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Dr. Claudiu CIOBOTARU

Scientific Researcher III

Laboratory of Functional Nanostructures

claudiu[DOT]ciobotaru[AT]infim[DOT]ro

Publications

1. Organic Light-Emitting Diodes with Electrospun Electrodes for Double-Side Emissions
Authors: Ciobotaru, IC; Enculescu, M; Polosan, S; Enculescu, I; Ciobotaru, CC

Published: MAR 2023, MICROMACHINES, 14, 543, DOI: 10.3390/mi14030543

Transparent conductive electrodes (TCE) obtained by the electrospinning method and gold covered were used as cathodes in the organic light-emitting diodes (OLEDs) to create double side-emission. The electro-active nanofibers of poly(methyl methacrylate) (PMMA) with diameters in the range of several hundreds of nanometers, were prepared through the electrospinning method. The nanofibers were coated with gold by sputtering deposition, maintaining optimal transparency and conductivity to increase the electroluminescence on both electrodes. Optical, structural, and electrical measurements of the as-prepared transparent electrodes have shown good transparency and higher electrical conductivity. In this study, two types of OLEDs consisting of indium tin oxide (ITO)/ poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT-PSS)/ Ir(III) complex (8-hydroxyquinolinat bis(2-phenylpyridyl) iridium-IrQ(ppy)(2) 20 wt% embedded in N, N '-Dicarbazolyl-4,4 '-biphenyl (CBP) sandwich structure and either gold-covered PMMA electrospun nanoweb (OLED with electrospun cathode) were fabricated together with a similar structure containing thin film gold cathodes (OLED with thin film cathode). The luminance-current-voltage characteristics, the capacitance-voltage, and the electroluminescence properties of these OLEDs were investigated.
2. Low-Cost Plant-Based Metal and Metal Oxide Nanoparticle Synthesis and Their Use in Optical and Electrochemical (Bio)Sensors
Authors: Ciobotaru, IC; Oprea, D; Ciobotaru, CC; Enache, TA

Published: DEC 2023, BIOSENSORS-BASEL, 13, 1031, DOI: 10.3390/bios13121031

Technological progress has led to the development of analytical tools that promise a huge socio-economic impact on our daily lives and an improved quality of life for all. The use of plant extract synthesized nanoparticles in the development and fabrication of optical or electrochemical (bio)sensors presents major advantages. Besides their low-cost fabrication and scalability, these nanoparticles may have a dual role, serving as a transducer component and as a recognition element, the latter requiring their functionalization with specific components. Different approaches, such as surface modification techniques to facilitate precise biomolecule attachment, thereby augmenting recognition capabilities, or fine tuning functional groups on nanoparticle surfaces are preferred for ensuring stable biomolecule conjugation while preserving bioactivity. Size optimization, maximizing surface area, and tailored nanoparticle shapes increase the potential for robust interactions and enhance the transduction. This article specifically aims to illustrate the adaptability and effectiveness of these biosensing platforms in identifying precise biological targets along with their far-reaching implications across various domains, spanning healthcare diagnostics, environmental monitoring, and diverse bioanalytical fields. By exploring these applications, the article highlights the significance of prioritizing the use of natural resources for nanoparticle synthesis. This emphasis aligns with the worldwide goal of envisioning sustainable and customized biosensing solutions, emphasizing heightened sensitivity and selectivity.
3. Charge transport mechanisms in free-standing devices with electrospun electrodes
Authors: Ciobotaru, IC; Polosan, S; Enculescu, M; Nitescu, A; Enculescu, I; Beregoi, M; Ciobotaru, CC

Published: SEP 24 2022, NANOTECHNOLOGY, 33, 395203, DOI: 10.1088/1361-6528/ac7ac1

Embedding electronic and optoelectronic devices in common, daily use objects is a fast developing field of research. New architectures are needed for migrating from the classic wafer- based substrates. Novel types of flexible PMMA/Au/Alq(3)/LiF/Al structures were obtained starting from electrospun polymer fibers. Thus, using an electrospinning process poly (methyl metacrylate) (PMMA) nanofibers were fabricated. A thin Au layer deposition rendered the fiber array conductive, this being further employed as the anode. The next steps consisted of the thermal evaporation of tris(8-hydroxyquinolinato) aluminum (Alq(3)) and aluminum deposition as the cathode. The Au covered PMMA nanofiber layer had a similar behavior with an indium tin oxide film i.e. low sheet resistance 10.6 omega/sq and high transparency. The low electrode resistivities allow an electron drift mobility of about 10(-6) cm(2) V-1 s(-1) at a low applied field, similar to the counterpart structures based on thin films. Concerning the relaxation processes in these structures, the Cole-Cole plots exhibit a slightly deformed semicircle, indicating a more complex equivalent circuit for the processes between metal electrodes and the active layer. This equivalent circuit includes reactance equivalent processes at the anode, cathode, in the active layer and most probably originates from the roughness of the metallic electrodes.
4. Highly Conductive Carbon-Based Thin Films Produced by Low-Energy Electron Irradiation
Authors: Ciobotaru, CC; Ciobotaru, IC; Iosub, DG; Polosan, S

Published: OCT 2021, JOURNAL OF ELECTRONIC MATERIALS, 50, 5541, DOI: 10.1007/s11664-021-09058-5

Highly conductive carbon-based thin films have been produced by low-energy electron irradiation. Low-energy electron irradiation at a lower density of electrons eliminates the sp(3) hybridization of the carbon atoms by reducing the chemical groups on the surface. Irradiated carbon-based thin films became highly conductive layers that could be used as electrodes for optoelectronic devices. The electrical conductivity sigma reached 3 x 10(4) S/m in the case of samples irradiated at a lower density, with a mean value between 3 x 10(5) S/m and 3.3 x 10(2) S/m for highly crystalline graphite structures. The increasing (002) peak diffraction and decreasing intensity ratio ID/IG in the Raman spectra as well as the decreasing bandgap in photoluminescence measurements demonstrated the reduction of oxygen-induced defects in these thin films.
5. Detailed Molecular and Structural Analysis of Dual Emitter IrQ(ppy)(2) Complex
Authors: Ciobotaru, IC; Crisan, DN; Sket, P; Ciobotaru, CC; Polosan, S

Published: APR 2020, MATERIALS, 13, DOI: 10.3390/ma13071617

The molecular structure of the 8-hydroxyquinoline-bis (2-phenylpyridyl) iridium (IrQ(ppy)(2)) dual emitter organometallic compound is determined based on detailed 1D and 2D nuclear magnetic resonance (NMR), to identify metal-ligands coordination, isomerization and chemical yield of the desired compound. Meanwhile, the extended X-ray absorption fine structure (EXAFS) was used to determine the interatomic distances around the iridium ion. From the NMR results, this compound IrQ(ppy)(2) exhibits a trans isomerization with a distribution of coordinated N-atoms in a similar way to facial Ir(ppy)(3). The EXAFS measurements confirm the structural model of the IrQ(ppy)(2) compound where the oxygen atoms from the quinoline ligands induce the splitting of the next-nearest neighboring C in the second shell of the Ir3+ ions. The high-performance liquid chromatography (HPLC), as a part of the detailed molecular analysis, confirms the purity of the desired IrQ(ppy)(2) organometallic compound as being more than 95%, together with the progress of the chemical reactions towards the final compound. The theoretical model of the IrQ(ppy)(2), concerning the expected bond lengths, is compared with the structural model from the EXAFS and XRD measurements.
6. Organometallic Coatings for Electroluminescence Applications
Authors: Polosan, S; Ciobotaru, IC; Ciobotaru, CC

Published: MAR 2020, COATINGS, 10, DOI: 10.3390/coatings10030277

Organometallic compounds embedded in thin films are widely used for Organic Light-Emitting Diodes (OLED), but their functionalities are strongly correlated with the intrinsic properties of those films. Controlling the concentration of the organometallics in the active layers influences the OLED performances through the aggregation processes. These aggregations could lead to crystallization processes that significantly modify the efficiency of light emission in the case of electroluminescent devices. For functional devices with organometallic-based thin films, some improvements, such as the optimization of the charge injection, are needed to increase the light output. One dual emitter IrQ(ppy)2 organometallic compound was chosen for the aggregation correlations from a multitude of macromolecular organometallics that exist on the market for OLED applications. The choice of additional layers like conductive polymers or small molecules as host for the active layer may significantly influence the performances of the OLED based on the IrQ(ppy)2 organometallic compound. The use of the CBP small molecule layer may lead to an increase in the electroluminescence versus the applied voltage.
7. Charge Transfer from Alq(3)-5Cl to Graphene Oxide in Donor-Acceptor Heterostructures
Authors: Polosan, S; Ciobotaru, CC; Ciobotaru, IC

Published: NOV 2019, JOURNAL OF ELECTRONIC MATERIALS, 48, DOI: 10.1007/s11664-019-07531-w

This paper describes an alternative active layer for the solar cells based on the organometallic compounds in two configurations: bulk heterojunction and donor/acceptor junction between the organometallic compounds as the electron donor and carbon-based layer as the electron acceptor. Both configurations depend on the band alignment which ensures optimal charge transport towards electrodes in the sandwich structures of these active layers, but the optimization also depends by the exciton diffusion length which limits the thicknesses of the active layer. In the bulk heterojunctions, the exciton diffusion length could be extended to 100 nm which allows a better efficiency then bilayer structures. The photoconductive behaviors of these two configurations have shown the superiority of the bulk heterojunctions, increasing the intensity of the measured photocurrent. The redshift of the photoluminescence of Alq3-5Cl in the bulk heterojunctions reveals a better charge transfer towards the acceptor layer, in this case, formed from graphene oxide. The alternative of organometallic compounds as donor materials ensures a better thermal and chemical stability compared with other organic materials like perovskites.
8. Organometallic compounds for photovoltaic applications
Authors: Ciobotaru, IC; Polosan, S; Ciobotaru, CC

Published: NOV 1 2018, INORGANICA CHIMICA ACTA, 483, 453, DOI: 10.1016/j.ica.2018.08.042

Organometallic compounds could be an excellent alternative to the organic active layers for solar cells due to several better properties like thermal and chemical stability. These organometallic compounds are electron donor materials which are easily used in donor-acceptor heterojunctions in these solar cells. One of the main problems for the active media in the solar cells is connected with the exciton diffusion length which limits the thickness of the donor layer in these donor-acceptor heterojunctions. A way to improve the exciton diffusion length is better charge transfer between the donor and acceptor facilitating the exciton diffusion towards the electrodes of the solar cells. The adding of electronegative ions or chemical groups could also influence the band alignment between the donor and acceptor smoothing the charge transport across the solar cells.
9. Electroluminescence Properties of IrQ(ppy)(2) Dual-Emitter Organometallic Compound in Organic Light-Emitting Devices
Authors: Ciobotaru, CC; Polosan, S; Ciobotaru, IC

Published: FEB 2018, JOURNAL OF ELECTRONIC MATERIALS, 47, 1496, DOI: 10.1007/s11664-017-5945-3

This paper reports the influence of the charge carrier mobility on the electroluminescent properties of a dual-emitter organometallic compound dispersed in two conjugated organic small-molecule host materials and embedded in organic light-emitting devices (OLEDs). The electroluminescent processes in OLEDs are strongly influenced by the host-guest interaction. The charge carrier mobility in the host material plays an important role in the electroluminescent processes but also depends on the triplet-triplet interaction with the organometallic compound. The low charge carrier mobility in 4,4'-bis(N-carbazolyl)-1,1'-biphenyl (CBP) host material reduces the electroluminescent processes, but they are slightly enhanced by the triplet-triplet exothermic charge transfer. The higher charge carrier mobility in the case of N, N'-bis(3-methylphenyl)-N, N'-diphenylbenzidine (TPD) host material influences the electroluminescent processes by the endothermic energy transfer at room temperature, which facilitates the triplet-triplet harvesting in the host-guest system. The excitation is transferred to the guest molecules by triplet-triplet interaction as a Dexter transfer, which occurs by endothermic transfer from the triplet exciton in the host to the triplet exciton in the guest.
10. Crystallization properties of IrQ(ppy)(2) organometallic complex films
Authors: Polosan, S; Ciobotaru, CC; Ciobotaru, IC; Tsuboi, T

Published: MAY 2017, JOURNAL OF MATERIALS RESEARCH, 32, 1740, DOI: 10.1557/jmr.2017.155

Comparative studies between doped conducting polymers and electrochemical deposited organometallic compounds reveals the interplay between crystalline-amorphous phases with significant contributions to the internal quantum efficiency in the OLED devices. The coexistence of the amorphous and crystalline phase in the electrodeposited film is revealed by the minor micro-crystal products which are present in the amorphous phase in thin films, while the many micro-crystals are randomly distributed in the thick films. Concerning the doped conducting polymers, the level of doping induces crystalline effects as a result of the - stacking between molecules, due to the Forester energy transfer processes in which the transfer rate is increased with decreasing of the distances between neighboring molecules. The crystallization processes change the emission properties of the active layers both for the luminance level and all over color, ranging from yellow to red in the case of IrQ(ppy)(2) compounds.
11. Enhancement of the electroluminescence of organic light emitting devices based on Ir(ppy)(3) by doping with metallic and magnetic nanoparticles
Authors: Ciobotaru, CC; Ciobotaru, IC; Schinteie, G; Negrea, R; Polosan, S

Published: DEC 2017, MATERIALS SCIENCE IN SEMICONDUCTOR PROCESSING, 72, 84, DOI: 10.1016/j.mssp.2017.09.019

Magnetic nanoparticles embedded in the active layer of the Organic Light Emitting Diodes (OLEDs) significantly increases the electroluminescence and the charge transport without influencing the transparency of these devices. A brief comparison was done in order to identify which parameter influences these properties, by comparing the CoFe2O4 magnetic nanoparticles with CoFe2 metallic magnetic nanoparticles, the latter one being obtained by thermal reduction in hydrogen of cobalt ferrite nanoparticles. CoFe2 have shown a better efficiency of the metallic nanoparticles where probably the main advantage is the higher magnetization property instead of the coercive field. Concerning the charge transport across the OLEDs, these nanoparticles reduce the electron injection, acting as filling traps, which directly increases the electroluminescence and the current at the same voltage.
12. Templateless electrodeposition ZnO nanowires for charge transport optimization in OLED structures
Authors: Polosan, S; Matei, E; Ciobotaru, IC; Ciobotaru, CC

Published: OCT 2016, MATERIALS RESEARCH EXPRESS, 3, DOI: 10.1088/2053-1591/3/10/105018

Passivated zinc oxide nanowires (NW) were used to improve the charge injection in organic lightemitting diode (OLED) structures. Conducting polymers, deposited on the well-dispersed ZnO NW, were used to modify the electrical conductivity across the OLED structure because the charge transport is influenced by the interface interactions. Passivation with polymers improves the transport characteristics of the device due to the interaction between ZnONWand PEDOT:PSS polymer. The hole current density increases with the ZnO NW concentration, which made the current injection more balanced and therefore enhanced the electroluminescence efficiency. A templateless electrochemical deposition method was used to grow zinc oxide nanowires on an ITO/glass substrate because parameters such as the densities and dimensions of the nanowires can be controlled to produce thin and well dispersed structures.
13. Structural characteristics of iridium dual-emitter organometallic compound
Authors: Polosan, S; Ciobotaru, IC; Enculescu, I; Ciobotaru, CC

Published: DEC 14 2014, JOURNAL OF MATERIALS RESEARCH, 29, 2904, DOI: 10.1557/jmr.2014.337

By combining two types of ligands, phenylpyridine and quinoline, a new type of organometallic IrQ(ppy)(2) compound has been synthesized, which exhibits two phosphorescences: green and red. Using an appropriate catalyst, the final IrQ(ppy)(2) compound has a good chemical yield up to 60% and becomes a stable dual emitter at room temperature. This compound is important because it exhibits stable red emission which is limited by the quantum yield due to the low energy band gap. As a result, an overlap between the ground state and the excited state occurs due to the vibrations that increase the nonradiative transitions, destroying the red emissions. Structural characteristics of the IrQ(ppy)(2) powder reveal a triclinic structure confirmed by x-ray diffraction and scanning electron microscopy images. Thermal analysis of the final compound confirms a good stability against decomposition and structural changes up to 350 degrees C. X-ray photoelectron spectroscopy reveals Ir-O chemical bonds and several differences between the intermediate and final compounds, such as Ir-Cl bonds. Cathodoluminescence patterns show a phosphorescent triclinic structure with a higher efficiency for the red color. Backscattering electron images prove that there is a uniform distribution of iridium ions in the IrQ(ppy)(2) nanocrystals.
14. Covalent Functionalization of Graphene Oxide with Cisplatin
Authors: Ciobotaru, CC; Damian, CM; Matei, E; Iovu, H

Published: MAR 2014, MATERIALE PLASTICE, 51, 80, DOI:

The objective of this study was to obtain graphene oxide starting from graphite and to covalently functionalize this nanomaterial with Cisplatin. The presence of the drug was pointed out using different methods like FTIR Spectroscopy, X-Ray Photoelectron Spectroscopy (XPS), Thermogravimetric analysis (TGA), RAMAN Spectroscopy, X-Ray Diffraction and Scanning electron microscopy (SEM).
15. COVALENT FUNCTIONALIZATION OF SINGLE WALLED CARBON NANOTUBES WITH DOXORUBICIN FOR CONTROLLED DRUG DELIVERY SYSTEMS
Authors: Ciobotaru, CC; Damian, CM; Polosan, S; Matei, E; Iovu, H

Published: JAN-MAR 2014, DIGEST JOURNAL OF NANOMATERIALS AND BIOSTRUCTURES, 9, 422, DOI:

The objective of this study was to obtain nanocomposites based on SWCNTs functionalized with carboxyl groups and doxorubicin (DOX) as a chemotherapeutic drug through covalent bonds formed by carboxyl groups from SWCNTs and amino groups from DOX. The formation of these nanocomposites was proved by using different characterization methods like Fourier transform Infrared spectroscopy and X-ray photoelectron spectroscopy (XPS). Also thermogravimetrical analysis was employed to study the thermal behavior of our nanocomposites. X-ray diffraction and Raman spectroscopy revealed that the surface was modified by the covalent bonding of DOX to SWCNTs. The in vitro drug release was studied by using UV-VIS Spectroscopy.
16. DRUG DELIVERY STUDY OF SINGLE-WALL CARBON NANOTUBES COVALENT FUNCTIONALIZED WITH CISPLATIN
Authors: Ciobotaru, CC; Damian, CM; Polosan, S; Prodana, M; Iovu, H

Published: APR-JUN 2014, DIGEST JOURNAL OF NANOMATERIALS AND BIOSTRUCTURES, 9, 868, DOI:

Carbon nanotubes are widely studied components for drug delivery systems due to their high surface area and low chemical reactivity. The research presented in this paper deals with the synthesis of drug delivery systems based on single walled carbon nanotubes (SWCNTs) and the well-known cancer treatment drug Cisplatin. The new nanomaterials obtained through covalent bonding between carboxyl groups from the SWCNTs surface and amino groups from the Cisplatin structure were characterized from structural point of view. To evaluate the content of drug released the Inductively Coupled Plasma Mass Spectrometry (ICP-MS) was employed. The releasing profile shows a slow rate in the beginning followed by a spectacular increase after 180 minutes which means that this type of system could be used for prolonged release.
17. Embedding of IrQ(ppy)(2) organometallic compounds in polypyrrole conducting polymer for OLED's applications
Authors: Ciobotaru, IC; Matei, E; Ciobotaru, CC; Polosan, S

Published: DEC 2014, SYNTHETIC METALS, 198, 328, DOI: 10.1016/j.synthmet.2014.10.041

Conducting polypyrrole:IrQ(ppy)(2) thin films were obtained by electrochemical method which ensure uniform dispersion of the organometallic in the polymer matrix. A thin layer of about 50 nm polypyrrole: IrQ(pPY)(2) thin films were deposited on the ITO/glass substrate and used for spectroscopic, structural, and electric characterization. The photoluminescence spectrum of polypyrrole:IrQ.(ppy)2 have shown the two main emissions of IrQ(ppy)(2) at 2.44 eV (508 nm) and 2 eV (620 nm) besides of the polypyrrole weak emission centered at 2.55 eV (485 nm). The electric conductivity of the doped polypyrrole thin layer has almost the same conductivity with the undoped polypyrrole thin film suggesting an homogenous polypyrrole:IrQ(ppy)(2) composite which can be used as emissive layer in the OLED's structures. (C) 2014 Elsevier B.V. All rights reserved.
18. Dual emitter IrQ(ppy)(2) for OLED applications: Synthesis and spectroscopic analysis
Authors: Ciobotaru, IC; Polosan, S; Ciobotaru, CC

Published: JAN 2014, JOURNAL OF LUMINESCENCE, 145, 262, DOI: 10.1016/j.jlumin.2013.07.067

The synthesis of organometallic compound with iridium and two types of ligands, quinoline and phenylpyridine, was done successfully. The absorption spectra of this compound have shown broad peaks in a visible region assigned to metal-to-ligands charge transfer and in UV region assigned to intraligand absorptions. The photoluminescence spectra exhibit dual character in which the red emission is more intense than the green one. In cathodoluminescence measurements, under electron beam, the powder obtained after recrystallization from dichloromethane, shows similar behaviors with photoluminescence spectra. The cathodoluminescence images have shown a luminescent crystalline powder with triclinic structure. This compound exhibits combined vibrational modes, which proves the presence in the same molecule of both ligands. Density Functional Theory calculation was involved in order to identify the main vibrations of this compound. (C) 2013 Elsevier B.V. All rights reserved.
19. Highly Conductive Carbon-Based Thin Films Produced by Low-Energy Electron Irradiation
Authors: Ciobotaru, CC; Ciobotaru, IC; Iosub, DG; Polosan, S

Published: , JOURNAL OF ELECTRONIC MATERIALS, DOI: 10.1007/s11664-021-09058-5

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