Browsing by Author "Usta, Hakan"

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Citation - WoS: 75
Citation - Scopus: 74
Perfluoroalkyl-Functionalized Thiazole Thiophene Oligomers as N-Channel Semiconductors in Organic Field-Effect and Light-Emitting Transistors
(Amer Chemical Soc, 2014) Usta, Hakan; Sheets, William Christopher; Denti, Mitchell; Generali, Gianluca; Capelli, Raffaella; Lu, Shaofeng; Facchetti, Antonio
Despite their favorable electronic and structural properties, the synthetic development and incorporation of thiazole-based building blocks into n-type semiconductors has lagged behind that of other pi-deficient building blocks. Since thiazole insertion into pi-conjugated systems is synthetically more demanding, continuous research efforts are essential to underscore their properties in electron-transporting devices. Here, we report the design, synthesis, and characterization of a new series of thiazolethiophene tetra- (1 and 2) and hexa-heteroaryl (3 and 4) co-oligomers, varied by core extension and regiochemistry, which are end-functionalized with electron-withdrawing perfluorohexyl substituents. These new semiconductors are found to exhibit excellent n-channel OFET transport with electron mobilities (mu(e)) as high as 1.30 cm(2)/(V center dot s) (I-on/I-off > 10(6)) for films of 2 deposited at room temperature. In contrary to previous studies, we show here that 2,2'-bithiazole can be a very practical building block for high-performance n-channel semiconductors. Additionally, upon 2,2'- and 5,5'-bithiazole insertion into a sexithiophene backbone of well-known DFH-6T, significant charge transport improvements (from 0.0010.021 cm(2)/(V center dot s) to 0.200.70 cm(2)/(V center dot s)) were observed for 3 and 4. Analysis of the thin-film morphological and microstructural characteristics, in combination with the physicochemical properties, explains the observed high mobilities for the present semiconductors. Finally, we demonstrate for the first time implementation of a thiazole semiconductor (2) into a trilayer light-emitting transistor (OLET) enabling green light emission. Our results show that thiazole is a promising building block for efficient electron transport in ?-conjugated semiconductor thin-films, and it should be studied more in future optoelectronic applications.
Citation - WoS: 36
Citation - Scopus: 34
A Dopant-Free 2,7-Dioctyl[1]Benzothieno[3,2 (C8-BTBT) Hole Transporting Layer for Highly Stable Perovskite Solar Cells With Efficiency Over 22%
(Royal Soc Chemistry, 2022) Kaya, Ismail Cihan; Ozdemir, Resul; Usta, Hakan; Sonmezoglu, Savas
In this study, for the first time, n-i-p PSCs were fabricated using dopant-free 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT) as the solution-processed hole transporting layer (HTL). The power conversion efficiency (PCE) of the optimized device with the C8-BTBT film that favored edge-on molecular alignment was 22.45% with negligible hysteresis. A thinner dopant-free C8-BTBT HTL effectively protected the perovskite layer from moisture resulting in better shelf-life stability for un-encapsulated PSCs, which maintained >80% of its initial PCE (after a period of 120 days) at a relative humidity level of 40-45%. In addition, the C8-BTBT-based PSCs kept their high performance with no obvious PCE loss at 60 degrees C for 20 days in the ambient atmosphere and retained 82% of their initial PCE at 85 degrees C for 10 days. Overall, our findings revealed that a thin solution-processed C8-BTBT HTL plays a critical role not only in hole extraction and transport but also in greatly improving the ambient and thermal stability of n-i-p PSCs.
Citation - WoS: 10
Citation - Scopus: 11
Enhanced Mass Transfer Rate and Solubility of Methane via Addition of Alcohols for Methylosinus Trichosporium OB3b Fermentation
(Elsevier Science inc, 2017) Kim, Kwangmin; Kim, Yujin; Yang, Jeongmo; Ha, Kyoung-Su; Usta, Hakan; Lee, Jinwon; Kim, Choongik
The effect of alcohol on methane-water volumetric mass transfer coefficient (1(0) and solubility of methane was investigated in this study. Various alcohols including methanol, ethanol, 1-propanol, butanol, and pentanol were added to aqueous solution and enhancement of both methane-water k(L)a (from 72h(-1) to 471 h(-1)) and solubility (from 21.72 mg/L to 30.41 mg/L) was observed, depending on alcohol type and concentration. Among all alcohols, 1-propanol exhibited largest enhancement via bubble coalescence inhibition effect. Enhanced methane-water kLa and methane solubility in aqueous solution were employed for the fermentation of Methylosinus trichosporium OB3b, and cell growth rate and maximum optical density were increased by 700% and 730%, respectively, by addition of 1-propanol. (C) 2016 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
Citation - Scopus: 19
Polymeric and Small-Molecule Semiconductors for Organic Field-Effect Transistors
(wiley, 2015) Usta, Hakan; Facchetti, A. F.
This chapter reviews the achievements in the development of molecular and polymeric semiconductors for charge transport in thin-film transistors (TFTs). In particular, it introduces the basic concepts of organic semiconductor structure and organic thin-film transistor (OTFT) operation and then focuses on initial studies and works. Organic semiconductors for OTFTs must possess two essential structural features for their successful implementation in printed electronics. The first feature is a π-conjugated core/chain composed of linked unsaturated units. The second feature is core functionalization with solubilizing substituents, which is essential for inexpensive manufacture by solution methods as well as for enhancing solid-state core interactions. There are several advantages in using polymeric versus molecular p-conjugated semiconductors. Isoindigo has become a popular conjugated moiety in polymer semiconductor design because of its strong electron-withdrawing character. Polymeric p-channel TFTs have reached new heights, with hole mobilities unthinkable only few years back and surpassing 10 cm2V-1 s-1. © 2018 Elsevier B.V., All rights reserved.
Citation - WoS: 11
Citation - Scopus: 11
Logarithmic Organic Photodetectors
(Elsevier Science SA, 2015) Elgazzar, Elsayed; Ozdemir, Mehmet; Usta, Hakan; Al-Ghamdi, Ahmed A.; Dere, A.; El-Tantawy, Farid; Yakuphanoglu, F.
A novel photodetector of Al/GO:C8-BTBT/n-Si/Au with various graphene oxide (GO) contents has been investigated. The electrical properties of the diodes were characterized by current-voltage (I-V) and capacitance-voltage (C-V) measurements. The values of barrier height, ideality factor, and series resistance of the diodes were determined from I-V characteristic curves by using Norde's equations. The photocurrent properties of the diode were studied under various illumination intensities. The photoconducting mechanism of the diodes is controlled by the traps. The photoresponse properties of the diodes are increased with GO contents. The obtained results indicate that graphene oxide doped 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene/n-Si heterojunctions can be used as a photodetector for optoelectronic applications. (C) 2015 Elsevier B.V. All rights reserved.
Yüksek Performanslı Organik Transistörler ve Güneş Pilleri Uygulamaları için Yeni Yarı İletken Malzemeler
(Abdullah Gül Üniversitesi, Fen Bilimleri Enstitüsü, 2022) Can, Ayşe; Usta, Hakan
In the first chapter, we review the historical and recent advances in the design and implementation of indenofluorene (IF)-based semiconductors in organic transistor and solar cell devices. In the second chapter, a series of n-type ambient-stable and solution- processable TIFDMT-based semiconducting molecules, β,β'-C8-TIFDMT, β,β'-C12- TIFDMT, and β,β'-C16-TIFDMT are reported. By utilizing alkyl chain engineering in TIFDMT-based molecules and semiconductor-dielectric interface engineering through PS-brush treatment onto the dielectric surface in their OFET devices, we optimize the semiconductors' morphologies and thin-film molecular packing motifs to attain high- performance OFETs. The PS-brush treated OFETs demonstrate high device performance with μe = 0.9 cm2/V.s and Ion/Ioff ratio = 107-108. In the third chapter, we demonstrate the design, synthesis, and characterizations of two novel meso-π-extended/-deficient BODIPY building blocks (2OD-T2BDY and 2OD-TTzBDY), a library of low band gap (Eg = 1.30-1.35 eV) donor-acceptor copolymers based on these building blocks, and the utilization of the D-A copolymers as donor materials in the bulk heterojunction organic photovoltaics. Power conversion efficiencies of up to 4.4% with a short-circuit current of 12.07 mA cm-2 are achieved. The findings of this thesis on molecular engineering and optoelectronic properties are unique and may provide critical insights into the future development of high performance materials for unconventional optoelectronics.
Citation - WoS: 13
Citation - Scopus: 13
The Hansen Solubility Approach Towards Green Solvent Processing: N-Channel Organic Field-Effect Transistors Under Ambient Conditions
(Royal Soc Chemistry, 2024) Deneme, Ibrahim; Yildiz, Tevhide Ayca; 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, 2,2' -(2,8-bis(3-dodecylthiophen-2-yl)indeno[1,2-b]fluorene-6,12-diylidene)dimalononitrile (beta,beta'-C-12-TIFDMT), and to analyze potential green solvents for thin-film processing. The Hansen solubility parameters were determined to be delta(D) = 20.8 MPa1/2, delta(P) = 5.8 MPa1/2, and delta(H) = 5.5 MPa1/2 with a radius (R-0) 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 (R-a's = 5.17-7.93 MPa1/2 < R-0). 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 (Delta H-fus) and melting temperature (T-mp) 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 mu es reaching similar to 0.2 cm(2) V-1 s(-1) (I-on/I-off similar to 10(6)-10(7) and V-on similar to 0-5 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.
Citation - WoS: 31
Citation - Scopus: 32
Naphthalene Diimide-Based Polymeric Semiconductors. Effect of Chlorine Incorporation and N-Channel Transistors Operating in Water
(Springer Heidelberg, 2016) Ryu, Gi-Seong; Chen, Zhihua; Usta, Hakan; Noh, Yong-Young; Facchetti, Antonio
We demonstrate here the design, synthesis and characterization of two new chlorinated polymers, P(NDI2HD-T2Cl2) and P(NDI2OD-T2Cl2) based on N,N-difunctionalized naphthalene diimide (NDI) and 3,3-dichloro-2,2-bithiophene (T2Cl2) moieties. Our results indicate that organic thin-film transistors (OTFTs) based on these new chlorinated polymers exhibit electron mobilities approaching 0.1 cm(2)V(-1)s(-1) (I-on:I-off similar to 10(6)-10(7)), with far less ambipolarity due to their lower highest occupied molecular orbital energies, and they are more stable under deleterious high-humidity conditions (RH similar to 60%) and upon submersion in water, compared with those fabricated with the parent non-chlorinated polymers. In addition, OTFTs fabricated with the new chlorinated polymers exhibit excellent operational stabilities with <3% degradations upon bias-stress test.
Citation - WoS: 20
Citation - Scopus: 20
Enhancement of Anhydrous Proton Conductivity of Poly(Vinylphosphonic Acid)-Poly(2,5 Membranes Via in Situ Polymerization
(Wiley-VCH Verlag GmbH, 2015) Sen, Unal; Usta, Hakan; Acar, Oktay; Citir, Murat; Canlier, Ali; Bozkurt, Ayhan; Ata, Ali
Polymer electrolyte membranes (PEMs) are synthesized via in situ polymerization of vinylphosphonic acid (VPA) within a poly(2,5-benzimidazole) (ABPBI) matrix. The characterization of the membranes is carried out by using Fourier transform infrared (FTIR) spectroscopy for the interpolymer interactions, thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) for the thermal properties, and scanning electron microscopy (SEM) for the morphological properties. The physicochemical characterizations suggest the complexation between ABPBI and PVPA and the formation of homogeneous polymer blends. Proton conductivities in the anhydrous state (150 degrees C) measured by using impedance spectroscopy are considerable, at up to 0.001 and 0.002 S cm(-1) for (1: 1) and (1: 2) molar ratios, respectively. These conductivities indicate signifi cant improvements (> 1000x) over the physically blended samples. The results shown here demonstrate the great potential of in situ preparation for the realization of new PEM materials in future high-temperature and non-humidified polymer electrolyte membrane fuel cell (PEMFC) applications.
Citation - WoS: 83
Citation - Scopus: 78
Organic Light-Emitting Physically Unclonable Functions
(Wiley-VCH Verlag GmbH, 2022) Kayaci, Nilgun; Ozdemir, Resul; Kalay, Mustafa; Kiremitler, N. Burak; Usta, Hakan; Onses, M. Serdar
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.
Citation - WoS: 12
Citation - Scopus: 14
Insights Into Interface Treatments in P-Channel Organic Thin-Film Transistors Based on a Novel Molecular Semiconductor
(IEEE-Inst Electrical Electronics Engineers Inc, 2017) Liguori, Rosalba; Usta, Hakan; Fusco, Sandra; Facchetti, Antonio; Licciardo, Gian Domenico; Di Benedetto, Luigi; Rubino, Alfredo
Organic thin-film transistors (OTFTs) were fabricated using a novel small molecule, C6-NTTN, as the semiconductor layer in several different architectures. The C6-NTTN layer was deposited via both vacuum evaporation at different substrate temperatures and via solution-processing, which yield maximum hole mobilities of 0.16 and 0.05 cm(2)/V . s, respectively. Surface treatments of the substrate, insulator, and metal contacts used for OTFT fabrication employing polymer films and different self-assembled monolayers were investigated. In particular, in bottom-gate devices, the insulator surface hydrophobicity was optimized by the deposition of poly(methyl methacrylate) or hexamethyldisilazane, while in the top-gate geometry, pentafluorobenzenethiol was efficiently used to modify the substrate surface energy and to change the contact work function. Atomic force microscopy analysis was exploited to understand the relationship between the semiconductor thin-film morphology and the device electrical performance. The results shown here indicate an inverse proportionality between the mobility and the interface trap density, with parameters depending especially on semiconductor-insulator interfacial properties, and a correlation between the threshold voltage and the characteristics of the semiconductor-metal interface.
Organic Semiconductor Based Surface-Enhanced Raman Spectroscopy Platforms
(Amer Chemical Soc, 2018) Demirel, Gokhan; Usta, Hakan; Facchetti, Antonio
Hibrit Kuantum Noktacık-Nanofiber Esnek Elektrolüminesant Aygıtlar
(TUBİTAK, 2019) Mutlugün, Evren; Usta, Hakan; Önses, Serdar
Yarı iletken kuantum noktacıklar üstün renk dönüşüm özellikleri, yüksek soğurma katsayıları_x000D_ ve kararlılıkları sebebiyle son yıllarda aydınlatma ve ekran teknolojileri için oldukça önemli_x000D_ malzemeler durumundadır. Genel itibariyle II-VI ve III-V malzemeler temelli kuantum_x000D_ noktacıklar, optik ya da elektriksel olarak uyarılma sayesinde yüksek verimlilikle ışık üretimi_x000D_ sağlamaktadırlar. Sahip oldukları spektral dar ışımaları sayesinde özellikle ekran teknolojileri_x000D_ için saf renk özelliklerini ön plana çıkaran kuantum noktacıklar, geleneksel olarak kullanılan_x000D_ fosfor katkılı ışıyıcıların yerini almaktadır. Renk saflığının oldukça ön planda olduğu ekran_x000D_ teknolojileri için de kuantum noktalar LCD arka plan aydınlatmada üstün nitelikli beyaz ışık_x000D_ üretimini sağlamak için kullanılmakta ve ticari açıdan da önem kazanmaktadır._x000D_ Nanofiberler ise organik yarıiletken malzemelerin optoelektronik uygulamalarda 3 boyutlu_x000D_ alanlar için önerdiği yüksek verimlilik, hafiflik, geniş alanlara uygulanabilme özelliklerini fiziksel_x000D_ olarak 1 boyutta gerçekleştirebilen, desenlenebilir ve elektroeğirme yöntemi ile farklı yüzeylere_x000D_ uygulanabilir çözümler sunmaktadır._x000D_ Gerçekleştirdiğimiz proje nano boyutlu fiber yapıları içerisinde kuantum noktaların üstün renk_x000D_ dönüştürücü özelliklerini ön plana çıkarmış, farklı mimarilerde enerji transferinin de çalışıldığı_x000D_ fotolüminesans ve elektrolüminesans temelli aygıtlar gerçekleştirilmiştir. Bu projede %16’ya_x000D_ ulaşan dış kuantum verimliliğine (external quantum efficiency) sahip aygıt gösterimleri ve_x000D_ yüksek kaliteli beyaz ışık eldesi gerçekleştirilmiştir. Aynı zamanda esnek, ayarlanabilir renk_x000D_ özelliklerinde aygıt üretimi için gösterilen kuantum nokta aygıtlar saf ve spektral olarak simetrik_x000D_ ışımayı sağlama yetisinde, üstün renk özellikleri ile yüksek kaliteli esnek elektrolüminesant_x000D_ aygıt üretimini mümkün kılmaktadır._x000D_ Önümüzdeki 10 yıl içerisinde küresel ekran teknolojileri pazarının 100 milyar dolarlar_x000D_ mertebesine ulaşacağı bilgisi doğrultusunda (Global Industry Analysts, Inc., raporu) en önemli_x000D_ aşamalardan biri de özellikle esnek mimarilerde üstün renk özelliklerine sahip malzemeleri_x000D_ gerçekleştirmek olacaktır. Yeni nesil esnek elektrolüminesant aygıtların aydınlatma ve ekran_x000D_ teknolojilerinde önemli bir paya sahip olacağı beklenmektedir. Bu tür yeni nesil yapıların_x000D_ gerçekleştirilmesi, fiziksel mekanizmaların araştırılması ve teknolojik problemlerine çözüm_x000D_ üretilme süreci büyük resimde çok kritik önemdedir. Teknolojiye yön verme doğrultusunda_x000D_ önerilen proje ekseninde yapılacak olan yatırımın ülkemiz için yüksek teknoloji üretme_x000D_ hamlesine büyük bir katkıda bulunacağı, yeni bilgi, ürün ve patent süreçlerini geliştireceği,_x000D_ ülkemizde bu alanda yetişmiş insan gücüne katkıda bulunup ülkemiz rekabet gücünü_x000D_ arttıracağı öngörülmektedir.
Citation - WoS: 16
Citation - Scopus: 15
Engineering Functionalized Low LUMO [1]Benzothieno[3,2-B][1]Benzothiophenes (BTBTs): Unusual Molecular and Charge Transport Properties
(Royal Soc Chemistry, 2020) Ozdemir, Resul; Ahn, Kyunghan; Deneme, Ibrahim; Zorlu, Yunus; Kim, Dojun; Kim, Myung-Gil; Usta, Hakan
Diacene-fused thienothiophenes (DAcTTs) have provided an excellent pi-framework for the development of high mobility p-type molecular semiconductors in the past decade. However, n-type DAcTTs are rare and their electron transport characteristics remain largely unexplored. Herein, a series of functionalized low LUMO (lowest unoccupied molecular orbital) [1]benzothieno[3,2-b][1]benzothiophene (BTBT)-based small molecules, D(C7CO)-BTBT, C7CO-BTBT-CC(CN)(2)C-7, and D(C7CC(CN)(2))-BTBT, have been developed. Detailed structural, physicochemical, optoelectronic, and single-crystal characterization were performed. The new molecules exhibit large optical band gaps (similar to 2.8-3.1 eV) and highly stabilized (-Delta E-LUMO = 1.2-1.4 eV)/pi-delocalized LUMOs as compared to p-type DAcTTs. Symmetric functionalization is found to be important to enable strong intermolecular interactions in the solid-state. All molecules exhibit alternately stacked layers of "F-BTBT-F" and "S" (F: functional group/S: substituent) with strong herringbone-like interactions (2.8-3.6 angstrom distances) between pi-cores. While carbonyls, regardless of the substituent, adopt nearly coplanar pi-backbones with BTBT, dicyanovinylenes are found to be twisted (47.5 degrees). The conformational difference at the molecular level has unusual effects on the pi-electron deficiencies, frontier molecular orbital energetics, thermal/photophysical properties, and pi-electronic structures. Dicyanovinylenes at the 2,7 positions, despite twisted conformations, are shown for the first time to yield good electron transport in DAcTTs. The D(C7CC(CN)(2))-BTBT thin film exhibits large 2D plate-like crystalline grains (similar to 1-2 mu m sizes) of terraced islands and becomes a rare example of an n-type DAcTT in organic field-effect transistors (OFETs). Although a stabilized/pi-delocalized LUMO, largely governed by functional groups and intramolecular twists, is essential for electron transport, our findings suggest that it should be combined with proper substituents to yield a favorable three-dimensional BTBT/functional group pi-electronic structure and a low intramolecular reorganization energy. Combined with our first n-type DAcTT semiconductor D(PhFCO)-BTBT, a molecular library with systematically varied chemical structures has been studied herein for the first time for low LUMO DAcTTs. The molecular engineering perspectives presented in this study may give unique insights into the design of novel electron transporting thienoacenes for unconventional optoelectronics.
Citation - WoS: 20
Citation - Scopus: 20
Frequency and Electric Field Controllable Photodevice: FYTRONIX Device
(Elsevier Science Bv, 2017) Tataroglu, A.; Al-Sehemi, Abdullah G.; Ozdemir, Mehmet; Ozdemir, Resul; Usta, Hakan; Al-Ghamdi, Ahmed A.; Yakuphanoglu, F.
Al/p-Si/BODIPY/Al diode was fabricated by forming BODIPY organic layer on p-Si having ohmic contact. The electrical and photoresponse properties of the prepared diode were investigated in detail. The current-voltage ( I-V) measurements were performed under dark and various illumination intensities. It is observed that the photocurrent under illumination is higher than the dark current. The transient measurements indicate that the device exhibits both photodiode and photocapacitor behavior. We called this device as FYTRONIX device. The photoresponse behavior of the FYTRONIX device is controlled simultaneously by frequency and electric field. The FYRONIX device can be used as a photoresponse sensor in optoelectronic applications.
Citation - WoS: 74
Citation - Scopus: 76
From 2-Methylimidazole to 1,2,3-Triazole: A Topological Transformation of ZIF-8 and ZIF-67 by Post-Synthetic Modification
(Royal Soc Chemistry, 2017) Erkartal, Mustafa; Erkilic, Ufuk; Tam, Benjamin; Usta, Hakan; Yazaydin, Ozgur; Hupp, Joseph T.; Sen, Unal
Bridging ligand replacement in zeolitic imidazolate frameworks, ZIF-8 and ZIF-67, by 1,2,3-triazole was investigated. A complete substitution of 2-methylimidazole by 1,2,3-triazole resulted in a topological transformation of the parent framework from a sodalite (SOD) network to a diamond (DIA) network.
Citation - WoS: 22
Citation - Scopus: 25
Revisiting the Role of Charge Transfer in the Emission Properties of Carborane-Fluorophore Systems: A TDDFT Investigation
(Amer Chemical Soc, 2022) Tahaoglu, Duygu; Usta, Hakan; Alkan, Fahri
In this study, we performed a detailed investigation of the S-1 potential energy surface (PES) of o-carborane-anthracene (o-CB-Ant) with respect to the C-C bond length on o-CB and the dihedral angle between o-CB and Ant moieties. The effects of different substituents (F, Cl, CN, and OH) on carbon- or boron-substituted o-CB, along with a pi-extended acene-based fluorophore, pentacene, on the nature and energetics of S-1 -> S-0 transitions are evaluated. Our results show the presence of a non-emissive S-1 state with an almost pure charge transfer (CT) character for all systems as a result of significant C-C bond elongation (C-C = 2.50-2.56 angstrom) on o-CB. In the case of unsubstituted o-CB-Ant, the adiabatic energy of this CT state corresponds to the global minimum on the S-1 PES, which suggests that the CT state could be involved in emission quenching. Despite large deformations on the o-CB geometry, predicted energy barriers are quite reasonable (0.3-0.4 eV), and the C-C bond elongation can even occur without a noticeable energy penalty for certain conformations. With substitution, it is shown that the dark CT state becomes even more energetically favorable when the substituent shows -M effects (e.g., -CN), whereas substituents showing +M effects (e.g., -OH) can result in an energy increase for the CT state, especially for partially stretched C-C bond lengths. It is also shown that the relative energy of the CT state on the PES depends strongly on the LUMO level of the fluorophore as this state is found to be energetically less favorable compared to other conformations when anthracene is replaced with pi-extended pentacene. To our knowledge, this study shows a unique example of a detailed theoretical analysis on the PES of the S-1 state in o-CB-fluorophore systems with respect to substituents or fluorophore energy levels. Our findings could guide future experimental work in emissive o-CB-fluorophore systems and their sensing/optoelectronic applications.
Citation - WoS: 40
Citation - Scopus: 40
Design, Synthesis, and Characterization of Α,ω-Disubstituted Indeno[1,2-B]Fluorene Molecular Semiconductors. Enhancement of Ambipolar Charge Transport Through Synthetic Tailoring of Alkyl Substituents
(Royal Soc Chemistry, 2016) Ozdemir, Mehmet; Choi, Donghee; Kwon, Guhyun; Zorlu, Yunus; Kim, Hyekyoung; Kim, Myung-Gil; Usta, Hakan
A series of indeno[1,2-b]fluorene-6,12-dione-thiophene derivatives with hydrocarbon substituents at alpha,omega-positions as side groups have been designed and synthesized. The new compounds were fully characterized by H-1/C-13 NMR, mass spectrometry, cyclic voltammetry, UV-vis absorption spectroscopy, differential scanning calorimetry, thermogravimetric analysis, and melting point measurements. The solid state structure of the indeno[1,2-b]fluorene-6,12-dione acceptor core has been identified based on single-crystal X-ray diffraction (XRD). The structural and electronic properties were also studied using density functional theory calculations, which were found to be in excellent agreement with the experimental findings and provided further insight. The detailed effects of alkyl chain size and orientation on the optoelectronic properties, intermolecular cohesive forces, thin-film microstructures, and charge transport performance of the new semiconductors were investigated. Two of the new solution-processable semiconductors, 2EH-TIFDKT and 2OD-TIFDKT, were deposited as thin-films via solution-shearing, drop-casting, and droplet-pinned crystallization methods, and their morphologies and microstructures were investigated by X-ray diffraction (XRD) and atomic force microscopy (AFM). The solution-processed thin-film transistors based on 2EH-TIFDKT and 2OD-TIFDKT showed ambipolar device operations with electron and hole mobilities as high as 0.12 cm(2) V-1 s(-1) and 0.02 cm(2) V-1 s(-1), respectively, with Ion/Ioff ratios of 105 to 106. Here, we demonstrate that rational repositioning of the b-substituents to molecular termini greatly benefits the p-core planarity while maintaining a good solubility, and results in favorable structural and optoelectronic characteristics for more efficient charge-transport in the solid-state. The ambipolar charge carrier mobilities were increased by two-three orders of magnitude in the new indeno[1,2-b]fluorene-6,12-dione-thiophene core on account of the rational side-chain engineering.
Polymeric Semiconductors Based on Meso-Substituted BODIPY for (Opto)electronic Applications
(Amer Chemical Soc, 2019) Usta, Hakan; Kim, Choongik; Kim, Bumjoon
Citation - WoS: 38
Citation - Scopus: 39
A New Rod-Shaped Bodipy-Acetylene Molecule for Solution-Processed Semiconducting Microribbons in N-Channel Organic Field-Effect Transistors
(Royal Soc Chemistry, 2017) Ozdemir, Mehmet; Choi, Donghee; Zorlu, Yunus; Cosut, Bunyemin; Kim, Hyungsug; Kim, Choongik; Usta, Hakan
BODIPY-based pi-conjugated small molecules have been extensively studied in various fields of sensing and biochemical labelling; however, their use in organic optoelectronic applications is very limited. A new solution-processable acceptor-donor-acceptor (A-D-A) type small molecule, BDY-PhAc-BDY, consisting of BODIPY pi-acceptors and a rod-shaped 1,4-bis-(thienylethynyl) 2,5-dialkoxybenzene pi-donor, has been synthesized and fully characterized as a novel n-channel semiconductor in bottom-gate/top-contact organic field-effect transistors (OFETs). The new semiconductor exhibits an electrochemical band gap of 2.12 eV with highly stabilized HOMO/LUMO energy levels of -5.68 eV/-3.56 eV. Single-crystal X-ray diffraction (XRD) analysis of BDY-PhAc-BDY reveals a relatively low "BODIPY-meso-thiophene" dihedral angle (theta = 44.94 degrees), antiparallel pi-stacked BODIPY dimers with an interplanar distance of 3.93 angstrom, and strong "C-H center dot center dot center dot pi (2.85 angstrom)" interactions. The OFET devices fabricated by solution processing show the formation of highly-crystalline, one-dimensional (1-D) microribbons, which results in clear n-channel semiconductivity with an electron mobility of 0.004 cm(2) V-1 s(-1) and an on/off current ratio of 10(5)-10(6). To date, this is the highest reported for BODIPY-based small molecular semiconductors with alkyne linkages. Our results clearly demonstrate that BODIPY is an effective pi-acceptor unit for the design of solution-processable, electron-transporting organic semiconductors and easily fabricable 1-D semiconductor micro-/nano-structures for fundamental/applied research in organic optoelectronics.