NIMP| Andrei TOMULESCU, Author at NIMP

Resume

Andrei Gabriel C. Tomulescu, Assistant scientific researcher (since 2013), born in 1990, graduated the Faculty of Applied Chemistry and Materials Science (FCASM) – Section “Oxide Materials Science and Engineering, and Nanomaterials” at University Politehnica of Bucharest (UPB) (2013), has a MSc degree in Chemical Engineering − Section “Micro and Nanomaterials” (UPB) (2015). Work experience: National Institute of Materials Physics (NIMP) (2013 – to date); work stage at the Linz Institute for Organic Solar Cells, JKU University, Austria. Main areas of interest/expertise: preparation of oxide powders and ceramics with electric, ferroelectric and piezoelectric properties through classical and sol-gel methods, deposition of organic and inorganic thin films through spin-coating wet chemistry, spray coating and magnetron sputtering for device manufacturing, solar cell fabrication and electrical characterization. Publications (last updated November 2022): 13 articles published in Web of Science® (WoS) journals with impact factor (e.g., Appl. Surf. Sci.; ACS J. Phys. Chem. Letters; J. Mater. Sci.); Hirsch index (WoS): 6; Citations (without self-citations): 275, co-authored one book chapter (Elsevier publishing). Professional profile web-links: Brainmap: https://www.brainmap.ro/andrei-gabriel-tomulescu; ORCID ID: 0000-0002-3025-6854; WoS ResearcherID: B-8700-2019.

Publications

1. Partial Replacement of Dimethylformamide with Less Toxic Solvents in the Fabrication Process of Mixed-Halide Perovskite Films

Authors: Stancu, V; Tomulescu, AG; Leonat, LN; Balescu, LM; Galca, AC; Toma, V; Besleaga, C; Derbali, S; Pintilie, I

Published: FEB 2023, COATINGS, 13, 378, DOI: 10.3390/coatings13020378

The technology of perovskite solar cells (PSC) is getting close to breaching the consumer market. Yet, one of the current challenges is to reduce the toxicity during their fabrication by reducing the use of the toxic solvents involved in the perovskite fabrication process. A good solubilization of lead halides used in hybrid perovskite preparation is required, and it is only possible with polar solvents. A mixture of dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) is the most popular solvent combination for a perovskite precursor solution. DMF is necessary to ensure a good dissolution of lead iodide, but it is also the most toxic solvent. In this paper, we study the replacement of the dimethylformamide with presumably less toxic alternatives, such as N-methyl-2-Pyrrolidone (NMP) and ethyl acetate (EA), for the preparation of the K(0.1)FA(0.7)MA(0.2)PbI(2.8)Cl(0.2) (KFAMA) hybrid perovskite. The perovskite thin films were investigated by various characterization techniques: X-ray diffraction, atomic force microscopy, scanning electron microscopy, and UV-vis spectroscopy, while the photovoltaic parameters were determined by measuring the IV curves of the corresponding solar cells. The present study shows that by keeping the same deposition parameters as when only DMF solvent is used, the partial solvent substitution with NMP and EA gives promising results for reducing the toxicity of the fabrication process of KFAMA-based PSCs. Thus, with no specific optimization of the deposition process, and for the maximum possible partial substitution of DMF with NMP and EA solvents, the loss in the power conversion efficiency (PCE) value is only 35% and 18%, respectively, associated with the more structural defects promoted by NMP and EA.

2. Partial replacement of Pb2+ in MAPbI(2.6)Cl(0.4) perovskite films and their photovoltaic performance

Authors: Derbali, S; Nouneh, K; Leonat, LN; Stancu, V; Tomulescu, AG; Galca, AC; Touhami, ME; Pintilie, I; Florea, M

Published: APR 2023, JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS, 34, 903, DOI: 10.1007/s10854-023-10318-9

Replacing lead atoms in halide perovskite materials is of significant importance for the development of environmentally friendly perovskite solar cells. In this paper, we investigated the effect of doping the MAPbI(2.6)Cl(0.4) hybrid perovskite (MA-methyl ammonium) with non-toxic elements, such as alkaline earth metal ions (Mg2+) and transition metal ions (Zn2+). The structural, morphological, and optical properties of the prepared samples were analyzed using X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), and UV-Vis. spectroscopy. Finally, the doped films were used as photoactive layers in solar devices in order to evaluate their photovoltaic performance. Zn proved to be more appropriate to replace partially Pb and films with higher quality were obtained. As a result, the MAPb1(-x)Zn(x)I(2.6)Cl(0.4) based solar cells have demonstrated a slight improvement of the photovoltaic performances, resulting in a uniform and narrower PCEs (power conversion efficiency) range, compared to pristine MAPbI(2.6)Cl(0.4) based devices.

3. Effect of chlorine and bromine on the perovskite crystal growth in mesoscopic heterojunction photovoltaic device

Authors: Mehdi, H; Leonat, LN; Stancu, V; Saidi, H; Enculescu, M; Tomulescu, AG; Toma, V; Pintilie, I; Bouazizi, A; Galca, AC

Published: JUN 1 2022, MATERIALS SCIENCE IN SEMICONDUCTOR PROCESSING, 143, 106558, DOI: 10.1016/j.mssp.2022.106558

Organic-inorganic hybrid perovskite solar cells are within the emerging photovoltaic technologies. The combination of different halogen ions, in certain fill fractions, is one of the methods to improve the perovskite film properties. Herein, fabrication and characterization of perovskite cells in standard mesoscopic architecture using one-step deposition method has been done. The role of the halogen ions (Chlorine or Bromine) on crystal structure growth and photoelectric performance has been investigated. X-ray diffraction, scanning electron microscopy, atomic force microscopy and optical microscopy analysis were performed. The microstructure, composition and morphology of CH3NH3PbI1.8Br1.2 and CH3NH3PbI1.8Cl1.2 films are dissimilar, although identical fabrication method was used. Same holds for optical properties, band gap energies of 1.84 eV and 1.63 eV, respectively, being obtained. Integrated in solar cells, the maximum power conversion efficiency of the Br based devices is beyond 10%, while for those based on Cl, the efficiency drops around 5%.

4. Potassium-containing triple-cation mixed-halide perovskite materials: Toward efficient and stable solar cells

Authors: Derbali, S; Nouneh, K; Florea, M; Leonat, LN; Stancu, V; Tomulescu, AG; Galca, AC; Secu, M; Pintilie, L; Touhami, ME

Published: MAR 25 2021, JOURNAL OF ALLOYS AND COMPOUNDS, 858, DOI: 10.1016/j.jallcom.2020.158335

In this paper, potassium based triple cation mixed-halide perovskite films were explored in order to enhance the stability and photovoltaic performance of perovskite based solar cells. It was found that adding potassium (K+) to a double cation mixed halide perovskite (FA(0.80)MA(0.20)PbI(2.8)Cl(0.2)), structural, morphological and optoelectronic properties of perovskites are improved. The perovskite films were prepared by one-step spin coating method with and without K+ and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), UV-Vis spectroscopy, X-ray photoelectron spectroscopy (XPS), and photoluminescence spectroscopy (PL). The results indicate that potassium incorporation reduces significantly the yellow non-perovskite delta-phase formation and improves the perovskite film quality, thus contributing to the reduction of hysteresis, improves the stability and increases the PCE up to 12.51%. Furthermore, the doped devices exhibit reduced hysteresis and provide remarkable shelf stability by retaining more than 70% of the initial efficiency with low humidity over 850 h. (C) 2020 Elsevier B.V. All rights reserved.

5. Accidental Impurities in Epitaxial Pb(Zr0.2Ti0.8)O-3 Thin Films Grown by Pulsed Laser Deposition and Their Impact on the Macroscopic Electric Properties

Authors: Boni, GA; Chirila, CF; Stancu, V; Amarande, L; Pasuk, I; Trupina, L; Istrate, CM; Radu, C; Tomulescu, A; Neatu, S; Pintilie, I; Pintilie, L

Published: MAY 2021, NANOMATERIALS, 11, DOI: 10.3390/nano11051177

Structural and electrical properties of epitaxial Pb(Zr0.2Ti0.8)O-3 films grown by pulsed laser deposition from targets with different purities are investigated in this study. One target was produced in-house by using high purity precursor oxides (at least 99.99%), and the other target was a commercial product (99.9% purity). It was found that the out-of-plane lattice constant is about 0.15% larger and the a domains amount is lower for the film grown from the commercial target. The polarization value is slightly lower, the dielectric constant is larger, and the height of the potential barrier at the electrode interfaces is larger for the film deposited from the pure target. The differences are attributed to the accidental impurities, with a larger amount in the commercial target as revealed by composition analysis using inductive coupling plasma-mass spectrometry. The heterovalent impurities can act as donors or acceptors, modifying the electronic characteristics. Thus, mastering impurities is a prerequisite for obtaining reliable and reproducible properties and advancing towards all ferroelectric devices.

6. Enhancing stability of hybrid perovskite solar cells by imidazolium incorporation

Authors: Tomulescu, AG; Leonat, LN; Neatu, F; Stancu, V; Toma, V; Derbali, S; Neatu, S; Rostas, AM; Besleaga, C; Patru, R; Pintilie, I; Florea, M

Published: AUG 1 2021, SOLAR ENERGY MATERIALS AND SOLAR CELLS, 227, DOI: 10.1016/j.solmat.2021.111096

Hybrid perovskites based solar cells have demonstrated high conversion efficiency but poor long-term stability. This study reports on the results obtained after doping the CH3NH3PbI2.6Cl0.4 mixed halide perovskite with imidazolium (C3N2H5+, denoted IM) on the "A site" position of a perovskite, to improve photovoltaic performances and stability of hybrid perovskite solar cells. The perovskite films were investigated exhaustively by different characterization techniques: X-ray diffraction, Atomic Force Microscopy, Scanning Electron Microscopy, UV-Vis, X-ray Photoelectron Electron Paramagnetic Resonance spectroscopies, Impedance Spectroscopy and Incident Photon-to-Electron Conversion Efficiency. The photovoltaic parameters were determined by measuring the IV curves of the corresponding solar cells. The amount of IM inserted in the perovskite play a key role on the film properties. The calculated new tolerance factors according to the "globularity factor" are experimentally proved and thus at doping concentrations greater than 20% for CH3NH3PbI2.6Cl0.4 perovskite the 3D structure is no longer obtained. However, below this value, the IM substituted perovskite film possesses an improved film quality and crystallinity as compared to the pristine film. Substituting MA+ with IM+ provides a favorable way to reduce recombination processes and shows great potential to achieve high stability, and an improved charge generation, resulting in increased PCE values. We find that the optimal percentage of imidazolium incorporation to achieve better stability of solar cells is 6%.

7. Influence of doping the inorganic cation with Eu or Sb on the properties of perovskite films

Authors: Stancu, V; Leonat, LN; Tomulescu, AG; Derbali, S; Pintilie, L; Besleaga, C; Galca, AC; Neatu, F; Neatu, T; Florea, M; Pintilie, I

Published: JUL 2020, PHYSICA SCRIPTA, 95, DOI: 10.1088/1402-4896/ab90be

This study reports on the results obtained after doping the [CH3NH3](0.94)[C3N2H5](0.06)PbI2.6Cl0.4 mixt halide perovskite with europium or antimony (Eu3+/Sb3+) at the 'B site'. This way two new complex compounds were obtained, [CH3NH3](0.94)[C3N2H5](0.06)Pb1-yByI2.6Cl0.4 (B = Eu or Sb and y = 0-0.05) as perovskite precursor solutions and deposited as thin films. The properties of the perovskite films were investigated by various characterization techniques: x-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), UV-vis spectroscopy while the photovoltaic parameters were determined by measuring the IV curves of the corresponding solar cells. We find that doping the mixt halide perovskite with very small quantities of Sb improves the quality of the perovskite films and further improves the stability of perovskite solar cells.

8. Exploring the effect of aliovalent substitution of Pb2+ by Eu3+ on structural, morphological and optical properties of CH3NH3PbI3 perovskite films

Authors: Derbali, S; Nouneh, K; Florea, M; Neatu, F; Neatu, S; Leonat, LN; Secu, M; Tomulescu, AG; Stancu, V; Pintilie, L; Touhami, ME; Galca, AC

Published: APR 2020, PHYSICA SCRIPTA, 95, DOI: 10.1088/1402-4896/ab5baa

In this work, the effect of aliovalent substitution of Pb2+ by Eu3+ on structural, morphological and optical properties of CH3NH3PbI3 (MAPbI(3)) was studied, aiming to improve the properties of perovskite films used in solar cells application. The surface morphology, the microstructure and the optical properties of the obtained films containing different Europium (Eu) concentrations were characterized by atomic force microscopy, x-ray photoelectron spectroscopy, x-ray diffraction, UV-vis spectroscopy and photoluminescence spectroscopy.

9. Reticulated Mesoporous TiO2 Scaffold, Fabricated by Spray Coating, for Large-Area Perovskite Solar Cells

Authors: Tomulescu, AG; Stancu, V; Besleaga, C; Enculescu, M; Nemnes, GA; Florea, M; Dumitru, V; Pintilie, L; Pintilie, I; Leonat, L

Published: JAN 2020, ENERGY TECHNOLOGY, 8, DOI: 10.1002/ente.201900922

Development of reproducible, low-cost fabrication technologies that are readily adaptable to large-scale production, is one of the main challenges in the field of perovskite solar cells (PSCs). So far, for all the other layers in a solar cell, large-area deposition methods have been adapted, except for mesoporous fabrication. Herein, the fabrication of mesoporous TiO2 scaffolds using a large-area deposition technique, such as spray coating, is shown. Moreover, this technique induces the formation of a very specific reticulated structure with well-delimited, oval-shaped cavities. The cavities have irregular dimensions, with diameters in the range of 3-7 mu m, approximate to 350 nm height, resulting in an overall increase in roughness of one order of magnitude, compared with the spin-coated mesoporous scaffold. Using this rough structured mesoporous TiO2 in PSCs not only does not affect the efficiency of solar cells but actually improves it from an average of 10% to 12% in comparison with the devices containing a spin-coated mesoporous scaffold.

10. Comparison between dielectric and pyroelectric properties of PZFNT and BST type ceramics

Authors: Stancu, V; Amarande, L; Botea, M; Iuga, A; Leonat, LN; Tomulescu, AG; Cioangher, M; Balescu, LM; Pintilie, L

Published: 2019, PROCESSING AND APPLICATION OF CERAMICS, 13, 276, DOI: 10.2298/PAC1903269S

Ba0.75Sr0.25TiO3 (BST) and PbZr0.68Fe0.14Nb0.14Ti0.04O3 (PZFNT) ceramic pellets were obtained by ceramic technology and their structural, ferroelectric and pyroelectric properties were investigated. The relative density of BST and PZFNT is about 93% and 90%, respectively, with an average grain size of 102 mu m and 6.45 mu m. Both materials have similar room temperature dielectric constants (similar to 2000), but PZFNT shows higher remnant polarization (similar to 15 mu C/cm(2)) and better pyroelectric properties (similar to 1.69 . 10(-4) C/m(2)K), which recommend it for pyroelectric detectors, infrared radiation- and laser pulse energy-meters.

11. Carbon-based sprayed electrodes for pyroelectric applications

Authors: Chirila, C; Botea, M; Iuga, A; Tomulescu, AG; Balescu, L; Galca, AC; Boni, AG; Leonat, L; Pintilie, I; Pintilie, L

Published: AUG 15 2019, PLOS ONE, 14, DOI: 10.1371/journal.pone.0221108

A carbon-based layer was deposited by spraying on top of a ferroelectric layer grown by sol-gel on Si (001) substrate and its properties as electrode and absorber for pyroelectric detection were tested. It was found that the electric properties of the ferroelectric capacitor with top carbon-based sprayed electrode (CBSE) are comparable with those of the capacitors with standard top SrRuO3 (SRO)/Au electrode. Pyroelectric measurements show that the pyroelectric signal recorded on ferroelectric capacitors with top CBSE electrode is 2.5 times greater than for top SRO/Au electrode for low frequency range. The value of the pyroelectric coefficient was estimated to 9.73.10(-4) C/m(2)K for CBSE electrodes and 3.36.10(-4) C/m(2)K for SRO/Au respectively. The fabrication process of CBSE is of low cost, easy to implement and with high throughput making it attractive for manufacturing various devices like pyroelectric detector, thermal imaging, solar cells, etc.

12. STRUCTURAL, DIELECTRIC AND PYROELECTRIC PROPERTIES OF Nb AND Fe DOPED PZT CERAMICS

Authors: Stancu, V; Amarande, L; Botea, M; Cioangher, M; Tomulescu, A; Iuga, A; Pintilie, L

Published: JAN-MAR 2019, DIGEST JOURNAL OF NANOMATERIALS AND BIOSTRUCTURES, 14, 230, DOI:

Lead zirconate titanate doped with iron and niobium (PZFNT) was prepared by conventional processing technique, solid state synthesis method. The influence of dopants on the microstructure, ferroelectric and pyroelectric properties was investigated. XRD data reveals a perovskite structure near to the lead zirconate phase. The relative density of PZFNT is approximate 90%, with average grains size of 6.45 mu m.

13. The hysteresis-free behavior of perovskite solar cells from the perspective of the measurement conditions

Authors: Nemnes, GA; Besleaga, C; Tomulescu, AG; Leonat, LN; Stancu, V; Florea, M; Manolescu, A; Pintilie, I

Published: MAY 14 2019, JOURNAL OF MATERIALS CHEMISTRY C, 7, 5274, DOI: 10.1039/c8tc05999c

We investigate how far the hysteresis-free behavior of perovskite solar cells can be reproduced using particular pre-conditioning and measurement conditions. As there are currently more and more reports of perovskite solar cells without J-V hysteresis it is crucial to distinguish between genuine performance improvements and measurement artifacts. We focus on two of the parameters that influence the dynamic J-V scans, namely the bias scan rate and the bias poling voltage, and point out measurement conditions for achieving a hysteresis-free behavior. In this context we discuss the suitability of defining a hysteresis index (HI) for the characterization of dynamic J-V scans. Using HI, aging effects are also investigated, establishing a potential connection between the sample degradation and the variation of the maximal hysteresis on one hand, and the relaxation time scale of the slow process on the other hand. Pre-poling induced recombination effects are identified. In addition, our analysis based on sample pre-biasing reveals potential indications regarding two types of slow processes, with two different relaxation time scales, which provides further insight regarding ionic migration.

14. How measurement protocols influence the dynamic J-V characteristics of perovskite solar cells: Theory and experiment

Authors: Nemnes, GA; Besleaga, C; Tomulescu, AG; Palici, A; Pintilie, L; Manolescu, A; Pintilie, I

Published: OCT 2018, SOLAR ENERGY, 173, 983, DOI: 10.1016/j.solener.2018.08.033

The dynamic effects observed in the J-V measurements represent one important hallmark in the behavior of the perovskite solar cells. Proper measurement protocols (MPs) should be employed for the experimental data reproducibility, in particular for a reliable evaluation of the power conversion efficiency (PCE), as well as for a meaningful characterization of the type and magnitude of the hysteresis. We discuss here several MPs by comparing the experimental J-V characteristics with simulated ones using the dynamic electrical model (DEM). Pre-poling conditions and bias scan rate can have a dramatic influence not only on the apparent solar cell performance, but also on the hysteretic phenomena. Under certain measurement conditions, a hysteresis-free behavior with relatively high PCEs may be observed, although the J-V characteristics may be far away from the stationary case. Furthermore, forward-reverse and reverse-forward bias scans show qualitatively different behaviors regarding the type of the hysteresis, normal and inverted, depending on the bias pre-poling. We emphasize here that correlated double-scans, forward-reverse or reverse-forward, where the second scan is conducted in the opposite sweep direction and begins immediately after the first scan is complete, are essential for a correct assessment of the dynamic hysteresis. In this context, we define a hysteresis index which consistently assigns the hysteresis type and magnitude. Our DEM simulations, supported by experimental data, provide further guidance for an efficient and accurate determination of the stationary J-V characteristics, showing that the type and magnitude of the dynamic hysteresis may be affected by unintentional pre-conditioning in typical experiments.

15. Dynamic electrical behavior of halide perovskite based solar cells

Authors: Nemnes, GA; Besleaga, C; Tomulescu, AG; Pintilie, I; Pintilie, L; Torfason, K; Manolescu, A

Published: JAN 2017, SOLAR ENERGY MATERIALS AND SOLAR CELLS, 159, 203, DOI: 10.1016/j.solmat.2016.09.012

A dynamic electrical model is introduced to investigate the hysteretic effects in the J-V characteristics of perovskite based solar cells. By making a simple ansatz for the polarization relaxation, our model is able to reproduce qualitatively and quantitatively detailed features of measured J-V characteristics. Pre-poling effects are discussed, pointing out the differences between initially over- and under-polarized samples. In particular, the presence of the current overshoot observed in the reverse characteristics is correlated with the solar cell pre-conditioning. Furthermore, the dynamic hysteresis is analyzed with respect to changing the bias scan rate, the obtained results being consistent with experimentally reported data: the hysteresis amplitude is maximum at intermediate scan rates, while at very slow and very fast ones it becomes negligible. The effects induced by different relaxation time scales are assessed. The proposed dynamic electrical model offers a comprehensive view of the solar cell operation, being a practical tool for future calibration of tentative microscopic descriptions. (C) 2016 Elsevier B.V. All rights reserved.

16. Properties of perovskite ferroelectrics deposited on F doped SnO2 electrodes and the prospect of their integration into perovskite solar cells

Authors: Pintilie, I; Stancu, V; Tomulescu, A; Radu, R; Stan, CB; Trinca, L; Pintilie, L

Published: DEC 5 2017, MATERIALS & DESIGN, 135, 121, DOI: 10.1016/j.matdes.2017.09.013

The integration of ferroelectrics in perovskite solar cells is proposed as possible way to enhance charge collection efficiency. First results on solar cellmanufactured with PbTiO3 (PTO) instead of TiO2 have shown negligible values for the power conversion efficiency (PCE). This is explained by the high serial resistance of sol-gel deposited PTO on F:SnO2 electrodes (FTO). Although PTO layer has remnant polarization of 22 mu C/cm(2), the high potential barrier (0.25 +/- 0.05 eV) at the FTO/PTO interface and lowcarriermobility (10(-8) cm(2) V-1 s(-1)) compared to TiO2 leads to high serial resistance. Better results were obtained with thinner PTO layers grown by pulsed laser deposition, with PCE values up to 0.6%. Further enhancement was obtained by replacing PTO with BaTiO3 (BTO), with PCE value reaching about 0.8% after poling the cell with +3 V. The most important finding was that the magnitude of the short circuit current increases with the amplitude of the poling voltage while the value of the open-circuit voltage remains about the same, around 0.9 V. This is explained through more efficient collection of the charges generated under illumination in the absorber layer due to the polarization that is present in the ferroelectric film. (C) 2017 Elsevier Ltd. All rights reserved.

17. Iodine Migration and Degradation of Perovskite Solar Cells Enhanced by Metallic Electrodes

Authors: Besleaga, C; Abramiuc, LE; Stancu, V; Tomulescu, AG; Sima, M; Trinca, L; Plugaru, N; Pintilie, L; Nemnes, GA; Iliescu, M; Svavarsson, HG; Manolescu, A; Pintilie, I

Published: DEC 15 2016, JOURNAL OF PHYSICAL CHEMISTRY LETTERS, 7, 5175, DOI: 10.1021/acs.jpclett.6b02375

We monitored the evolution in time of pinhole-free structures based on FTO/TiO2/CH3NH3PbI2.6Cl0.4 layers, with and without spiro-OMeTAD and counter electrodes (Ag, Mo/Ag, and Au), aged at 24 degrees C in a dark nitrogen atmosphere. In the absence of electrodes, no degradation occurs. While devices with Au show only a 10% drop in power conversion efficiency, remaining stable after a further overheating at 70 degrees C, >90% is lost when using Ag, with the process being slower for Mo/Ag. We demonstrate that iodine is dislocated by the electric field between the electrodes, and this is an intrinsic cause for electromigration of I- from the perovskite until it reaches the anode. The iodine exhaustion in the perovskite layer is produced when using Ag electrodes, and AgI is formed. We hypothesize that in the presence of Au the iodine migration is limited due to the buildup of I- negative space charge accumulated at the perovskite-OMeTAD interface.

Andrei TOMULESCU

Assistant Researcher