Control of Rectification in Molecular Junctions: Contact Effects and Molecular Signature.

Thin layers of oligomers with thickness between 7 and 9 nm were deposited on flat gold electrode surfaces by electrochemical reduction of diazonium reagents, then a Ti(2 nm)/Au top contact was applied to complete a solid-state molecular junction. The molecular layers investigated included donor molecules with relatively high energy HOMO, molecules with high HOMO-LUMO gaps and acceptor molecules with low energy LUMO and terminal alkyl chain. Using an oligo(bisthienylbenzene) based layer, a molecule whose HOMO energy level in a vacuum is close to the Fermi level of the gold bottom electrode, the devices exhibit robust and highly reproducible rectification ratios above 1000 at low voltage (2.7 V). Higher current is observed when the bottom gold electrode is biased positively. When the molecular layer is based on a molecule with a high HOMO-LUMO gap, i.e., tetrafluorobenzene, no rectification is observed, while the direction of rectification is reversed if the molecular layer consists of naphtalene diimides having low LUMO energy level. Rectification persisted at low temperature (7 K), and was activationless between 7 and 100 K. The results show that rectification is induced by the asymmetric contact but is also directly affected by orbital energies of the molecular layer. A "molecular signature" on transport through layers with thicknesses above those used when direct tunneling dominates is thus clearly observed, and the rectification mechanism is discussed in terms of Fermi level pinning and electronic coupling between molecules and contacts.

Unidirectional Spin-Dependent Molecule-Ferromagnet Hybridized States Anisotropy in Cobalt Phthalocyanine Based Magnetic Tunnel Junctions.

Organic or molecular spintronics is a rising field of research at the frontier between condensed matter physics and chemistry. It aims to mix spin physics and the richness of chemistry towards designing new properties for spin electronics devices through engineering at the molecular scale. Beyond the expectation of a long spin lifetime, molecules can be also used to tailor the spin polarization of the injected current through the spin-dependent hybridization between molecules and ferromagnetic electrodes. In this Letter, we provide direct evidence of a hybrid interface spin polarization reversal due to the differing hybridization between phthalocyanine molecules and each cobalt electrode in Co/CoPc/Co magnetic tunnel junctions. Tunnel magnetoresistance and anisotropic tunnel magnetoresistance experiments show that interfacial hybridized electronic states have a unidirectional anisotropy that can be controlled by an electric field and that spin hybridization at the bottom and top interfaces differ, leading to an inverse tunnel magnetoresistance.

Combined spin filtering actions in hybrid magnetic junctions based on organic chains covalently attached to graphene.

We present a bias-controlled spin-filtering mechanism in spin-valves including a hybrid organic chain/graphene interface. Wet growth conditions of oligomeric molecular chains would usually lead, during standard CMOS-compatible fabrication processes, to the quenching of spintronics properties of metallic spin sources due to oxidation. We demonstrate by X-ray photoelectron spectroscopy that the use of a protective graphene layer fully preserves the metallic character of the ferromagnetic surface and thus its capability to deliver spin polarized currents. We focus here on a small aromatic chain of controllable lengths, formed by nitrobenzene monomers and derived from the commercial 4-nitrobenzene diazonium tetrafluoroborate, covalently attached to the graphene passivated spin sources thanks to electroreduction. A unique bias dependent switch of the spin signal is then observed in complete spin valve devices, from minority to majority spin carriers filtering. First-principles calculations are used to highlight the key role played by the spin-dependent hybridization of electronic states present at the different interfaces. Our work is a first step towards the exploration of spin transport using different functional molecular chains. It opens the perspective of atomic tailoring of magnetic junction devices towards spin and quantum transport control, thanks to the flexibility of ambient electrochemical surface functionalization processes.

Giant spin signals in chemically functionalized multiwall carbon nanotubes.

Transporting quantum information such as the spin information over micrometric or even millimetric distances is a strong requirement for the next-generation electronic circuits such as low-voltage spin-logic devices. This crucial step of transportation remains delicate in nontopologically protected systems because of the volatile nature of spin states. Here, a beneficial combination of different phenomena is used to approach this sought-after milestone for the beyond-Complementary Metal Oxide Semiconductor (CMOS) technology roadmap. First, a strongly spin-polarized charge current is injected using highly spin-polarized hybridized states emerging at the complex ferromagnetic metal/molecule interfaces. Second, the spin information is brought toward the conducting inner shells of a multiwall carbon nanotube used as a confined nanoguide benefiting from both weak spin-orbit and hyperfine interactions. The spin information is finally electrically converted because of a strong magnetoresistive effect. The experimental results are also supported by calculations qualitatively revealing exceptional spin transport properties of this system.

Charge injection and transport properties of large area organic junctions based on aryl thin films covalently attached to a multilayer graphene electrode.

The quantum interaction between molecules and electrode materials at molecule/electrode interfaces is a major ingredient in the electron transport properties of organic junctions. Driven by the coupling strength between the two materials, it results mainly in the broadening and energy shift of the interacting molecular orbitals. Using new electrode materials, such as the recently developed semi-conducting two-dimensional nanomaterials, has become a significant advancement in the field of molecular/organic electronics that opens new possibilities for controlling the interfacial electronic properties and thus the charge injection properties. In this article, we report the use of atomically thin two-dimensional multilayer graphene films as the base electrode in organic junctions with a vertical architecture. The interfacial electronic structure dominated by the covalent bonding between bis-thienyl benzene diazonium-based molecules and the multilayer graphene electrode has been probed by ultraviolet photoelectron spectroscopy and the results are compared with those obtained on junctions with standard Au electrodes. Room temperature injection properties of such interfaces have also been explored by electron transport measurements. We find that, despite strong variations of the density of states, the Fermi energy and the injection barriers, both organic junctions with Au base electrodes and multilayer graphene base electrodes show similar electronic responses. We explain this observation by the strong orbital coupling occurring at the bottom electrode/bis-thienyl benzene molecule interface and by the pinning of the hybridized molecular orbitals.

Charge transport through one-dimensional Moiré crystals.

Moiré superlattices were generated in two-dimensional (2D) van der Waals heterostructures and have revealed intriguing electronic structures. The appearance of mini-Dirac cones within the conduction and valence bands of graphene is one of the most striking among the new quantum features. A Moiré superstructure emerges when at least two periodic sub-structures superimpose. 2D Moiré patterns have been particularly investigated in stacked hexagonal 2D atomic lattices like twisted graphene layers and graphene deposited on hexagonal boron-nitride. In this letter, we report both experimentally and theoretically evidence of superlattices physics in transport properties of one-dimensional (1D) Moiré crystals. Rolling-up few layers of graphene to form a multiwall carbon nanotube adds boundaries conditions that can be translated into interference fringes-like Moiré patterns along the circumference of the cylinder. Such a 1D Moiré crystal exhibits a complex 1D multiple bands structure with clear and robust interband quantum transitions due to the presence of mini-Dirac points and pseudo-gaps. Our devices consist in a very large diameter (>80 nm) multiwall carbon nanotubes of high quality, electrically connected by metallic electrodes acting as charge reservoirs. Conductance measurements reveal the presence of van Hove singularities assigned to 1D Moiré superlattice effect and illustrated by electronic structure calculations.

Self-assembled monolayers based spintronics: from ferromagnetic surface functionalization to spin-dependent transport.

Chemically functionalized surfaces are studied for a wide range of applications going from medicine to electronics. Whereas non-magnetic surfaces have been widely studied, functionalization of magnetic surfaces is much less common and has almost never been used for spintronics applications. In this article we present the functionalization of La2/3Sr1/3MnO3, a ferromagnetic oxide, with self-assembled monolayers for spintronics. La2/3Sr1/3MnO3 is the prototypical half-metallic manganite used in spintronics studies. First, we show that La2/3Sr1/3MnO3 can be functionalized by alkylphosphonic acid molecules. We then emphasize the use of these functionalized surfaces in spintronics devices such as magnetic tunnel junctions fabricated using a nano-indentation based lithography technique. The observed exponential increase of tunnel resistance as a function of alkyl chain length is a direct proof of the successful connection of molecules to ferromagnetic electrodes. For all alkyl chains studied we obtain stable and robust tunnel magnetoresistance, with effects ranging from a few tens to 10 000%. These results show that functionalized electrodes can be integrated in spintronics devices and open the door to a molecular engineering of spintronics.

Fabrication and transfer of flexible few-layers MoS2 thin film transistors to any arbitrary substrate.

Recently, transition metal dichalcogenides (TMDCs) have attracted interest thanks to their large field effective mobility (>100 cm(2)/V · s), sizable band gap (around 1-2 eV), and mechanical properties, which make them suitable for high performance and flexible electronics. In this paper, we present a process scheme enabling the fabrication and transfer of few-layers MoS2 thin film transistors from a silicon template to any arbitrary organic or inorganic and flexible or rigid substrate or support. The two-dimensional semiconductor is mechanically exfoliated from a bulk crystal on a silicon/polyvinyl alcohol (PVA)/polymethyl methacrylane (PMMA) stack optimized to ensure high contrast for the identification of subnanometer thick flakes. Thin film transistors (TFTs) with structured source/drain and gate electrodes are fabricated following a designed procedure including steps of UV lithography, wet etching, and atomic layer deposited (ALD) dielectric. Successively, after the dissolution of the PVA sacrificial layer in water, the PMMA film, with the devices on top, can be transferred to another substrate of choice. Here, we transferred the devices on a polyimide plastic foil and studied the performance when tensile strain is applied parallel to the TFT channel. We measured an electron field effective mobility of 19 cm(2)/(V s), an I(on)/I(off)ratio greater than 10(6), a gate leakage current as low as 0.3 pA/µm, and a subthreshold swing of about 250 mV/dec. The devices continue to work when bent to a radius of 5 mm and after 10 consecutive bending cycles. The proposed fabrication strategy can be extended to any kind of 2D materials and enable the realization of electronic circuits and optical devices easily transferrable to any other support.

Unveiling self-assembled monolayers' potential for molecular spintronics: spin transport at high voltage.

Molecular magnetic tunnel junctions using self-assembled monolayers (SAMs) as tunnel barriers show stable and efficient spin transport properties. Large tunnel magnetoresistance with a flat bias voltage dependence of the magnetoresistance is observed in La(2/3) Sr(1/3) MnO(3) /dodecylphosphonic acid SAM/Co nanocontacts. This opens the door to spintronic tailoring though SAM engineering and could also lead to new venues for spin injection in organic devices.

Self-assembled monolayer-functionalized half-metallic manganite for molecular spintronics.

(La,Sr)MnO(3) manganite (LSMO) has emerged as the standard ferromagnetic electrode in organic spintronic devices due to its highly spin-polarized character and air stability. Whereas organic semiconductors and polymers have been mainly envisaged to propagate spin information, self-assembled monolayers (SAMs) have been overlooked and should be considered as promising materials for molecular engineering of spintronic devices. Surprisingly, up to now the first key step of SAM grafting protocols over LSMO surface thin films is still missing. We report the grafting of dodecyl (C12P) and octadecyl (C18P) phosphonic acids over the LSMO half-metallic oxide. Alkylphosphonic acids form ordered self-assembled monolayers, with the phosphonic group coordinated to the surface and alkyl chains tilted from the surface vertical by 43° (C12P) and 27° (C18P). We have electrically characterized these SAMs in nanodevices and found that they act as tunnel barriers, opening the door toward the integration of alkylphosphonic acid//LSMO SAMs into future molecular/organic spintronic devices such as spin OLEDs.