Heterojunction Organic Solar Cells with Efficient Charge Mobility and Separation Capabilities Studied by DFT.

The properties of the active layer materials play a decisive role in determining the power conversion efficiency of organic solar cells (OSCs). Chlorophyll and its derivatives are abundant and environmentally friendly functional organic molecular materials. Using density functional theory (DFT) and time-dependent density functional theory (TD-DFT), we have calculated the absorption spectra and their excited state properties based on optimized ground state structures. It was found that bacteriochlorin exhibits superior structural properties, a smaller energy gap and hole reorganization energy, redshifted absorption spectra, and higher hole mobility compared to the donor D18. This suggests that bacteriochlorin exhibits superior donor properties. Comparative studies between o-AT-2Cl and m-AT-2Cl showed that o-AT-2Cl had superior acceptor properties, implying that differences in substitution positions can influence the physicochemical properties of non-fullerene acceptors (NFAs). Subsequently, six bulk heterojunctions (BHJs) were constructed by combining three donors with nonfused ring electron acceptors, o-AT-2Cl and m-AT-2Cl. The bacteriochlorin-based BHJs performed well among them, with BChl3/o-AT-2Cl and BChl4/o-AT-2Cl having the largest interfacial charge separation rate. The results suggested that BHJs composed of bacteriochlorin and NFAs can improve OSCs' photovoltaic performance, providing a feasible scheme for designing efficient OSCs.

Study of the microscopic mechanism of stepwise charge injection in co-sensitive DSSCs in the framework of a D-π-A dye and chlorophyll.

The newly synthesized dye molecules TY6 and CXC22 were selected to explain the influence of anthracene and acetylene groups on the power conversion efficiency (PCE) of the molecules at the microscopic level. Theoretical simulation was carried out to understand the properties of the two molecules, including frontier molecular orbitals, absorption spectra, light absorption efficiency, intramolecular charge transfer (ICT), dye regeneration, I-V prediction, etc. The results suggest that for CXC22, adding an anthracene and acetylene group in the conjugate bridge greatly enhances the molecule's absorption wavelength and molar extinction coefficient; CXC22 also has significant advantages in the intramolecular charge transfer and comparatively better dye regeneration and electron injection. These parameters cause CXC22 to have a higher PCE. Subsequently, CXC22 and the chlorophyll molecule (CHL7) were selected for co-sensitization to regulate performance. The stable structure in the co-sensitization configuration was screened, and the absorption spectrum characteristics and charge transfer mechanisms were revealed for the co-sensitization system. The designed evaluation model predicted that the PCE of CO1 (the cosensitive system of CXC22 and TY6 in H-H configuration is referred to as CO1) could reach 16.78%. This work provides an idea for developing an efficient dye-sensitized solar cell system.

Molecular engineering and structure-property relationship based on D-A chlorophyll derivative and the application in organic solar cells.

The photoactive layer materials of organic solar cells (OSCs) play a critical role in achieving excellent performance. Chlorophyll derivatives are commonly used due to their environmental friendliness, low cost, and easy accessibility. However, the efficiency of OSCs based on chlorophyll is limited by their photoelectric properties. Here, we focused on the D-A structure of chlorophyll derivative ZnChl-1 and designed four molecules through rational molecular engineering. The photoelectric properties at the microscopic level were systematically studied using density functional theory (DFT). Our findings reveal that T-ZnChl-1 with triphenylamine donor unit has a smaller energy gap and ionization energy, as well as a larger spectral red shift and absorption range. This suggests that intramolecular charge transfer will be enhanced, leading to an improvement in short-circuit current. Furthermore, Y6 is used as the acceptor to construct the heterojunction interfaces. The results indicate that the T-ZnChl-1/Y6 interface exhibits more charge transfer states and higher exciton dissociation rate KCS, which will promote charge separation and lead to excellent photovoltaic performance. This work clarifies the structure-property relationship of chlorophyll derivatives and the photo-response mechanism of intermolecular charge transfer, providing a theoretical basis for developing valuable chlorophyll-based OSCs.

Photovoltaic performance and power conversion efficiency prediction of double fence porphyrins.

To explore high efficiency dye-sensitized solar cells (DSSCs), two experimentally derived (single fence and double fence porphyrins) and two theoretically designed zinc porphyrin molecules with D-D-π-A-A configurations were studied. Density functional theory and time-dependent density functional theory were employed to simulate these two experimental dyes and dye@TiO2 systems to understand why the double fence porphyrin molecule exhibits better photovoltaic performance than the single fence porphyrin molecule. For the short-circuit current (JSC), the various parameters that affected the experimental magnitude of JSC were analyzed from different aspects of absorption, charge transfer and chemical parameters as well as an electron injection process. The almost equal open-circuit voltages (VOC) in the experiment were predicted by theoretical VOC calculations. Our model predicted power conversion efficiencies (PCEs) of 1.993% and 10.866% for the single and double fence molecules, respectively, which are in accordance with the experimental values of 3.48% and 10.69%, respectively. In addition, one designed two new molecules based on the double fence porphyrin molecule with a 2-methyl-2H-benzo[d][1,2,3]triazole (BTA) unit bearing one fluorine and two fluorine atoms as the guest acceptor, respectively. Compared to the original molecules, the engineered molecules significantly improved the photovoltaic parameters, JSC and VOC, thereby causing excellent PCEs. The most outstanding designed molecule reached a PCE of 12.155%, and is considered a candidate dye for high-efficiency DSSC. This study provides insights into the photoelectric properties of single and double fence porphyrins. It also demonstrated that the strong electron-withdrawing ability of fluorine atoms would enhance the photovoltaic performance and provide a guideline for the further design of double fence porphyrins.

Accurate High-Level Ab Initio-Based Global Potential Energy Surface and Quantum Dynamics Calculation for the First Excited State of CH2.

A full three-dimensional global potential energy surface (PES), covering the whole configuration space, is reported first for the title system by fitting high-level ab initio energies at the multireference configuration interaction level with the aug-cc-pV6Z basis set. In this work, the many-body expansion method is invoked to fit the innate character of the CH2+(12A″) PES. The topographical features are examined in detail based on the new global PES and in accordance with the other calculations from the ab initio energies, which show the correct behavior at the C+(2P) + H2(X1Σg+) and CH+(a3Π) + H(2S) dissociation limits. Using a time-dependent wave packet method, we provide insights into the dynamics behavior for reaction of C+(2P) + H2(X1Σg+) → CH+(a3Π) + H(2S). The integral cross sections and reaction probabilities increase monotonically in terms of the collision energy.

Effect of Polymerization on the Charge-Transfer Mechanism in the One (Two)-Photon Absorption Process of D-A-Type Triphenylamine Derivatives.

To investigate the effect of polymerization (n = 1, 2, 3, and 4) on the charge-transfer (CT) mechanisms in the one (two)-photon absorption (OPA and TPA) process of D-A-type triphenylamine derivatives, charge density difference is used to graphically represent the CT characteristics. A transition density matrix is utilized to reveal the direction of CT on different groups quantitatively. With the n increasing, electrons are mainly transferred between the groups in the middle position of the molecular chain during OPA and TPA processes. Simulated results show that the energy gap and excitation energy have a good linear relationship with the reciprocal of the polymerization degree. Importantly, the polymerization effect can effectively increase the electronic transmission capability, TPA performance, and second hyperpolarizability. Besides, the simplified sum over state model reveals the variation factor of the TPA cross-section and the second static hyperpolarizability. The McRae formula and Bakhshiev formula are used to estimate the difference of dipole moments, which is an important parameter of the second hyperpolarizability. The comprehensive analysis of the nonlinear optical (NLO) parameters of triphenylamine derivatives can provide some significant guidance for molecular design and improve the NLO performance of D-A molecular materials. Also, the thermodynamic parameters can provide some theoretical supports for solving practical problems.

Effect of graphene between photoanode and sensitizer on the intramolecular and intermolecular electron transfer process.

The main goal of this work is to investigate the effects of a graphene layer between the photosensitive layer and semiconductor substrates on the electron transport performance of dye-sensitized solar cells from the perspective of intramolecular arrangement and interfaces. The benzothiadiazole sensitizer YKP-88 is used as the photosensitive layer and the influence of the graphene layer on the short-circuit current density (Jsc) and open-circuit voltage (Voc) is also discussed by exploring the frontier molecular orbitals, intramolecular charge transfer, weak interaction, interfacial electron dynamic propagations and other microscopic parameters after the anchoring of the graphene layer. The results demonstrate that the graphene layer can accelerate the electron injection of dye molecules into the semiconductor substrate, which not only has a qualitative reduction in injection time, but also has a qualitative change in the increase of the injection amount. In addition, it is also found that the graphene layer increases the stereoscopic effect, the absorption of long wavelength (>700 nm) photon flu and the amount of electron injection into the photoanode, which benefits the intramolecular charge transfer and increases the Jsc and Voc of solar cells. The combination of intermolecular and interfacial perspectives indicates that the appropriate configuration of graphene layers can effectively improve the photoelectric conversion efficiency of dye-sensitized solar cells.

Second-Order Nonlinear Optical Switch Manipulation of Photosensitive Layer by an External Electric Field Coupled with Graphene Quantum Dots.

The main purpose of this work is to explore the effect of graphene quantum dots (GR) filling the photosensitive layer. The multibranched dye JH-1 as the photoactive layer material was used to analyze the non-negligible role of graphene quantum dots from the perspectives of optimized structure, electrochemical parameters, optical properties, nonlinear optical (NLO) switch, and external electric field. The results demonstrated that the graphene quantum dots not only improve the optical properties of solar cells but also control the electron transfer in the photosensitive layer molecules under the manipulation of a specific external electric field. When the external electric field intensity is below 20 × 10-4 au, the excess electron orbital does not change. When the external electric field reaches 25 × 10-4 au, the excess electron orbital on the graphene quantum dots evolves. This discovery allows the electron transfer from the photosensitive layer, which should be controlled by the NLO switch. In addition, the optical properties of sensitizers showed regular evolution in the external electric field, which provides an effective way to improve the performance. Comprehensive analysis indicated that the doping of graphene quantum dots with the photosensitive layer can be used as a new way to improve the photoelectric conversion efficiency of solar cells.

Plasmon-Exciton Coupling Interaction for Surface Catalytic Reactions.

In this review, we firstly reveal the physical principle of plasmon-exciton coupling interaction with steady absorption spectroscopy, and ultrafast transition absorption spectroscopy, based on the pump-prop technology. Secondly, we introduce the fabrication of electro-optical device of two-dimensional semiconductor-nanostructure noble metals hybrid, based on the plasmon-exciton coupling interactions. Thirdly, we introduce the applications of plasmon-exciton coupling interaction in the field of surface catalytic reactions. Lastly, the perspective of plasmon-exciton coupling interaction and applications closed this review.

Charge-transfer channel in quantum dot-graphene hybrid materials.

The energy band theory of a classical semiconductor can qualitatively explain the charge-transfer process in low-dimensional hybrid colloidal quantum dot (QD)-graphene (GR) materials; however, the definite charge-transfer channels are not clear. Using density functional theory (DFT) and time-dependent DFT, we simulate the hybrid QD-GR nanostructure, and by constructing its orbital interaction diagram, we show the quantitative coupling characteristics of the molecular orbitals (MOs) of the hybrid structure. The main MOs are derived from the fragment MOs (FOs) of GR, and the Cd13Se13 QD FOs merge with the GR FOs in a certain proportion to afford the hybrid system. Upon photoexcitation, electrons in the GR FOs jump to the QD FOs, leaving holes in the GR FOs, and the definite charge-transfer channels can be found by analyzing the complex MOs coupling. The excited electrons and remaining holes can also be localized in the GR or the QD or transfer between the QD and GR with different absorption energies. The charge-transfer process for the selected excited states of the hybrid QD-GR structure are testified by the charge difference density isosurface. The natural transition orbitals, charge-transfer length analysis and 2D site representation of the transition density matrix also verify the electron-hole delocalization, localization, or coherence chacracteristics of the selected excited states. Therefore, our research enhances understanding of the coupling mechanism of low-dimensional hybrid materials and will aid in the design and manipulation of hybrid photoelectric devices for practical application in many fields.

Reaction Mechanism of Photodeamination Induced by Excited-State Intramolecular Proton Transfer of the Anthrol Molecule.

The photodeamination reaction of the anthrol molecule generating the high-activity quinone methide intermediate has been investigated ( J. Org. Chem. 2017 , 82 , 6006 - 6021 ), though lacking careful explanation for its reaction mechanism. In our research, the mechanism of the anthrol molecule photodeamination induced by excited-state intramolecular proton transfer was reported for the first time. Absorption and emission spectra calculated for the work presented here agreed well with experimental results. To propose a molecular-level explanation of the photodeamination reaction, we calculated bond parameters, corresponding infrared vibrational frequencies, Mayer bond orders, and visualized frontier molecular orbitals of different molecules, and the hydrogen bond strengthening behavior in excited states was confirmed, enhancing the excited state intramolecular proton transfer of the anthrol molecule. Moreover, we concluded that photoisomerization weakened the bond strength between nitrogen and carbon atoms, which promoted the photodeamination reaction. Finally, for visually and quantificationally revealing the photodeamination mechanism, we have established the three-dimensional potential energy surfaces for the deamination reaction in different electronic states and calculated the corresponding reaction Gibbs free energies, it can be confirmed that the photodeamination reaction of the anthrol molecule must be induced by a proton transfer reaction in the excited state.

Tuning the Electron-Transport and Electron-Accepting Abilities of Dyes through Introduction of Different π-Conjugated Bridges and Acceptors for Dye-Sensitized Solar Cells.

A series of dyes, containing thiophene and thieno[3,2-b]thiophene as π-conjugated bridging units and six kinds of groups as electron acceptors, were designed for dye-sensitized solar cells (DSSCs). The ground- and excited-state properties of the designed dyes were investigated by using density functional theory (DFT) and time-dependent DFT, respectively. Moreover, the parameters affecting the short-circuit current density and open-circuit voltage were calculated to predict the photoelectrical performance of each dye. In addition, the charge difference density was presented through a three-dimensional (3D) real-space analysis method to investigate the electron-injection mechanism in the complexes. Our results show that the longer conjugated bridge would inhibit the intramolecular charge transfer, thereby affecting the photoelectrical properties of DSSCs. Similarly, owing to the lowest chemical hardness, largest electron-accepting ability, dipole moment (µnormal ) and the change in the energy of the TiO2 conduction band (ΔECB ), the dye with a (E)-3-(4-(benzo[c][1,2,5]thiadiazol-4-yl)phenyl)-2-cyanoacrylic acid (TCA) acceptor group would exhibit the most significant photoelectrical properties among the designed dyes.

Vibronic quantized tunneling controlled photoinduced electron transfer in an organic solar cell subjected to an external electric field.

In this work, vibration-resolved photoinduced electron transfer of an organic conjugated DA system subjected to an external electric field was theoretically investigated. The ground and excited state vibrational relaxation energies were quantitatively characterized. The effective high frequency, ωeff, could be estimated from the variation in energy of the excited-state equilibrium geometries of acceptor and donor sites as well as the analysis of the vibrational modes upon electron transfer. For a PCDTBT:PC70BM blend in an external electric field, the vibronic modes affected the charge separation process differently from the charge recombination process. The simulated results indicated that the vibrational quantum tunneling effect facilitated the charge recombination process to a large extent. Thus, for electron transfer reactions, considering the vibrational excitation influence and perturbed nucleus-electron interactions is essential. These results provide a feasible way to enhance the efficiency in yielding the electron transfer process products.

Photoinduced Electron Transfer in Organic Solar Cells.

Electron transfer (ET) is the key process in light-driven charge separation reactions in organic solar cells. The current review summarizes the progress in theoretical modelling of ET in these materials. First we give an account of ET, with a description originating from Marcus theory. We systematically go through all the relevant parameters and show how they depend on different material properties, and discuss the consequences such dependencies have for the performance of the devices. Finally, we present a set of visualization methods which have proven to be very useful in analyzing the elementary processes in absorption and charge separation events. Such visualization tools help us to understand the properties of the photochemical and photobiological systems in solar cells.

A questionable excited-state double-proton transfer mechanism for 3-hydroxyisoquinoline.

Two excited state proton transfer mechanisms of 3-hydroxyisoquinoline (3HIQ) in cyclohexane and acetic acid (ACID) were investigated based on the time-dependent density functional theory (TDDFT), suggesting a different double-proton transfer mechanism from the one proposed previously (J. Phys. Chem. B, 1998, 102, 1053). Instead of the formation of keto-enol complexes for 3HIQ self-association in cyclohexane, our theoretical results predicted that 3HIQ self-association exists in two forms: the normal form (enol/enol) and the tautomer form (keto/keto) in cyclohexane. A high barrier (37.023 kcal mol(-1)) between the 3HIQ enol monomer and 3HIQ keto monomer form indicated that the 3HIQ keto monomer in the ground state should not exist. In addition, the constructed potential energy surfaces of the ground state and excited state have been used to explain the proton transfer process. Upon optical excitation, the enol/enol form is excited to the first excited state, then transfers one proton, in turn, transition to the ground state to transfer another proton. A relatively low barrier (8.98 kcal mol(-1)) demonstrates two stable structures in the ground state. In view of the acetic acid solvent effect, two protons of 3HIQ/ACID transfer along the dihydrogen bonds in the first excited state, which is a different transfer mechanism to 3HIQ self-association. In addition, the proton transfer process provides a possible explanation for the fluorescence quenching observed.

Organic nonlinear optical materials: the mechanism of intermolecular covalent bonding interactions of Kekulé hydrocarbons with significant singlet biradical character.

The ground- and excited-state properties of benzene-linked bisphenalenyl (B-LBP), naphthaline-linked bisphenalenyl (N-LBP), and anthracene-linked bisphenalenyl (A-LBP) Kekulé molecules and their respective one-dimensional (1D) stacks are investigated using time-dependent density functional theory (TD-DFT) and a range of extensive multidimensional visualization techniques. The results reveal a covalent π-π bonding interaction between overlapping phenalenyl radicals whose bond length is shorter than the van der Waals distance between carbon atoms. Increasing the linker length and/or number of molecules involved in the 1D stack decreases the HOMO-LUMO energy gap and increases the wavelength of the systems. The charge-transfer mechanism and electron coherence both differ with changes in the linker length and/or number of molecules involved in the 1D stack.

Optical absorption spectroscopy and electronic properties of D-A dyes and chlorophyll derivatives for co-sensitization in DSSCs.

The photophysical and photochemical processes of the experimental dyes ZS11 and ZS12 containing phenyl-cyanoacrylic acid (PCA) and ethynyl-PCA (EPCA) group were studied by DFT and TD-DFT systems to develop their applications in solar cells. First, their geometry, absorption spectra, chemical reaction parameters, electron transfer and dye activity were systematically studied. The photoelectric conversion efficiency (PCE) was predicted, and it was found that the PCE of ZS12 (9.974 %) was higher than ZS11 (7.171 %), which was consistent with the experimental trend (the PCE of ZS12 is 10.4 ± 0.3 % and the PCE of ZS11 is 9.0 ± 0.3 %). Secondly, the dye was co-sensitized with the chlorophyll derivative CHL-1c, and the co-sensitization system's interaction force, excited state characteristics, electron transfer mechanism and electron transfer rates were studied. The results show that the JSC of all co-sensitive systems (the JSC of ZS12-CHL is 22.363 mA/cm2 and the JSC of ZS11-CHL is 23.978 mA/cm2) is significantly higher than that of monomers (the JSC of ZS12 is 16.112 mA/cm2 and the JSC of ZS11 is 11.051 mA/cm2). It can be inferred that the optoelectronic performance of co-sensitizing systems is better than that of monomers. This study demonstrates that the use of dye molecules co-sensitized with chlorophyll derivatives can enhance DSSC performance from multiple perspectives, providing insights for further improvements.

Substituent effects on the ESIPT process and the potential applications in materials transport field of 2'-aminochalcone derivatives.

This work investigates the different charge transfer characteristics and excited state intramolecular proton transfer process (ESIPT) of 2'-aminochalcones derivatives carrying different electron-withdrawing groups. Four new molecules are designed in the experiment and named as 2c, 3c, 4c and 5c, respectively. (Dyes and Pigments, 2022, 202.) Based on these four molecules, the effect of substituents on the ESIPT process and the charge transfer process are discussed in detail in our work. According to the study of the related parameters at the hydrogen bond site, infrared vibration spectrum, interaction region indicator isosurface (IRI) and scatter plots, it is concluded that the hydrogen bond interaction is enhanced under photoexcitation, and the descending order of the excited state hydrogen bond strength is 3c > 5c > 4c > 2c. The hydrogen bond energy is calculated by atoms in moleculs (AIM) topological analysis and core-valence bifurcation (CVB) index. The potential energy curve reveals the ESIPT mechanism. Frontier molecular orbital and electron-hole analyses explain the reasons for the changes in the ESIPT process at the electronic level. In addition, the ionization potentials (IPa and IPv), affinity energies (EAa and EAv) and reorganization energies are calculated to evaluate the potential application value of organic molecules in material transport field.

Accurate double many-body expansion potential energy surface by extrapolation to the complete basis set limit and dynamics calculations for ground state of NH2.

An accurate single-sheeted double many-body expansion potential energy surface is reported for the title system. A switching function formalism has been used to warrant the correct behavior at the H2(X1Σg+)+N(2D) and NH (X3Σ-)+H(2S) dissociation channels involving nitrogen in the ground N(4S) and first excited N(2D) states. The topographical features of the novel global potential energy surface are examined in detail, and found to be in good agreement with those calculated directly from the raw ab initio energies, as well as previous calculations available in the literature. The novel surface can be using to treat well the Renner-Teller degeneracy of the 12A″ and 12A' states of NH 2. Such a work can both be recommended for dynamics studies of the N(2D)+H2 reaction and as building blocks for constructing the double many-body expansion potential energy surface of larger nitrogen/hydrogen-containing systems. In turn, a test theoretical study of the reaction N(2D)+H2(X1Σg+)(ν=0,j=0)→NH (X3Σ-)+H(2S) has been carried out with the method of quantum wave packet on the new potential energy surface. Reaction probabilities, integral cross sections, and differential cross sections have been calculated. Threshold exists because of the energy barrier (68.5 meV) along the minimum energy path. On the curve of reaction probability for total angular momentum J = 0, there are two sharp peaks just above threshold. The value of integral cross section increases quickly from zero to maximum with the increase of collision energy, and then stays stable with small oscillations. The differential cross section result shows that the reaction is a typical forward and backward scatter in agreement with experimental measurement result.

Effect of electronic acceptor segments on photophysical properties of low-band-gap ambipolar polymers.

Stimulated by a recent experimental report, charge transfer and photophysical properties of donor-acceptor ambipolar polymer were studied with the quantum chemistry calculation and the developed 3D charge difference density method. The effects of electronic acceptor strength on the structure, energy levels, electron density distribution, ionization potentials, and electron affinities were also obtained to estimate the transporting ability of hole and electron. With the developed 3D charge difference density, one visualizes the charge transfer process, distinguishes the role of molecular units, and finds the relationship between the role of DPP and excitation energy for the three polymers during photo-excitation.