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.

Tungsten disulfide thin films via electrodeposition from a single source precursor.

We report a simple process for the electrodeposition of tungsten disulfide thin films from a CH2Cl2-based electrolyte using a tailored single source precursor, [NEt4]2[WS2Cl4]. This new precursor incorporates the 1 : 2 W : S ratio required for formation of WS2, and eliminates the need for an additional proton source in the electrolyte to remove excess sulfide. The electrochemical behaviour of [NEt4]2[WS2Cl4] is studied by cyclic voltammetry and electrochemical quartz crystal microbalance techniques, and the WS2 thin films are grown by potentiostatic electrodeposition.

Improving the longevity of optically-read quantum dot physical unclonable functions.

Quantum dot physically unclonable functions (QD-PUFs) provide a promising solution to the issue of counterfeiting. When quantum dots are deposited on a surface to create a token, they form a unique pattern that is unlikely to ever be reproduced in another token that is manufactured using the same process. It would also be an extreme engineering challenge to deterministically place quantum dots to create a forgery of a specific device. The degradation of the optical response of quantum dots over time, however, places a limitation on their practical usefulness. Here we report methods to minimise the degradation of photoluminescence (PL) from InP/ZnS quantum dots suspended in a polymer and demonstrate reliable authentication using a fingerprinting technique to extract a signature from PL, even after significant degradation has occurred. Using these techniques, it was found that the addition of a polylauryl methacrylate (PLMA) copolymer improved the longevity of devices. The best performing example of this was the Polystyrene-PLMA based material. From this, it is projected that 1000 bits of information could be extracted and read after a period of years, therefore providing a compelling solution to the issue of counterfeiting.

Hotspot generation for unique identification with nanomaterials.

Nanoscale variations in the structure and composition of an object are an enticing basis for verifying its identity, due to the physical complexity of attempting to reproduce such a system. The biggest practical challenge for nanoscale authentication lies in producing a system that can be assessed with a facile measurement. Here, a system is presented in which InP/ZnS quantum dots (QDs) are randomly distributed on a surface of an aluminium-coated substrate with gold nanoparticles (Au NPs). Variations in the local arrangement of the QDs and NPs is shown to lead to interactions between them, which can suppress or enhance fluorescence from the QDs. This position-dependent interaction can be mapped, allowing intensity, emission dynamics, and/or wavelength variations to be used to uniquely identify a specific sample at the nanoscale with a far-field optical measurement. This demonstration could pave the way to producing robust anti-counterfeiting devices.

Mercury Telluride Quantum Dot Based Phototransistor Enabling High-Sensitivity Room-Temperature Photodetection at 2000 nm.

Near-to-mid-infrared photodetection technologies could be widely deployed to advance the infrastructures of surveillance, environmental monitoring, and manufacturing, if the detection devices are low-cost, in compact format, and with high performance. For such application requirements, colloidal quantum dot (QD) based photodetectors stand out as particularly promising due to the solution processability and ease of integration with silicon technologies; unfortunately, the detectivity of the QD photodetectors toward longer wavelengths has so far been low. Here we overcome this performance bottleneck through synergistic efforts between synthetic chemistry and device engineering. First, we developed a fully automated aprotic solvent, gas-injection synthesis method that allows scalable fabrication of large sized HgTe QDs with high quality, exhibiting a record high photoluminescence quantum yield of 17% at the photoluminescence peak close to 2.1 µm. Second, through gating a phototransistor structure we demonstrate room-temperature device response to reach >2 × 1010 cm Hz1/2 W-1 (at 2 kHz modulation frequency) specific detectivity beyond the 2 µm wavelength range, which is comparable to commercial epitaxial-grown photodetectors. To demonstrate the practical application of the QD phototransistor, we incorporated the device in a carbon monoxide gas sensing system and demonstrated reliable measurement of gas concentration. This work represents an important step forward in commercializing QD-based infrared detection technologies.