Controllable molecular modulation of conductivity in silicon-based devices.

The electronic properties of silicon, such as the conductivity, are largely dependent on the density of the mobile charge carriers, which can be tuned by gating and impurity doping. When the device size scales down to the nanoscale, routine doping becomes problematic due to inhomogeneities. Here we report that a molecular monolayer, covalently grafted atop a silicon channel, can play a role similar to gating and impurity doping. Charge transfer occurs between the silicon and the molecules upon grafting, which can influence the surface band bending, and makes the molecules act as donors or acceptors. The partly charged end-groups of the grafted molecular layer may act as a top gate. The doping- and gating-like effects together lead to the observed controllable modulation of conductivity in pseudometal-oxide-semiconductor field-effect transistors (pseudo-MOSFETs). The molecular effects can even penetrate through a 4.92-mum thick silicon layer. Our results offer a paradigm for controlling electronic characteristics in nanodevices at the future diminutive technology nodes.

Electronic properties of molecular memory circuits on a nanoscale scaffold.

Significant challenges exist in assembling and interconnecting the building blocks of a nanoscale device and being able to electronically address or measure responses at the molecular level. Here we demonstrate the usefulness of engineered proteins as scaffolds for bottom-up self-assembly for building nanoscale devices out of multiple components. Using genetically engineered cowpea mosaic virus, modified to express cysteine residues on the capsid exterior, gold nanoparticles were attached to the viral scaffold in a specific predetermined pattern to produce specific interparticle distances. The nanoparticles were then interconnected using thiol-terminated conjugated organic molecules, resulting in a three-dimensional network. Network properties were engineered by using molecular components with different I-V characteristics. Networks consisting of molecular wires alone were compared with networks containing voltage controlled molecular switches with two stable conductance states. Using such bistable molecules enabled the formation of switchable molecular networks that could be used in nanoscale memory circuits.

Controlled modulation of conductance in silicon devices by molecular monolayers.

We have controllably modulated the drain current (I(D)) and threshold voltage (V(T)) in pseudo metal-oxide-semiconductor field-effect transistors (MOSFETs) by grafting a monolayer of molecules atop oxide-free H-passivated silicon surfaces. An electronically controlled series of molecules, from strong pi-electron donors to strong pi-electron acceptors, was covalently attached onto the channel region of the transistors. The device conductance was thus systematically tuned in accordance with the electron-donating ability of the grafted molecules, which is attributed to the charge transfer between the device channel and the molecules. This surface grafting protocol might serve as a useful method for controlling electronic characteristics in small silicon devices at future technology nodes.

Scaling constraints in nanoelectronic random-access memories.

Nanoelectronic molecular and magnetic tunnel junction (MTJ) MRAM crossbar memory systems have the potential to present significant area advantages (4 to 6F(2)) compared to CMOS-based systems. The scalability of these conductivity-switched RAM arrays is examined by establishing criteria for correct functionality based on the readout margin. Using a combined circuit theoretical modelling and simulation approach, the impact of both the device and interconnect architecture on the scalability of a conductivity-state memory system is quantified. This establishes criteria showing the conditions and on/off ratios for the large-scale integration of molecular devices, guiding molecular device design. With 10% readout margin on the resistive load, a memory device needs to have an on/off ratio of at least 7 to be integrated into a 64 x 64 array, while an on/off ratio of 43 is necessary to scale the memory to 512 x 512.

Clustering effects on discontinuous gold film NanoCells.

Reproducible negative differential resistance (NDR)-like switching behavior is observed in NanoCells. This behavior is attributed to the formation of filaments and clusters between the discontinuous gold films. Control experiments are performed by self-assembly of insulating molecules between the gold islands and conducting molecules on these islands. Additional control experiments are performed by removing the filaments and clusters between islands using a piranha bath. The results are consistent with theoretical predictions and extend the domain of molecular electronics based in organic molecules to include nanosized clusters as active units. This facilitates a scenario where synthetically accessible organic molecules, with defined characteristics, can be adjusted by metallic nanoclusters as an in situ fine-tuning element, able to compensate for the lack of addressing in the nanosize regime.

NanoCell electronic memories.

NanoCells are disordered arrays of metallic islands that are interlinked with molecules between micrometer-sized metallic input/output leads. In the past, simulations had been conducted showing that the NanoCells may function as both memory and logic devices that are programmable postfabrication. Reported here is the first assembly of a NanoCell with disordered arrays of molecules and Au islands. The assembled NanoCells exhibit reproducible switching behavior and two types of memory effects at room temperature. The switch-type memory is characteristic of a destructive read, while the conductivity-type memory features a nondestructive read. Both types of memory effects are stable for more than a week at room temperature, and bit level ratios (0:1) of the conductivity-type memory have been observed to be as high as 10(4):1 and reaching 10(6):1 upon ozone treatment, which likely destroys extraneous leakage pathways. Both molecular electronic and nanofilamentary metal switching mechanisms have been considered, though the evidence points more strongly toward the latter. The approach here demonstrates the efficacy of a disordered nanoscale array for high-yielding switching and memory while mitigating the arduous task of nanoscale patterning.