Determination of electric and thermoelectric properties of molecular junctions by AFM in peak force tapping mode.

Molecular thin films, such as self-assembled monolayers (SAMs), offer the possibility of translating the optimised thermophysical and electrical properties of high-Seebeck-coefficient single molecules to scalable device architectures. However, for many scanning probe-based approaches attempting to characterise such SAMs, there remains a significant challenge in recovering single-molecule equivalent values from large-area films due to the intrinsic uncertainty of the probe-sample contact area coupled with film damage caused by contact forces. Here we report a new reproducible non-destructive method for probing the electrical and thermoelectric (TE) properties of small assemblies (10-103) of thiol-terminated molecules arranged within a SAM on a gold surface, and demonstrate the successful and reproducible measurements of the equivalent single-molecule electrical conductivity and Seebeck values. We have used a modified thermal-electric force microscopy approach, which integrates the conductive-probe atomic force microscope, a sample positioned on a temperature-controlled heater, and a probe-sample peak-force feedback that interactively limits the normal force across the molecular junctions. The experimental results are interpreted by density functional theory calculations allowing quantification the electrical quantum transport properties of both single molecules and small clusters of molecules. Significantly, this approach effectively eliminates lateral forces between probe and sample, minimising disruption to the SAM while enabling simultaneous mapping of the SAMs nanomechanical properties, as well as electrical and/or TE response, thereby allowing correlation of the film properties.

Using intrinsic properties of quantum dots to provide additional security when uniquely identifying devices.

Unique identification of optical devices is important for anti-counterfeiting. Physical unclonable functions (PUFs), which use random physical characteristics for authentication, are advantageous over existing optical solutions, such as holograms, due to the inherent asymmetry in their fabrication and reproduction complexity. However, whilst unique, PUFs are potentially vulnerable to replication and simulation. Here we introduce an additional benefit of a small modification to an established model of nanoparticle PUFs by using a second measurement parameter to verify their authenticity. A randomly deposited array of quantum dots is encapsulated in a transparent polymer, forming a tag. Photoluminescence is measured as a function of excitation power to assess uniqueness as well as the intrinsic nonlinear response of the quantum material. This captures a fingerprint, which is non-trivial to clone or simulate. To demonstrate this concept practically, we show that these tags can be read using an unmodified smartphone, with its built-in flash for excitation. This development over constellation-style optical PUFs paves the way for more secure, facile authentication of devices without requiring complex fabrication or characterisation techniques.