructure, confirming efficient excitation transfer from WS 2 to PdSe 2 . Femtosecond transient absorption measurements with various pump/probe configurations showed that both electrons and holes photoexcited in the WS 2 layer of the heterostructure can efficiently transfer to PdSe 2 , while neither type of carriers excited in PdSe 2 can transfer to WS 2 . These experimental findings establish a type-I band alignment between monolayer WS 2 and trilayer PdSe 2 . Furthermore, our results further highlight PdSe 2 as an important 2D material for constructing van der Waals heterostructures with emergent electronic and optoelectronic properties.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Syngas Production at Si Hybrid Photoelectrodes Modified with Re(I) and Mn(I) Tricarbonyl Phenanthroline Complexes Containing Reactive Aryl Azide Groups

We installed molecular CO 2 reduction (CO 2 R) catalysts directly onto Si (photo)electrodes. The highly reactive M(5-azido-1,10-phenanthroline)(CO) 3 X (where M = Mn or Re, X = Br or Cl) complexes readily bubbled when dissolved in polar organic solvents, in both the presence and absence of an ultraviolet light source. When placed on hydrogen-terminated Si (H-Si) and native silicon oxide (SiOx), similar amounts of the complex were attached to the surface under illumination (367 nm, 50–200 mW/cm 2 ) or in the dark. Surprisingly, these films revealed submonolayer coverages instead of the multilayered structures we expected. DFT analyses support monolayer formation, showing that the triplet-state nitrene of the complex is more energetically favorable than the singlet state. Using controlled-potential electrolysis experiments, we showed that Re- and Mn-containing films on pSi photoelectrodes generated small amounts of CO when exposed to 1 atm of CO 2 and 1 sun illumination. These amounts of CO were an order of magnitude greater than control surfaces, producing 5.59 × 10 –7 mol CO/h for Re(az-phen) and 7.83 × 10 –7 mol CO/h for Mn(az-phen) films. Much of the charge passed at the pSi electrodes was consumed by the competing hydrogen evolution reaction, which we attribute to the low molecular coverage and the presence of native oxide on the electrode surface after attachment. Finally, this work demonstrates the feasibility of reacting azide-containing ligands with Si surfaces. Still, it highlights the need for alternative ligand structures and reaction conditions to form multilayer films.

azides↗

Functionalization of Monolayer MoS 2 with Layered Multimolecular Architectures

Two dimensional van der Waals materials have attracted attention due to their unique properties that arise in the monolayer versus bulk limits. Monolayer MoS 2 has been at the forefront of 2D materials due to its broad applicability in catalysis, photovoltaics, and spintronics. To realize the capabilities of MoS 2 enabled technology, it is necessary to engineer interfaces where charge carriers can be funneled toward or away from the surface. Molecular systems are a versatile strategy to enable this. Ion-linked molecular architectures have been used previously to circumvent difficult and taxing synthetic methods. Here, we demonstrate the growth of metal ion-linked bilayers (ILBs) on monolayer MoS 2 consisting of a first layer spacer (4-mercaptobenzoic acid, MBA) with a Zn(II) ion linked to a fluorophore (BODIPY). Using a combination of Atomic Force Microscopy and Raman spectroscopy, we resolved intrinsic S-vacancies in the MoS 2 lattice via S–H bond breaking of MBA. X-ray Photoelectron Spectroscopy confirmed that Zn(II) acetate can coordinate to carboxylate groups on MBA. Furthermore, with photoluminescence microscopy, we determined that BODIPY emission is observable only in the presence of a metal ion, confirming the growth of a multimolecular ion-linked supramolecular assembly on MoS 2 .

36 MATERIALS SCIENCE↗

Determining Concentration of Nanoparticles from Ellipsometry

A method of using ellipsometry or polarization analysis of light in total internal reflection of a surface to determine the number density of gold nanoparticles on a smooth substrate has been developed. The method can be modified to enable determination of densities of sparse distributions of nanoparticles in general, and is expected to be especially useful for measuring gold-nanoparticle-labeled biomolecules on microarrays. The method is based on theoretical calculations of the ellipsometric responses of gold nanoparticles. Elements of the calculations include the following: For simplicity, the gold nanoparticles are assumed to be spherical and to have the same radius. The distribution of gold nanoparticles is assumed to be a sub-monolayer (that is, sparser than a monolayer). The optical response of the sub-monolayer is modeled by use of a thin-island-film theory, according to which the polarizabilities parallel and perpendicular to the substrate are functions of the wavelength of light, the dielectric functions (permittivities expressed as complex functions of frequency or wavelength) of the gold and the suspending medium (in this case, the suspending medium is air), the fraction of the substrate area covered by the nanoparticles, and the radius of the nanoparticles. For the purpose of the thin-island-film theory, the dielectric function of the gold nanoparticles is modeled as the known dielectric function of bulk gold plus a correction term that is necessitated by the fact that the mean free path length for electrons in gold decreases with decreasing radius, in such a manner as to cause the imaginary part of the dielectric function to increase with decreasing radius (see figure). The correction term is a function of the nanoparticle radius, the wavelength of light, the mean free path and the Fermi speed of electrons in bulk gold, the plasma frequency of gold, and the speed of light in a vacuum. These models are used to calculate ellipsometric responses for various concentrations of gold nanoparticles having an assumed radius. The modeled data indicates distinct spectral features for both the real and the imaginary part of the dielectric function. An ellipsometric measurement would determine this distinct feature and thus can be used to measure nanoparticle concentration. By "ellipsometric responses" is meant the intensities of light measured in various polarization states as functions of the angle of incidence and the polarization states of the incident light. These calculated ellipsometric responses are used as calibration curves: Data from subsequent ellipsometric measurements on real specimens are compared with the calibration curves. The concentration of the nanoparticles on a specimen is assumed to be that of the calibration curve that most closely matches the data pertaining to that specimen.

Venkatasubbarao, Srivatsa↗

Toward Spatial Control of Reaction Selectivity on Photocatalysts Using Area-Selective Atomic Layer Deposition on the Model Dual Site Electrocatalyst Platform

Photocatalytic water splitting is a promising route to low-cost, green H 2 . However, this approach is currently limited in its solar-to-hydrogen conversion efficiency. One major source of efficiency loss is attributed to the high rates of undesired side and back reactions, which are exacerbated by the proximity of neighboring oxidation and reduction sites. Nanoscopic oxide coatings have previously been used to selectively block undesired reactants from reaching active sites; however, a coating encapsulating the entire photocatalyst particle limits activity as it cannot facilitate both half-reactions. In this work, area selective atomic layer deposition (AS-ALD) was used to selectively deposit semipermeable TiO 2 films onto model metallic cocatalysts for enhancing reaction selectivity while maintaining a high overall activity. Pt and Au were used as exemplary reduction and oxidation cocatalyst sites, respectively, where Au was deactivated toward ALD growth through self-assembled thiol monolayers while TiO 2 was coated onto Pt sites. Electroanalytical measurements of monometallic thin film electrodes showed that the TiO 2 -encapsulated Pt effectively suppressed undesired H 2 oxidation and Fe(II)/Fe(III) redox reactions while still permitting the desired hydrogen evolution reaction (HER). A planar model photocatalyst platform containing patterned interdigitated arrays of Au and Pt microelectrodes was further assessed using scanning electrochemical microscopy (SECM), demonstrating the successful use of AS-ALD to enable local reaction selectivity in a dual-reaction-site (photo)electrocatalytic system. Finally, interdigitated microelectrodes having independent potential control were used to show that selectively deposited TiO 2 coatings can suppress the rate of back reactions on neighboring active sites by an order of magnitude compared with uncoated control samples.

08 HYDROGEN↗

Photoelectrochemical Proton-Coupled Electron Transfer of TiO 2 Thin Films on Silicon

TiO 2 thin films are often used as protective layers on semiconductors for applications in photovoltaics, molecule–semiconductor hybrid photoelectrodes, and more. Experiments reported here show that TiO 2 thin films on silicon are electrochemically and photoelectrochemically reduced in buffered acetonitrile at potentials relevant to photoelectrocatalysis of CO 2 reduction, N 2 reduction, and H 2 evolution. On both n-type Si and irradiated p-type Si, TiO 2 reduction is proton-coupled with a 1e – :1H + stoichiometry, as demonstrated by the Nernstian dependence of the Ti 4+/3+ E 1/2 on the buffer pK a . Experiments were conducted with and without illumination, and a photovoltage of ∼0.6 V was observed across 20 orders of magnitude in proton activity. The 4 nm films are almost stoichiometrically reduced under mild conditions. The reduced films catalytically transfer protons and electrons to hydrogen atom acceptors, based on cyclic voltammogram, bulk electrolysis, and other mechanistic evidence. TiO 2 /Si thus has the potential to photoelectrochemically generate high-energy H atom carriers. Characterization of the TiO 2 films after reduction reveals restructuring with the formation of islands, rendering TiO 2 films as a potentially poor choice as protecting films or catalyst supports under reducing and protic conditions. Altogether, this work demonstrates that atomic layer deposition TiO 2 films on silicon photoelectrodes undergo both chemical and morphological changes upon application of potentials only modestly negative of RHE in these media. While the results should serve as a cautionary tale for researchers aiming to immobilize molecular monolayers on “protective” metal oxides, the robust proton-coupled electron transfer reactivity of the films introduces opportunities for the photoelectrochemical generation of reactive charge-carrying mediators.

Electrodes↗

Selective Plasma Deposition of Fluorocarbon Films on SAMs

A dry plasma process has been demonstrated to be useful for the selective modification of self-assembled monolayers (SAMs) of alkanethiolates. These SAMs are used, during the fabrication of semiconductor electronic devices, as etch masks on gold layers that are destined to be patterned and incorporated into the devices. The selective modification involves the formation of fluorocarbon films that render the SAMs more effective in protecting the masked areas of the gold against etching by a potassium iodide (KI) solution. This modification can be utilized, not only in the fabrication of single electronic devices but also in the fabrication of integrated circuits, microelectromechanical systems, and circuit boards. In the steps that precede the dry plasma process, a silicon mold in the desired pattern is fabricated by standard photolithographic techniques. A stamp is then made by casting polydimethylsiloxane (commonly known as silicone rubber) in the mold. The stamp is coated with an alkanethiol solution, then the stamp is pressed on the gold layer of a device to be fabricated in order to deposit the alkanethiol to form an alkanethiolate SAM in the desired pattern (see figure). Next, the workpiece is exposed to a radio-frequency plasma generated from a mixture of CF4 and H2 gases. After this plasma treatment, the SAM is found to be modified, while the exposed areas of gold remain unchanged. This dry plasma process offers the potential for forming masks superior to those formed in a prior wet etching process. Among the advantages over the wet etching process are greater selectivity, fewer pin holes in the masks, and less nonuniformity of the masks. The fluorocarbon films formed in this way may also be useful as intermediate layers for subsequent fabrication steps and as dielectric layers to be incorporated into finished products.

Crain, Mark M., III↗

Dynamic processes in transient phases during self-assembly of organic semiconductor thin films

Understanding and manipulating crystallization processes has been an important challenge for solution-processed organic thin films, both for fundamental studies and for fabricating thin films with near-intrinsic charge transport properties. We report an in situ X-ray scattering study of the crystallization of 2-decyl-7-phenyl-[1]benzothieno[3,2-b][1]benzothiophene (Ph-BTBT-C 10 ) during its deposition from solution. At temperatures modestly below the smectic-E/crystalline phase boundary, the crystallization goes through a transient liquid crystal state before reaching the final stable crystalline phase. Significant dynamics occur in the first few seconds of the transition, which are observed through fluctuations in the X-ray scattering intensity, and are correlated with the time interval that the transient thin film coexists with the evaporating solvent. The transition to the stable crystalline phase takes minutes or even hours under these conditions, which may be a result of the asymmetry of the molecule. Transient phases are of potential interest for applications, since they can act as a route to self-assembly of organic thin films. However, our observations show that the long-lived monolayer-stacked intermediate state does not act as a template for the bilayer-stacked crystalline phase. Rather, the grain structure is replaced through nucleation, where the nucleation free-energy barrier is related to a potential barrier that prevents molecules to flip their long axis by 180°.

36 MATERIALS SCIENCE↗

Fixed-target serial crystallography at the Structural Biology Center

Serial synchrotron crystallography enables the study of protein structures under physiological temperature and reduced radiation damage by collection of data from thousands of crystals. The Structural Biology Center at Sector 19 of the Advanced Photon Source has implemented a fixed-target approach with a new 3D-printed mesh-holder optimized for sample handling. The holder immobilizes a crystal suspension or droplet emulsion on a nylon mesh, trapping and sealing a near-monolayer of crystals in its mother liquor between two thin Mylar films. Data can be rapidly collected in scan mode and analyzed in near real-time using piezoelectric linear stages assembled in an XYZ arrangement, controlled with a graphical user interface and analyzed using a high-performance computing pipeline. Here, the system was applied to two β-lactamases: a class D serine β-lactamase from Chitinophaga pinensis DSM 2588 and L1 metallo-β-lactamase from Stenotrophomonas maltophilia K279a.

59 BASIC BIOLOGICAL SCIENCES↗

Eutectic bonding of boron-aluminum structural components. II

Eutectic bonding is a diffusion brazing process developed for fabricating boron-aluminum components from composite monolayer. This process relies on the diffusion of a thin surface film of copper into the aluminum matrix to form a liquid phase when heated above the copper-aluminum eutectic temperature of 1018 F. This type of fabrication offers design flexibility in that skin thickness may be varied, the stiffness geometry and orientation can be varied, and local reinforcement can be added. In addition, this type of boron-aluminum structure offers high efficiency. Also, this method of construction can be cost-comparative with complex titanium shapes; simple tooling permits easy layup, bonding is a one-step operation, and little finish machining is required.

Niemann, J. T.↗

Visualization of defect induced in-gap states in monolayer MoS 2

Atomic-scale intrinsic defects play a key role in controlling functional electronic properties of two-dimensional (2D) materials. Here, we present a low-temperature scanning–tunneling microscopy and spectroscopy investigation of a common point-defect in monolayer molybdenum disulfide (MoS 2 ). We employ a sample preparation method in which the film surface is never exposed to air so that the native dangling bonds surrounding the defects in the film are preserved. Molybdenum vacancies are identified by their three characteristic in-gap resonances by combining scanning–tunneling measurements with parallel Green’s function-based theoretical modeling. The relative energy shifts between the various in-gap states allow us to identify a relative charge difference between two of the observed vacancies. The role of the substrate on the band structure of the defective MoS 2 monolayer is unveiled. Our study highlights the effects of the substrate on the in-gap states of common defects found in MoS 2 providing a pathway in designing and optimizing 2D materials for electronic applications.

36 MATERIALS SCIENCE↗

Ferroelectric control of magnetic anisotropy of 5 d transition metal monolayers

Electric field control of magnetism using ferroelectric materials offers promising applications in low-power spintronics. We have conducted systematic density functional theory calculations to investigate the magnetic properties of epitaxial 5 d transition metal monolayers on a ferroelectric substrate: PbTi⁢O 3 (PTO). Our study reveals that the magnetocrystalline anisotropy energy of the osmium monolayer is significantly enhanced to 18.1 meV/Os in the upward polarization state and, moreover, the anomalous Hall coefficient of osmium/PTO film is tunable by reversing the electric polarization of the PTO substrate. Additionally, the electric polarization reversal in PTO rotates the easy magnetization axis of the iridium and platinum monolayers by 90°, which is attributed to the rearrangement of interfacial charges. In conclusion, our findings suggest an efficient approach to control the magnetization direction of monoatomic layers and provide valuable insights for the development of low-energy spintronics devices.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Evidence of hexagonal germanium grains on annealed monolayer MoS 2

Growing three-dimensional (3D) materials on two-dimensional (2D) van der Waals surface has shown its effectiveness in overcoming materials incompatibility for stacking transferrable membranes toward advanced device manufacturing. Herein, we demonstrate that the nucleation of hexagonal germanium (Ge) grains within a continuous crystalline film, which has been unfeasible through traditional epitaxy techniques, is realized by chemical vapor deposition on top of n-type monolayer molybdenum disulfide (MoS 2 ) substrates. Suggested by quantum molecular dynamics calculation, the hexagonal Ge nucleation is thermodynamically preferable to cubic Ge when growing on monolayer MoS 2 with sulfur vacancies. The strained hexagonal Ge grains have been confirmed by transmission electron microscopy analyses from both real space and reciprocal space. Scanning probe microscopy shows that the hexagonal Ge film possesses higher reflectivity in infrared spectral range, implying a higher carrier concentration resulted from the narrower band gap, as compared to cubic Ge.

36 MATERIALS SCIENCE↗

Tunable 1D and 2D Polyacrylonitrile Nanosheet Superstructures

Carbon superstructures are widely applied in energy and environment-related areas. Among them, the flower-like polyacrylonitrile (PAN)-derived carbon materials have shown great promise due to their high surface area, large pore volume, and improved mass transport. In this work, we report a versatile and straightforward method for synthesizing one-dimensional (1D) nanostructured fibers and two-dimensional (2D) nanostructured thin films based on flower-like PAN chemistry by taking advantage of the nucleation and growth behavior of PAN. The resulting nanofibers and thin films exhibited distinct morphologies with intersecting PAN nanosheets, which formed through rapid nucleation on existing PAN. We further constructed a variety of hierarchical PAN superstructures based on different templates, solvents, and concentrations. These PAN nanosheet superstructures can be readily converted to carbon superstructures. As a demonstration, the nanostructured thin film exhibited a contact angle of ~180° after surface modification with fluoroalkyl monolayers, which is attributed to high surface roughness enabled by the nanosheet assemblies. In conclusion, this study offers a strategy for the synthesis of nanostructured carbon materials for various applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗