Christoph Busche

Design and fabrication of memory devices based on nanoscale polyoxometalate clusters

Flash memory devices—that is, non-volatile computer storage media that can be electrically erased and reprogrammed—are vital for portable electronics, but the scaling down of metal–oxide–semiconductor (MOS) flash memory to sizes of below ten nanometres per data cell presents challenges. Molecules have been proposed to replace MOS flash memory, but they suffer from low electrical conductivity, high resistance, low device yield, and finite thermal stability, limiting their integration into current MOS technologies. Although great advances have been made in the pursuit of molecule-based flash memory, there are a number of significant barriers to the realization of devices using conventional MOS technologies. Here we show that core–shell polyoxometalate (POM) molecules can act as candidate storage nodes for MOS flash memory. Realistic, industry-standard device simulations validate our approach at the nanometre scale, where the device performance is determined mainly by the number of molecules in the storage media and not by their position. To exploit the nature of the core–shell POM clusters, we show, at both the molecular and device level, that embedding [(Se(iv)O3)2]4− as an oxidizable dopant in the cluster core allows the oxidation of the molecule to a [Se(v)2O6]2− moiety containing a {Se(v)–Se(v)} bond (where curly brackets indicate a moiety, not a molecule) and reveals a new 5+ oxidation state for selenium. This new oxidation state can be observed at the device level, resulting in a new type of memory, which we call ‘write-once-erase’. Taken together, these results show that POMs have the potential to be used as a realistic nanoscale flash memory. Also, the configuration of the doped POM core may lead to new types of electrical behaviour. This work suggests a route to the practical integration of configurable molecules in MOS technologies as the lithographic scales approach the molecular limit.

Trinuclear {M1}CN{M2}2 Complexes (M1 = CrIII, FeIII, CoIII; M2 = CuII, NiII, MnII). Are Single Molecule Magnets Predictable?

The reaction of the hexacyanometalates K3[M(1)(CN)6] (M(1) = Cr(III), Fe(III), Co(III)) with the bispidine complexes [M(2)(L(1))(X)](n+) and [M(2)(L(2))(X)](n+) (M(2) = Mn(II), Ni(II), Cu(II); L(1) = 3-methyl-9-oxo-2,4-di-(2-pyridyl)-7-(2-pyridylmethyl)-3,7-diazabicyclo[3.3.1]nonane-1,5-dicarboxylic acid dimethyl ester; L(2) = 3-methyl-9-oxo-7-(2-pyridylmethyl)-2,4-di-(2-quinolyl)-3,7-diazabicyclo[3.3.1]nonane-1,5-dicarboxylic acid dimethyl ester; X = anion or solvent) in water-methanol mixtures affords trinuclear complexes with cis- or trans-arrangement of the bispidine-capped divalent metal centers around the hexacyanometalate. X-ray structural analyses of five members of this family of complexes (cis-Fe[CuL(2)]2, trans-Fe[CuL(1)]2, cis-Co[CuL(2)]2, trans-Cr[MnL(1)]2, trans-Fe[MnL(1)]2) and the magnetic data of the entire series are reported. The magnetic data of the cyanide bridged, ferromagnetically coupled cis- and trans-Fe[ML]2 compounds (M = Ni(II), Cu(II)) with S = 3/2 (Cu(II)) and S = 5/2 (Ni(II)) ground states are analyzed with an extended Heisenberg Hamiltonian which accounts for anisotropy and zero-field splitting, and the data of the Cu(II) systems, for which structures are available, are thoroughly analyzed in terms of an orbital-dependent Heisenberg Hamiltonian, in which both spin-orbit coupling and low-symmetry ligand fields are taken into account. It is shown that the absence of single-molecule magnetic behavior in all spin clusters reported here is due to a large angular distortion of the [Fe(CN)6](3-) center and the concomitant quenching of orbital angular momentum of the Fe(III) ((2)T2g) ground state.

Nanoscale Growth of Molecular Oxides: Assembly of a {V6} Double Cubane Between Two Lacunary {P2W15} Polyoxometalates

POM-in-POM: A Wells–Dawson polyoxometalate sandwich compound with a double cubane core consisting of six vanadium atoms has been synthesized (see structure). Cluster formation was followed by mass spectrometry and the reduction of the double cubane was studied by a novel technique combining mass spectrometry and spectroelectrochemistry.

Synthesis and characterisation of a lanthanide-capped dodecavanadate cage

The synthesis of a series of discrete lanthanide-capped polyoxovanadate cages is presented along with magnetic and electrochemical measurements which reveal a redox active dodecavanadate cluster with potential as a new functional building unit in polyoxovanadate chemistry.

Towards Polyoxometalate-Cluster-Based Nano-Electronics

We explore the concept that the incorporation of polyoxometalates (POMs) into complementary metal oxide semiconductor (CMOS) technologies could offer a fundamentally better way to design and engineer new types of data storage devices, due to the enhanced electronic complementarity with SiO2, high redox potentials, and multiple redox states accessible to polyoxometalate clusters. To explore this we constructed a custom-built simulation domain bridge. Connecting DFT, for the quantum mechanical modelling part, and mesoscopic device modelling, confirms the theoretical basis for the proposed advantages of POMs in non-volatile molecular memories (NVMM) or flash-RAM.

Naphthoxanthenyl, a New Stable Phenalenyl Type Radical Stabilized by Electronic Effects

Naphthoxanthenyl 1 is a new stable phenalenyl-type radical. Electrochemical studies indicate that 1 has two reversible redox processes that occur on comparatively short time scales. Crystals containing 1 can be grown by electrocrystallization, suggesting that they are conductive.

Following the Reaction of Heteroanions inside a {W18O56} Polyoxometalate Nanocage by NMR Spectroscopy and Mass Spectrometry

By incorporating phosphorus(III)-based anions into a polyoxometalate cage, a new type of tungsten-based unconventional Dawson-like cluster, [W18O56(HPIIIO3)2(H2O)2]8−, was isolated, in which the reaction of the two phosphite anions [HPO3]2− within the {W18O56} cage could be followed spectroscopically. As well as full X-ray crystallographic analysis, we studied the reactivity of the cluster using both solution-state NMR spectroscopy and mass spectrometry. These techniques show that the cluster undergoes a structural rearrangement in solution whereby the {HPO3} moieties dimerize to form a weakly interacting (O3PH⋅⋅⋅HPO3) moiety. In the crystalline state the cluster exhibits a thermally triggered oxidation of the two PIII template moieties to form PV centers (phosphite to phosphate), commensurate with the transformation of the cage into a Wells–Dawson {W18O54} cluster.

Polyoxometalate {W18O56XO6} Clusters with Embedded Redox-Active Main-Group Templates as Localized Inner-Cluster Radicals†

Non-mixed-valent reduced polyoxometalates, namely {W18O56XO6} Dawson-like clusters (X=IVII or TeVI) with a localized redox active template have been synthesized and redox properties compared with the pure tungsten control (that is, X=WVI). Upon one-electron reduction, the electron localizes on the main-group element, giving IVI or TeV, respectively. These clusters have potential as a new type of electron-transfer reagent.

Real-time ion-flux imaging in the growth of micrometer-scale structures and membranes.

Real-time ion flux imaging: an ion-sensitive field-effect transistor (ISFET) array is coupled with optical microscopy to image the growth of, and ion flux through, micrometer-scale tubes and membranes built from polyoxometalate clusters. The correlation between the optical and ionic imaging data is excellent, showcasing the use of ISFET arrays for high-resolution spatial and temporal mapping of ionic movements.

Optimization and Evaluation of Variability in the Programming Window of a Flash Cell With Molecular Metal–Oxide Storage

We report a modeling study of a conceptual nonvolatile memory cell based on inorganic molecular metal-oxide clusters as a storage media embedded in the gate dielectric of a MOSFET. For the purpose of this paper, we developed a multiscale simulation framework that enables the evaluation of variability in the programming window of a flash cell with sub-20-nm gate length. Furthermore, we studied the threshold voltage variability due to random dopant fluctuations and fluctuations in the distribution of the molecular clusters in the cell. The simulation framework and the general conclusions of our work are transferrable to flash cells based on alternative molecules used for a storage media.