How to regulate energy levels and hole mobility of spiro-type hole transport materials in perovskite solar cells.

Methoxyaniline-based organic small molecules with three-dimensional structure have been proven as the most promising hole conductor for state-of-the-art perovskite devices. A fundamental understanding of the electronic properties and hole transport behavior of spiro-CPDT analogues, which is dependent on the number and position of the -OCH3 groups, is significant for their potential applications as hole transport materials of perovskite solar cells. Our results from density functional theory calculations indicate that meta-substitution is more beneficial to reduce the highest occupied molecular orbital (HOMO) levels of molecules compared with ortho- and para-substitution. Furthermore, the hole mobility can be improved by ortho-substitution or mixed ortho- and para-substitution. Most interestingly, it is found that the improvement in hole mobility is at the expense of raising the HOMO level of spiro-CPDT analogues. These results can be useful in the process of designing and synthesizing excellent hole transport materials with suitable HOMO levels and high hole mobility.

Effects of water molecules on the chemical stability of MAGeI3 perovskite explored from a theoretical viewpoint.

The stability of perovskite in humid environments is one of the biggest obstacles for its potential applications in light harvesting and electroluminescent displays. Understanding the detailed degradation mechanism of MAGeI3 in moisture is a critical way to explore the practicability of MAGeI3 perovskite. In this study, we report a quantitative and systematic investigation of MAGeI3 degradation processes by exploring the effects of H2O molecules on the structural and electronic properties of the most stable MAGeI3(101) surface under various simulated environmental conditions with different water coverage based on first-principles calculations. The results show that H2O molecules can easily diffuse into the inner side of the perovskite and gradually corrode the structure as the number of H2O molecules increases. As a result of the interactions between perovskite and H2O molecules, a hydrated intermediate will be generated as the first step in the degradation mechanism; the perovskite will further decompose to HI and GeI2. In terms of one MAGeI3 molecule, it will be dissociated completely to GeI2 as a result of hydrolysis reactions with a minimum of 4H2O molecules. In addition, the degradation of the perovskite will also affect the electronic structure, causing a decrease in optical absorption across the visible region of the spectrum and a distinct deformation change in the crystal structure of the material. These findings further illustrate the degradation of the hydrolysis process of MAGeI3 perovskite in humid environments, which should be helpful to inspire experimentalists to take action to prolong the lifetimes of perovskite solar cells to achieve high conversion efficiency in their applications.

The theoretical investigation on the 4-(4-phenyl-4-α-naphthylbutadieny)-triphenylamine derivatives as hole transporting materials for perovskite-type solar cells.

The electronic structures, optical properties and hole mobilities of 4-(4-phenyl-4-α-naphthylbutadieny)-triphenylamine and its five derivatives are investigated by density functional theory (DFT). The results show that the highest occupied molecular orbital (HOMO) of all molecules is almost fully delocalized throughout the whole molecule, and the substituents -N(CH3)2 and -C6H5 denoted as molecules 6 and 2, respectively, have the largest contribution to the HOMO, which is favorable for hole transfer integral and hole mobility. Spectrum analysis indicates that all molecules have large Stokes shifts based on absorption and emission spectra. In addition, it is found that the hole reorganization energy of all molecules is about 0.5 times compared to that of electrons, which implies that hole mobility is bigger than electron mobility. On the basis of predicted packing motifs, the hole mobilities (u) of all molecules are also obtained. The largest hole mobility of molecule 2 (0.1063 cm(2) V(-1) s(-1)) is found to be higher than that of other molecules due to the face-to-face stacking mode, which suggests that -C6H5 is a good substituent group for improving hole mobility compared to other electron releasing groups. We hope that our results will be helpful for the further rational molecular design and synthesis of novel hole transport materials (HTMs) for high performance perovskite-type solar cells.

Strategy for designing stable and powerful nitrogen-rich high-energy materials by introducing boron atoms.

One of the most important aims in the development of high-energy materials is to improve their stability and thus ensure that they are safe to manufacture and transport. In this work, we theoretically investigated open-chain N4B2 isomers using density functional theory in order to find the best way of stabilizing nitrogen-rich molecules. The results show that the boron atoms in these isomers are aligned linearly with their neighboring atoms, which facilitates close packing in the crystals of these materials. Upon comparing the energies of nine N4B2 isomers, we found that the structure with alternating N and B atoms had the lowest energy. Structures with more than one nitrogen atom between two boron atoms had higher energies. The energy of N4B2 increases by about 50 kcal/mol each time it is rearranged to include an extra nitrogen atom between the two boron atoms. More importantly, our results also show that boron atoms stabilize nitrogen-rich molecules more efficiently than carbon atoms do. Also, the combustion of any isomer of N4B2 releases more heat than the corresponding isomer of N4C2 does under well-oxygenated conditions. Our study suggests that the three most stable N4B2 isomers (BN13, BN24, and BN34) are good candidates for high-energy molecules, and it outlines a new strategy for designing stable boron-containing high-energy materials. Graphical abstract The structural characteristics, thermodynamic stabilities, and exothermic properties of nitrogen-rich N4B2 isomers were investigated by means of density functional theory.

Exploring the electrochemical properties of hole transport materials with spiro-cores for efficient perovskite solar cells from first-principles.

Perovskite solar cells (PSCs) with organic small molecules as hole transport materials (HTMs) have attracted considerable attention due to their power conversion efficiencies as high as 20%. In the present work, three new spiro-type hole transport materials with spiro-cores, i.e. Spiro-F1, Spiro-F2 and Spiro-F3, are investigated by using density functional theory combined with the Marcus theory and Einstein relation. Based on the calculated and experimental highest occupied molecular orbital (HOMO) levels of 30 reference molecules, an empirical equation, which can predict the HOMO levels of hole transport materials accurately, is proposed. Moreover, a simplified method, in which the hole transport pathways are simplified to be one-dimensional, is presented and adopted to qualitatively compare the molecular hole mobilities. The calculated results show that the perovskite solar cells with the new hole transport materials can have higher open-circuit voltages due to the lower HOMO levels of Spiro-F1 (-5.31 eV), Spiro-F2 (-5.42 eV) and Spiro-F3 (-5.10 eV) compared with that of Spiro-OMeTAD (-5.09 eV). Furthermore, the hole mobilities of Spiro-F1 (1.75 × 10(-2) cm(2) V(-1) s(-1)) and Spiro-F3 (7.59 × 10(-3) cm(2) V(-1) s(-1)) are 3.1 and 1.4 times that of Spiro-OMeTAD (5.65 × 10(-3) cm(2) V(-1) s(-1)) respectively, due to small reorganization energies and large transfer integrals. Interestingly, the stability properties of Spiro-F1 and Spiro-F2 are shown to be comparable to that of Spiro-OMeTAD, and the dimers of Spiro-F2 and Spiro-F3 possess better stability than that of Spiro-OMeTAD. Taking into consideration the appropriate HOMO level, improved hole mobility and enhanced stability, Spiro-F1 and Spiro-F3 may become the most promising alternatives to Spiro-OMeTAD. The present work offers a new design strategy and reliable calculation methods towards the development of excellent organic small molecules as HTMs for highly efficient and stable PSCs.

A strategy to improve the efficiency of hole transporting materials: introduction of a highly symmetrical core.

The electronic, optical and hole transport properties of three new hole transporting materials (HTMs) with a planar core have been investigated by using density functional theory and Marcus theory. A reliable semi-rational formula was adopted to calculate the highest occupied molecular orbital (HOMO) levels of new HTMs. The results showed that the HOMO levels of new HTMs were 0.07-0.30 eV lower than those of Spiro-OMeTAD, and their absorption peaks appeared outside or close to the visible region and overlapped slightly with the absorption band of perovskites. Moreover, the Stokes shifts of the designing molecules were calculated to lie in a range from 72 to 124 nm, meaning that they could undergo large geometrical changes on excitation. More importantly, the hole mobility of new HTMs (0.099-0.27 cm2 v-1 s-1) was approximately two orders of magnitude higher than that of Spiro-OMeTAD (0.0056 cm2 v-1 s-1) due to strong hole coupling from a face-to-face packing pattern. Our results indicated that planar core-based HTMs could become potential candidates to replace the widely established Spiro-OMeTAD.

Looking for high energy density compounds among polynitraminecubanes.

Based on fully optimized geometric structures at DFT-B3LYP/6-311G** level, we calculated electronic structures, heats of formation, strain energies, bond dissociation energies and detonation performance (detonation velocity and detonation pressure) for a series of polynitraminecubanes. Our results have shown that energy gaps of cubane derivatives are much higher than that of triaminotrinitrobenzene (TATB), which means that cubane derivatives may be more sensitive than TATB. Polynitraminecubanes have high and positive heats of formation, and a good linear relationship between heats of formation and nitramine group numbers was presented. As the number of nitramine groups in the molecule increases, the enthalpies of combustion values are increasingly negative, but the specific enthalpy of combustion values decreases. It is found that all cubane derivatives have high strain energies, which are affected by the number and position of nitramine group. The calculated bond dissociation energies of C-NHNO(2) and C-C bond show that the C-C bond should be the trigger bond in the pyrolysis process. It is found that detonation velocity (D), detonation pressure (P) and molecule density (ρ) have good linear relationship with substituented group numbers. Heptanitraminecubane and octanitraminecubane have good detonation performance over 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX), and they can be regarded as potential candidates of high energy density compounds (HEDCs). The results have not only shown that these compounds may be used as HEDCs, but also provide some useful information for further investigation.

Theoretical investigation on detonation performances and thermodynamic stabilities of the prismane derivatives.

Based on DFT-B3LYP/6-311G** method, the molecular geometric structures of polynitramineprismanes are fully optimized. The detonation performances, energy gaps, strain energies, as well as their stability were investigated to look for high energy density compounds (HEDCs). Our results show that all polynitramineprismanes have high and positive heat of formation. To construct the relationship between stabilities and structures, energy gaps and bond dissociation energies are calculated, and these results show that the energy gaps of prismane derivatives are much higher than that of TATB (0.1630). In addition, the C-C bonds on cage are confirmed as trigger bond in explosive reaction. All polynitramineprismanes have large strain energies, and the strain energies of all compounds are slightly smaller than prismane, which indicated that the strain energies were somewhat released compared to prismane. Considering the quantitative criteria of HEDCs, hexanitramineprismane is a good candidate of high energy compounds.

Computational studies on polynitropurines as potential high energy density materials.

As part of a search for high energy density materials (HEDMs), a series of purine derivatives with nitro groups were designed computationally. The relationship between the structures and the performances of these polynitropurines was studied. Density functional theory (DFT) at the B3LYP/6-311G** level was employed to evaluate the heats of formation (HOFs) of the polynitropurines by designing an isodesmic reaction method. Results indicated that the HOFs were influenced by the number and positions of substituent groups. Detonation properties were evaluated using the Kamlet-Jacobs equations, based on the theoretical densities and heats of formation of the polynitropurines. The relative stabilities of the polynitropurines were studied via the pyrolysis mechanism and the UB3LYP/6-311G** method. Homolysis of the ring-NO2 bond is predicted to be the initial step in the thermal decomposition of these purine derivatives. Considering their detonation properties and relative stabilities, the tetranitropurine (D1) derivatives may be regarded as potential candidates for practical HEDCs. These results may provide useful information for further investigations.

Density functional calculations for a high energy density compound of formula C6H 6-n (NO 2) n.

A series of polynitroprismanes, C(6)H(6-n )(NO(2))(n) (n = 1-6) intended for use as high energy density compounds (HEDCs) were designed computationally. Their electronic structures, heats of formation, interactions between nitro groups, specific enthalpies of combustion, bond dissociation energies, and explosive performances (detonation velocities and detonation pressures) were calculated using density functional theory (DFT) with the 6-311 G** basis set. The results showed that all of the polynitroprismanes had high positive heats of formation that increased with the number of substitutions for the prismane derivatives, while the specific enthalpy of combustion decreased as the number of nitro groups increased. In addition, the range of enthalpy of combustion reducing is getting smaller. Interactions between ortho (vicinal) groups deviate from the group additivity rule and decrease as the number of nitro groups increases. In terms of thermodynamic stability, all of the polynitroprismanes had higher bond dissociation energies (BDEs) than RDX and HMX. Detonation velocities and detonation pressures were estimated using modified Kamlet-Jacobs equations based on the heat of detonation (Q) and the theoretical density of the molecule (ρ). It was found that ρ, D, and P are strongly linearly related to the number of nitro groups. Taking both their energetic properties and thermal stabilities into account, pentanitroprismane and hexanitroprismane are potential candidate HEDCs.