Writing chemical patterns using electrospun fibers as nanoscale inkpots for directed assembly of colloidal nanocrystals

Kiremitler, N. Burak; Torun, Ilker; Altıntas, Yemliha; Patarroyo, Javier; Demir, Hilmi Volkan; Puntes, Víctor; Mutlugün, Evren; Önses, M. Serdar

doi:10.1039/c9nr08056b

Cited by 6 publications

(4 citation statements)

References 78 publications

(96 reference statements)

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“…We then spin-coat a film of P2VP. The choice of P2VP stems from several considerations: (i) this polymer consists of a structural unit comprising a pyridine moiety, providing a universal attachment chemistry for colloidal nanomaterials of varying size, shape, geometry, and composition , and (ii) P2VP has a surface energy (54.5 mN/m, Figure S1) higher than PS, making its thin films vulnerable to dewetting using moderate temperatures and sufficiently thick films. Heating these films at a temperature higher than the glass transition temperature of P2VP resulted in spontaneous dewetting of the films into randomly positioned features with sizes and separation distances that depend on the thickness of the P2VP film and annealing conditions.…”

Section: Resultsmentioning

confidence: 99%

Physically Unclonable Surfaces via Dewetting of Polymer Thin Films

Torun

Sakir

et al. 2021

ACS Appl. Mater. Interfaces

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From anti-counterfeiting to biotechnology applications, there is a strong demand for encoded surfaces with multiple security layers that are prepared by stochastic processes and are adaptable to deterministic fabrication approaches. Here, we present dewetting instabilities in nanoscopic (thickness <100 nm) polymer films as a form of physically unclonable function (PUF). The inherent randomness involved in the dewetting process presents a highly suitable platform for fabricating unclonable surfaces. The thermal annealinginduced dewetting of poly(2-vinyl pyridine) (P2VP) on polystyrenegrafted substrates enables fabrication of randomly positioned functional features that are separated at a microscopic length scale, a requirement set by optical authentication systems. At a first level, PUFs can be simply and readily verified via reflection of visible light. Area-specific electrostatic interactions between P2VP and citrate-stabilized gold nanoparticles allow for fabrication of plasmonic PUFs. The strong surface-enhanced Raman scattering by plasmonic nanoparticles together with incorporation of taggants facilitates a molecular vibration-based security layer. The patterning of P2VP films presents opportunities for fabricating hybrid security labels, which can be resolved through both stochastic and deterministic pathways. The adaptability to a broad range of nanoscale materials, simplicity, versatility, compatibility with conventional fabrication approaches, and high levels of stability offer key opportunities in encoding applications.

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Section: Resultsmentioning

confidence: 99%

Physically Unclonable Surfaces via Dewetting of Polymer Thin Films

Torun

Sakir

et al. 2021

ACS Appl. Mater. Interfaces

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“…The PS and PMMA are hydrophobic and mostly inert polymers. PVP and PEO are hydrophilic, biocompatible, and biodegradable polymers. , P2VP can form strong electrostatic bonds with many different nanomaterials, thanks to the pyridine group. − Collectively, these results position the electrospraying as a versatile approach for the fabrication of high performance PUFs.…”

Section: Resultsmentioning

confidence: 99%

Unclonable Features via Electrospraying of Bulk Polymers

Esidir

Kiremitler

Kalay

et al. 2022

ACS Appl. Polym. Mater.

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The ability to encode unclonable information using low-cost materials and processes is of significant interest for anti-counterfeiting and information security applications. In this study, we present a versatile approach based on electrospraying of polymer solutions to generate randomly positioned complex features as a form of physically unclonable function (PUF). The key advantage of this approach is that readily available low-cost bulk polymeric materials can form small and complex features using a simple process. Polymers of varying composition and molecular weight, together with different solvents and electrospraying conditions, are systematically explored to construct the parameter space for PUFs of varying characteristics. Besides the randomness in the spatial positions and sizes of features, the key advantage of the presented approach is the ability to generate complex 3D shapes, which are very difficult, if not impossible to fabricate with the most advanced fabrication techniques. The inclusion of photoluminescent molecules establishes an additional security layer. The additive nature of operation enables multiplexing, i.e., deposition of multiple materials on the same substrate. The fabricated PUFs have an average uniformity of 0.533 and uniqueness of 0.495, which are highly close to an ideal value of 0.5. The authentication is effectively performed using a feature detection algorithm without the need for markers and precisely defined rotation angles, greatly relaxing constraints associated with the imaging. Direct application of PUFs on the label of goods and authentication via a handheld microscope demonstrate the practical utility of the presented approach.

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“…[36] The choice of P2VP [37,38] stems from the ability of selective adsorption of colloidal nanomaterials through electrostatic interactions as demonstrated with spherical [39] and rod-shaped [40] gold nanoparticles, and nanoplatelets. [41] An additional characteristic of this polymer is the protonation and deprotonation of the pyridine group allowing for pH tunable assembly of QDs. The pH of the dispersion is exploited for the tunable assembly QDs in two routes: (i) The adsorption density of QDs and fluorescence from the patterns can be tuned with the pH, (ii) randomized QD domains emerge from the patterned region for pH ≤ ≈4.…”

Section: Introductionmentioning

confidence: 99%

pH Tunable Patterning of Quantum Dots

Torun,

Huang,

Kalay

et al. 2023

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Patterning of quantum dots (QDs) is essential for many, especially high‐tech, applications. Here, pH tunable assembly of QDs over functional patterns prepared by electrohydrodynamic jet printing of poly(2‐vinylpyridine) is presented. The selective adsorption of QDs from water dispersions is mediated by the electrostatic interaction between the ligand composed of 3‐mercaptopropionic acid and patterned poly(2‐vinylpyridine). The pH of the dispersion provides tunability at two levels. First, the adsorption density of QDs and fluorescence from the patterns can be modulated for pH > ≈4. Second, patterned features show unique type of disintegration resulting in randomly positioned features within areas defined by the printing for pH ≤ ≈4. The first capability is useful for deterministic patterning of QDs, whereas the second one enables hierarchically structured encoding of information by generating stochastic features of QDs within areas defined by the printing. This second capability is exploited for generating addressable security labels based on unclonable features. Through image analysis and feature matching algorithms, it is demonstrated that such patterns are unclonable in nature and provide a suitable platform for anti‐counterfeiting applications. Collectively, the presented approach not only enables effective patterning of QDs, but also establishes key guidelines for addressable assembly of colloidal nanomaterials.

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Writing chemical patterns using electrospun fibers as nanoscale inkpots for directed assembly of colloidal nanocrystals

Abstract: Applications that range from electronics to biotechnology will greatly benefit from low-cost, scalable and multiplex fabrication of spatially defined arrays of colloidal inorganic nanocrystals.

Cited by 6 publications

References 78 publications

Physically Unclonable Surfaces via Dewetting of Polymer Thin Films

Physically Unclonable Surfaces via Dewetting of Polymer Thin Films

Unclonable Features via Electrospraying of Bulk Polymers

pH Tunable Patterning of Quantum Dots

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