Enhanced photovoltaic performance of quinoxaline-based small molecules through incorporating trifluoromethyl substituents

Abstract

Two D-A-D type quinoxaline-based small molecules have been synthesized by Suzuki coupling reaction for solution-processable organic photovoltaic cells (OPVs). The electron-donating triphenylamine was connected to both ends of an electron-withdrawing 2,3-diphenylquinoxaline core through thiophene bridge to produce QxTPA. In addition, QxCF₃TPA was formed by introducing strong electron-withdrawing trifluoromethyl (CF₃) groups into the para-position of the phenyl ring at the 2,3-position of quinoxaline core in QxTPA to explore their effect on the various properties of small molecules. The finding revealed the significant contributions of CF₃ substituents in enhancing the photovoltaic performances of OPVs with QxCF₃TPA compared to the reference case with QxTPA.     

Syntheses and Photovoltaic Properties of Octyl Cyanoacetate Terminated Small Molecules Based on Benzo[1,2-b:4,5-b’]dithiophene for OPVs

There have been tremendous efforts to synthesize photoactive materials that are consisted of both donor and acceptor components together to increase the power conversion efficiency (PCE) of organic photovoltaic cells (OPVs). In order to improve the performance of the OPVs, in this study, we proposed new A-D-A (Acceptor-Donor-Acceptor) type small molecular donors based on the donor unit of benzo[1,2-b:4.5-b’]dithiophene (BDT) with an acceptor unit of alkyl cyanoacetate. We characterized prepared photoactive materials using ¹H NMR spectroscopy, DSC, CV (cyclic voltammetry), and UV/Vis spectroscopy. We also investigated the relationship between PCEs of OPVs and the active materials with variation of substituted methyl groups. The OPVs based on synthesized photoactive materials with different methyl substitutions showed different PCEs. Our results indicate that synthesized small molecular donor materials are promising donor materials for performance OPVs     

Synthesis of quinoxaline-based D-A type conjugated polymers for photovoltaic applications

Abstract

Two quinoxaline-based conjugated polymers were successfully synthesized for application in polymer solar cells (PSCs). The quinoxaline unit with an electron-donating dimethylamino substituent was used as the electron-accepting (A) moiety, whereas indacenodithiophene (IDT) and indacenodithieno-thiophene (IDTT) were chosen as the electron-donating (D) groups to synthesize D-A type conjugated polymers. To investigate the photovoltaic properties of the polymers, an inverted-type device with the configuration of ITO/ZnO/polymer:PC₇₁BM/MoO₃/Ag was fabricated. It has been observed that the overall performances of the organic photovoltaic cells were significantly improved by changing the electron-donating components from IDT to IDTT. Therefore, this study can provide insights into the design and structure–property correlation of quinoxaline-based conjugated polymers for PSCs.     

Synthesis of a BDT-based small-molecule acceptor with dye end groups for organic photovoltaic cell application

ABSTRACT

An acceptor-donor-acceptor (A–D–A)-type small molecule, BDT-IN, having a benzo[1,2-b:4,5-b']dithiophene (BDT) unit as its electron-donating core (D) and an 1,3-indanedione (IN) unit as its electron-withdrawing end group (A), was synthesized by Knoevenagel condensation. The BDT-IN film showed broader UV absorption with a greater red shift (λ_max = 622 nm) than that of the BDT-IN solution (λ_max = 570 nm). The organic photovoltaic cells were fabricated with an ITO/PEDOT:PSS/poly(3-hexylthiophene): BDT-IN/LiF/Al configuration, and showed a power conversion efficiency of 0.23%.     

Structure engineering of small molecules for organic solar cells

Abstract

Two 1,3-bis(thiophen-2-yl)?5,7-bis(2-ehtylhexyl)benzo-[1,2-c:4,5-c]-dithiophene-4,8-dione (BDD) based small molecules, SM1 and SM2 are designed and synthesized by incorporating benzodithiophene (BDT) central core, BDD dual accepting units and 3-ethyl rhodamine as endcap group with various number of BDT units. We systematically investigated the synthesis, optical and electrochemical properties, and photovoltaic characteristics of these donor materials. The number of BDT units have a significant influence on Jsc due to interconnected structure and results in a broader absorption on thin film. The inverted devices employed for both small molecules exhibited power conversion efficiencies of 0.41% for SM1 and 0.82% for SM2.     

Emission from Charge-Transfer States in Bulk Heterojunction Organic Photovoltaic Cells Based on Ethylenedioxythiophene-Fluorene Polymers

We investigated the electroluminescence (EL) from charge-transfer (CT) in the interface state of PEDOTF/PC₇₀BM, known to be empirically related to V_oc, to elucidate a difference in V_oc of 0.24 V in bulk heterojunction (BHJ) organic photovoltaic cells (OPVs) based on two polymers (H-PEDOTF and S-PEDOTF with a high and low molecular weight, respectively) having almost the same HOMO energy levels. The difference in the energies of CT EL peaks is relatively small (0.06 eV) compared to the difference in the V_ocs. Consequently, we mainly attribute the excessive loss of V_oc in S-PEDOTF-based OPVs to a trap assisted recombination mechanism.     

Wide band-gap organic molecules containing benzodithiophene and difluoroquinoxaline derivatives for solar cell applications

Abstract

Two new semiconducting organic small molecules, namely BDTQ-BDT(EH) and BDTQ-BDT(OC), were prepared by attaching electron accepting 2,3-didodecyl-6,7-difluoro-5,8-di(thiophen-2-yl)quinoxaline (DTQ) unit on 2,6-position of electron donating 4,8-bis(2-ethylhexyloxy)benzo[1,2-b:4,5-b']dithiophene (BDT(EH)) and 4,8-bis(octyloxy)benzo[1,2-b:4,5-b']dithiophene (BDT(OC)) units. Molecule BDTQ-BDT(EH) showed higher thermal stability (5% weight loss temperature, T_d “349 ^оC), slightly lower band-gap (E_g “2.10?eV) and deeper highest occupied molecular orbital energy level (HOMO “–5.36?eV) level compared to those (T_d “336 ^оC, E_g “2.11?eV, and HOMO “–5.30?eV, respectively.) of the molecule BDTQ-BDT(OC). The organic solar cells (OSCs) made with the synthesized molecules as an electron donor and [6,6]-phenyl C₇₁ butyric acid methyl ester (PC₇₀BM) as an electron acceptor gave a maximum power conversion efficiency (PCE) of 1.20% and 0.83%, respectively, for BDTQ-BDT(EH) and BDTQ-BDT(OC). This study confirmed that the substituents attached on the 4,8-position of BDT unit greatly alter the properties of the resulting molecules.     

Effect of fused thiazolothiazole on the photovoltaic performance of fluorene-thiazole-based conjugated polymers

In this work, we utilized two fluorene-based polymers (F8TBTT and F8TTZT) as donor materials in organic photovoltaic cells (OPVs) and compared their performance to explain the effect of substituting fused thiazolothiazole for the bithiazole moiety. The OPV device based on F8TTZT showed a power conversion efficiency of 0.24%, which is three times higher than that of F8TBTT (0.07%) under the same conditions. The better performance can be explained by the increased planarity and enhanced intermolecular charge transport.     

Thermally activated delayed fluorescence host materials based on triphenylphosphine oxide derivatives

Abstract

Novel thermally activated delayed fluorescence (TADF) host molecules for blue electrophosphorescence were developed by combining the electron donor acridine derivatives with the electron acceptor triphenylphosphine oxide unit in a single molecule based on density functional theory. We obtained the energies of the first excited singlet (S₁) and triplet (T₁) states of the TADF materials by performing procedures in accordance with density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations to the ground state using dependence on the charge transfer amounts for the optimal Hartree-Fock percentage in the exchange-correlation of TD-DFT. Using DFT and TD-DFT calculations, the significant separation between the HOMO and LUMO caused a small difference in energy (ΔE_ST) between the S₁ and T₁ states. The host molecules retained high triplet energy and showed great potential for use in blue phosphorescent organic light-emitting diodes. The results also showed that these molecules are promising TADF host materials because they demonstrate a low barrier to hole and electron injection, balanced charge transport for both holes and electrons, and small ΔE_ST.     

Small molecular electrolytes as the interlayer for enhanced performance of organic solar cellsExperimental

Abstract

New non-conjugated small molecules (C4-OH and C6-OH) were synthesized and applied to the inverted organic solar cells (OSCs) as the cathode interlayer (CIL). The power conversion efficiencies (PCEs) of 9.35 and 9.21% were obtained in the device based on ZnO/C4-OH and ZnO/C6-OH, which are better than those of pristine ZnO (8.74%). The work function of ZnO/C4-OH and ZnO/C6-OH are also decreased from ?4.5?to ?4.27?eV and ?4.37?eV, respectively. Consequently, OSCs with two small molecules exhibited enhanced photovoltaic properties due to the formation of interface dipole.     

Low Temperature Crystal Structures of Two Rhodanine Derivatives, 3-Amino Rhodanine and 3-Methyl Rhodanine: Geometry of the Rhodanine Ring

Abstract  Rhodanines (2-thio-4-oxothiazolidines) are synthetic small molecular weight organic molecules with diverse applications in biochemistry, medicinal chemistry, photochemistry, coordination chemistry and industry. The X-ray crystal structure determination of two rhodanine derivatives, namely (I), 3-aminorhodanine [3-amino-2-thio-4-oxothiazolidine], C₃H₄N₂OS_2, and (II) 3-methylrhodanine [3-methyl-2-thio-4-oxothiazolidine], C₄H₅NOS₂, have been conducted at 100 K. I crystallizes in the monoclinic space group P2₁/n with unit cell parameters a = 9.662(2), b = 9.234(2), c = 13.384(2) ?, β = 105.425(3)°, V = 1151.1(3) ?³, Z = 8 (2 independent molecules per asymmetric unit), density (calculated) = 1.710 mg/m³, absorption coefficient = 0.815 mm⁻¹. II crystallizes in the orthorhombic space group Iba2 with unit cell a = 20.117(4), b = 23.449(5), c = 7.852(2) ?, V = 3703.9(12) ?³, Z = 24 (three independent molecules per asymmetric unit), density (calculated) = 1.584 mg/m³, absorption coefficient 0.755 mm⁻¹. For I in the final refinement cycle the data/restraints /parameter ratios were 2639/0/161, goodness-of-fit on F² = 0.934, final R indices [I > 2sigma(I)] were R1 = 0.0299, wR2 = 0.0545 and R indices (all data) R1 = 0.0399, wR2 = 0.0568. The largest difference peak and hole were 0.402 and −0.259 e ?⁻³. For II in the final refinement cycle the data/restraints/parameter ratios were 3372/1/221, goodness-of-fit on F² = 0.950, final R indices [I > 2sigma(I)] were R1 = 0.0407, wR2 = 0.1048 and R indices (all data) R1 = 0.0450, wR2 = 0.1088. The absolute structure parameter = 0.19(9) and largest difference peak and hole 0.934 and −0.301 e ?⁻³. Details of the geometry of the five molecules (two for I and three for II) and the crystal structures are fully discussed. Corresponding features of the molecular geometry are highly consistent and firmly establish the geometry of the rhodanine ring. Index Abstract  Low temperature X-ray structures of (I) 3-aminorhodanine [3-amino-2-thio-4-oxothiazolidine] and (II) 3-methylrhodanine3-methyl-2-thio-4-oxothiazolidine are presented. Crystals of I are monoclinic and occupy space group P2₁/n with eight molecules (2 per asymmetric unit cell) and (II) is orthorhombic in space group Iba2 with 24 molecules (3 per asymmetric unit). This study has provided five highly consistent copies of the rhodanine ring at high resolution thus enabling its geometry to be established with confidence. The two independent molecules in the asymmetric unit of 3-aminorhodanine (left) and the three independent molecules in the asymmetric unit of 3-methylrhodanine (right) showing space filling and van der Waals contacts (drawn with MERCURY [Bruno et al. Acta Cryst B58:389, 2002]).     

Formation of ordered nanostructures in liquid-crystalline block copolymers with side-chain semiconductor materials

ABSTRACT

We developed a novel block copolymer composed of poly(ethylene oxide) (PEO) and polymethacrylate functionalized with liquid–cryst-alline oligothiophene by using the atom transfer radical polymerization (ATRP), aiming at application to organic photovoltaic (OPV) cells. Thermal investigation showed that the resultant polymer exhibits liquid–crystalline phases both on heating and cooling. Morphologies of the thin films of the block copolymer were investigated by atomic force microscopy (AFM). Microphase separation with a small size of almost 10 nm (nano-phase-separated structures) was observed upon annealing.     

Synthesis and crystal structure of the coordination compound of pyridoxine with manganese sulfate

The reaction of pyridoxine with manganese sulfate in an aqueous solution gave the coordination compound MnSO₄ · 2C₈H₁₁O₃N · 2H₂O (I). The structure of I was determined from single-crystal X-ray diffraction data. In the centrosymmetric complex (sp. gr. P[`1]P\bar 1, Z = 1), the Mn atom is coordinated by two pyridoxine molecules and two water molecules, thus adopting an octahedral coordination. The sulfate anion is also at a center of symmetry and, consequently, is disordered. The pyridoxine molecules are coordinated to the metal atom through the oxygen atoms of the deprotonated hydroxyl group and the CH₂OH group that retains the hydrogen atom. The nitrogen atom is protonated in such a way that the heterocycle assumes a pyridinium character. The crystal structure also contains six water molecules of crystallization. A thermogravimetric study showed that the decomposition of I occurs in several successive steps, such as dehydration, the combustion of organic ligands, and the formation of an inorganic residue.     

Enhancement of organic thin-film solar cells by incorporating hybrid Au nanospheres and Au nanorods on a metallic grating surface

Abstract

In this study, we demonstrate the fabrication of hybrid plasmonic solar cells using gold nanoparticles (AuNPs). Two types of AuNPs, gold nanospheres (AuNSs) and gold nanorods (AuNRs), were incorporated in a hole transport layer (HTL) (PEDOT:PSS) on a metallic grating electrode. The organic solar cells (OSCs) structure comprised an indium-tin-oxide (ITO)-coated glass substrate/PEDOT:PSS:AuNSs:AuNRs/P3HT:PCBM/Al grating electrode. Adding AuNPs induced localized surface plasmon resonance (LSPR), while grating structured Al at the interface with a photoactive layer excited the propagating surface plasmons. Compared with a flat reference device, the proposed OSCs exhibited improved photovoltaic properties by increasing both the short-circuit current density (J_SC) and the power conversion efficiency (PCE) with large enhancements of 16.23% and 14.06%, respectively. The efficiency improvement was attributed to increased broadband absorption and improved electrical properties inside the thin-film devices.     

The Electronic Structures of (PH4)3C60 and (ClO4)3C60

Abstract

We have studied theoretically the electronic structures of a hypothetical donor-type material, (PH₄)₃C₆₀, and a hypothetical acceptor-type material, (ClO₄)₃C₆₀ from first principles by using a full-potential linear-combination-of-atomic-orbitals method based on the density-functional theory within the local-density approximation. It is found that the charge transfer from the PH₄ molecules to the C₆₀ molecules is perfect while the charge transfer from the ClO₄ molecules to the C₆₀ molecules is not perfect. We compare the latter result with the electronic structures of two typical acceptor-type organic conductors, (TMTSF)₂ClO₄ and (TMTSF)₂PF₆, and discuss the differences.     

Isomorphism of inclusion compounds built with composite host lattices of thiadiazole and V-shaped molecules with the existence of tetrabutylammonium guest template

By using 4,4′-dihydroxydiphenylsulfone (BPS) and 4,4′-dihydroxydiphenylsulfide (BTS) react with amidinethiourea and tetrabutylammonium respectively, two isomorphs of inclusion compounds of (n-C₄H₉)₄N⁺·C₁₂H₉O₄S^?·C₂H₄N₄S (1) and (n-C₄H₉)₄N⁺·C₁₂H₉O₂S^?·C₂H₄N₄S (2) were prepared and characterized by Single crystal X-ray diffraction. Although two varied types of V-shaped molecules were selected to react in the actual experimental process, two isomorphs with similar packing modes were finally obtained. Interestingly, amidinothiourea molecule occurred in situ oxidation reaction to generate a new compound of 3,5-dimido-1,2,4,-thiadiazole during the experiments, and these two inclusion compounds here are the pioneer examples of thiadiazole and tetraalkylammonium and can be regarded as two isomorphs due to their similar crystallization modes. In these two isomorphs, thiadiazole molecules derived from amidinothiourea link with various V-type molecules to develop the similar dumbbell-type hydrogen-bonded ribbons by the alike hydrogen bonding modes, then the ribbons interpenetrate with tetrabutylammonium to result in two stable isomorphism structures.     

Synthesis of the Copolymer Based on Diketopyrrolopyrrole with Didecyl Chain for OPVs

A new accepter unit, diphenylpyrrolo[3,2-b]pyrrole-2,5-dione with didecyl chain, was prepared and utilized for the synthesis of the conjugated polymer containing electron donor-acceptor pair for OPVs. The iDPP, part of the structure of a natural dye found in lichens, is the regioisomer of the known DPP with switched position of the carbonyl group and nitrogen atom. At the 4-positions of the N-substituted phenyl groups of 1,4-bis(4-butylphenyl)-pyrrolo[3,2-b]-pyrrole-2,5-dione unit in P-butyl, the butyl group was substituted with decyl group to increase solubility. The absorption spectrum of polymer with diphenylpyrrolo[3,2-b]pyrrole-2,5-dione unit exhibit two maximum peaks at about 365 and 542 nm. The spectrum of the P1 as the solid thin film shows absorption band with maximum peaks at 370 and 536 nm, and the absorption onset at 703 nm, corresponding to band gap of 1.76 eV. The oxidation and reduction potential onset of the synthesized polymer were estimated to be 0.84 and ?1.22 V, which correspond to HOMO and LUMO energy levels of ?5.64 and ?3.58 eV, respectively. The devices comprising P1 with PC₆₁BM annealed at 100°C showed a V_OC of 0.79 V, a J_SC of 1.75 mA/cm², and a FF of 0.31, leading to the power conversion efficiency of 0.43% under white light illumination (AM 1.5 G, 100 mW/cm²).     

Synthesis and Structural Characterization of Dibromidobis(N,N′-dimethylthiourea-κS)cadmium(II) and Diiodidobis(N,N′-dimethylthiourea-κS)cadmium(II)

Abstract  

Cadmium(II) complexes, dibromidobis(N,N′-dimethylthiourea-S)cadmium(II), [Cd(Dmtu)₂Br₂] (1) and diiodidobis(N,N′-dimethylthiourea-S)cadmium(II), [Cd(Dmtu)₂I₂] (2), have been prepared and their structures have been determined by X-ray crystal structure analysis. Compound 1 crystallized in the monoclinic space group C2/c, and the metal ion is situated on a twofold rotation axis. Compound 2 also crystallized in a monoclinic space group, P2₁/c, but here the molecules have no crystallographic symmetry. In both compounds the cadmium atom is bonded to two halide ions and to two dimethylthiourea molecules through the sulfur atoms in a tetrahedral environment. The molecules are linked via N–H⋯Halide hydrogen bonds to form infinite one-dimensional chains in 1 and infinite two dimensional networks in 2. The complexes were also characterized by IR and NMR spectroscopy and the data are consistent with the structures of the compounds.     

Quantum-chemical simulation and experimental study of some magnetic nanoparticles stabilized in fluid suspensions by using organic coating

Abstract

The biomedical applications of magnetic nanoparticles require the surface modification with organic, hydrophilic molecules, able to ensure the stability of the resulted colloidal suspensions. We present the quantum mechanical approach of two molecules developing stable interfaces with magnetic Co_0.5Fe_2.5O₄ nanoparticles. Sodium oleate, and citric acid, ensuring steric and respectively electrostatic stabilization are comparatively analyzed. The roles of dipole moment and frontier orbitals energies were emphasized to better understanding of some interface phenomena for the optimization of magnetic nanoparticle suspension preparation. Further, practical yielding of colloidal Co_0.5Fe_2.5O₄ nanoparticles by coating with sodium oleate and respectively with citric acid is discussed.     

Stereochemistry and hydrogen bonding of cytokinins: Crystal and molecular structure of 6-(4-hydroxy-3-methyl-cis-2-butenyl) aminopurine (cis-zeatin)

The title compound is C₁₀H₁₃N₅O, monoclinic,P2₁/a,a=13.829 (7),b=7.834 (7),c=20.138 (9) Å, and =100.75 (6)°. The structure was solved by direct methods and refined by least-squares techniques to anR factor of 0.079 for 1581 observed reflections. There are two crystallographically independent molecules (I andI). The N⁶-substituent is distal to the imidazole ring of the adenine moiety. It is interesting to note that the conformation of the N⁶-substituent relative to the adenine ring base in these two crystallographically independent molecules shows considerable resemblance with the preferred one usually adopted in other cytokinins. The angles between the mean planes of the adenine base and the N⁶-substituent are 65.6 and 63.3° for theI andI molecules, respectively. The molecules are linked by pairs of N(9)-H·N(3) hydrogen bonds. The dimer-like structures are stabilized by a three-dimensional network of O-H·O, O-H·N, N-H·O, and C-H·N hydrogen bonds.