Browsing by Author "Kayaci, Nilgun"

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The Hansen solubility approach towards green solvent processing: n-channel organic field-effect transistors under ambient conditions
(Royal Society of Chemistry, 2024) Deneme, Ibrahim; Yıldız, Tevhide Ayça; Kayaci, Nilgun; Usta, Hakan; 0000-0001-9415-0242; 0000-0002-0618-1979; AGÜ, Mühendislik Fakültesi, Malzeme Bilimi ve Nanoteknoloji Mühendisliği Bölümü; Deneme, Ibrahim; Yıldız, Tevhide Ayça; Kayaci, Nilgun; Usta, Hakan
The adoption of green solvents is of utmost importance for the solution-based fabrication of semiconductor thin films and for the commercialization of (opto)electronic devices, especially in response to evolving regulatory mandates for handling organic materials. Despite the increasing interest in this area, the scarcity of green solvent-processed n-channel OFETs, especially functioning under ambient conditions, highlights the need for further research. In this study, we demonstrated the Hansen solubility approach to study the solubility behavior of an ambient-stable n-type semiconductor, 2,20 - (2,8-bis(3-dodecylthiophen-2-yl)indeno[1,2-b]fluorene-6,12-diylidene)dimalononitrile (b,b0 -C12-TIFDMT), and to analyze potential green solvents for thin-film processing. The Hansen solubility parameters were determined to be dD = 20.8 MPa1/2, dP = 5.8 MPa1/2, and dH = 5.5 MPa1/2 with a radius (R0) of 8.3 MPa1/2. A green solvent screening analysis based on the minimal distance constraint and quantitative sustainability score identified ethoxybenzene, anisole, 2-methylanisole, and 2-methyltetrahydrofuran as suitable green solvents (Ra0s = 5.17–7.93 MPa1/2 o R0). A strong thermodynamic correlation was identified between the solubility and the semiconductor–solvent distance in the 3D Hansen solubility space, in which the maximum solubility limit could be estimated with the enthalpy of fusion (DHfus) and melting temperature (Tmp) of the semiconductor. To the best of our knowledge, this relationship between the maximum solubility limit and thermal properties has been established for the first time for organic semiconductors. Bottom-gate/top-contact OFETs fabricated by spin-coating the semiconductor green solutions exhibited mes reaching B0.2 cm2 V1 s 1 (Ion/Ioff B106 –107 and Von B0–5 V) under ambient conditions. This device performance, to our knowledge, is the highest reported for an ambient-stable green solvent-processed n-channel OFET. Our HSP-based rational approach and unique findings presented in this study can shed critical light on how green solvents can be efficiently incorporated in solution processing in organic (opto)electronics, and whether ambient-stable n-type semiconductors can continue to play an important role in green OFETs.
Organic Light-Emitting Physically Unclonable Functions
(WILEY-V C H VERLAG GMBHPOSTFACH 101161, 69451 WEINHEIM, GERMANY, 2021) Kayaci, Nilgun; Ozdemir, Resul; Kalay, Mustafa; Kiremitler, N. Burak; Usta, Hakan; Onses, M. Serdar; AGÜ, Mühendislik Fakültesi, Malzeme Bilimi ve Nanoteknoloji Mühendisliği Bölümü; Ozdemir, Resul; Usta, Hakan
The development of novel physically unclonable functions (PUFs) is of growing interest and fluorescent organic semiconductors (f-OSCs) offer unique advantages of structural versatility, solution-processability, ease of processing, and great tuning ability of their physicochemical/optoelectronic/spectroscopic properties. The design and ambient atmosphere facile fabrication of a unique organic light-emitting physically unclonable function (OLE-PUF) based on a green-emissive fluorescent oligo(p-phenyleneethynylene) molecule is reported. The OLE-PUFs have been prepared by one-step, brief (5 min) thermal annealing of spin-coated nanoscopic films (approximate to 40 nm) at a modest temperature (170 degrees C), which results in efficient surface dewetting to form randomly positioned/sized hemispherical features with bright fluorescence. The random positioning of molecular domains generated the unclonable surface with excellent uniformity (0.50), uniqueness (0.49), and randomness (p > 0.01); whereas the distinctive photophysical and structural properties of the molecule created the additional security layers (fluorescence profile, excited-state decay dynamics, Raman mapping/spectrum, and infrared spectrum) for multiplex encoding. The OLE-PUFs on substrates of varying chemical structures, surface energies and flexibility, and direct deposition on goods via drop-casting are demonstrated. The OLE-PUFs immersed in water, exposed to mechanical abrasion, and read-out repeatedly via fluorescence imaging showed great stability. These findings clearly demonstrate that rationally engineered solution-processable f-OSCs have a great potential to become a key player in the development of new-generation PUFs.
Structurally Colored Physically Unclonable Functions with Ultra-Rich and Stable Encoding Capacity
(WILEY-Advanced, 2025) Esidir, Abidin; Ren, Miaoning; Pekdemir, Sami; Kalay, Mustafa; Kayaci, Nilgun; Gunaltay, Nail; Usta, Hakan; Huang, Xian; Onses, Mustafa Serdar; 0000-0002-0618-1979; AGÜ, Mühendislik Fakültesi, Malzeme Bilimi ve Nanoteknoloji Mühendisliği Bölümü; Usta, Hakan
Identity security and counterfeiting assume a critical importance in the digitized world. An effective approach to addressing these issues is the use of physically unclonable functions (PUFs). The overarching challenge is a simultaneous combination of extremely high encoding capacity, stable operation, practical fabrication, and a widely available readout mechanism. Herein this challenge is addressed by designing an optical PUF via exploiting the thickness-dependent structural color formation in nanoscopic films of ZnO. The structural coloration ensures authentication using widely available bright-field-based optical readout, whereas the metal oxide provides a high degree of structural stability. True physical randomness in spatial position is achieved by physical vapor deposition of ZnO through stencil masks that are fabricated by pore formation in polycarbonate membranes via photothermal processing of stochastically positioned plasmonic nanoparticles. Structural coloration emerges from thin film interference as confirmed via simulation studies. The rich color variation and stochastic definition of domain size and geometry result in chaotic features with an encoding capacity that approaches (6.4 x 105)(2752x2208). Deep learning-based authentication is further demonstrated by transforming these chaotic features into unbreakable codes without field limitations. This ultra-rich encoding capacity, coupled with outstanding thermal and chemical stability, forms a new cutting edge for state-of-the-art PUF-based encoding systems.