Specific features of dissipation of electronic excitation energy in coupled molecular solid systems based on silicon nanocrystals on intense optical pumping

A phenomenological model of transfer and dissipation of electronic excitation energy in the case of intense optical pumping of coupled systems based on arrays of silicon nanocrystals is developed. The calculated dependences of the relative concentrations of donors of energy and acceptors of energy on the intensity of optical pumping are compared with the experimental data on photoluminescence of structures containing silicon nanocrystals surrounded by oxygen molecules and erbium ions. From the comparison between the calculated and experimental dependences, the parameter of coupling of excitons in the silicon nanocrystals with the surrounding acceptors of energy is estimated.     

Native defects and dopants in gan studied through photoluminescence and optically detected magnetic resonance

Native defects and dopants in GaN grown by organometallic chemical vapor deposition have been studied with photoluminescence and optically detected magnetic resonance. For undoped samples, the combined results indicate the presence of residual shallow donors and acceptors and deep donors. A model for the capture and recombination among these defects is developed. For Mg-doped samples, the experiments reveal shallow and perturbed acceptors and shallow and deep donors. Hence, shallow and deep states for the native donor or donors appear in all samples. The Mg-acceptor is perturbed from its effective-mass state by nearby point defects.     

Effects of Halogenation of Small-Molecule and Polymeric Acceptors for Efficient Organic Solar Cells

Tuning the properties of non-fullerene acceptors (NFAs) through halogenation, including fluorination and chlorination, represents one of the most promising strategies to boost the performance of organic solar cells (OSCs). However, it remains unclear how the F and Cl choice influences the molecular packing and performance between small-molecule and polymeric acceptors. Here, a series of small-molecule and polymeric acceptors with different amounts and types of halogenation is synthesized, and the effects of fluorination and chlorination between small-molecule and polymeric acceptors are investigated. It is found that chlorinated small-molecule acceptors lead to longer exciton diffusion length and better performance compared to the corresponding fluorinated ones, which attributes to their stronger intermolecular packing mode. For polymer acceptors, in contrast, the fluorinated polymers achieve a denser packing mode and better performance, because chlorinated polymers exhibit reduced intrachain conjugation between end group moieties and linker units. This study demonstrates different halogenation effects on the packing modes and performances for small-molecule and polymeric acceptors, which provides important guidance for the molecule design of high-performance acceptors for OSCs.     

施受主共掺杂对BaTiO3陶瓷介电性能的影响

通过传统的球磨工艺,分别以MnCO3、Co2O3为受主杂质,La2O3、Nb2O5、Bi2(SnO3)3为施主杂质对BaTiO3陶瓷进行掺杂。实验表明,BaTiO3陶瓷介电性能跟施主杂质与受主杂质的比例有关。当施主杂质与受主杂质的比例较大时,介电常数-温度(-εT)曲线趋于平缓,BaTiO3陶瓷呈强铁电弥散性,介电损耗-温度(tan-δT)曲线趋于平滑,介电损耗-频率(tan-δf)曲线呈松弛极化损耗特性。当施主杂质与受主杂质的比例较小时,-εT曲线出现较大的居里峰值,BaTiO3陶瓷呈普通铁电体的性质,tan-δT曲线也出现较大峰值,tan-δf曲线表现为电导损耗特征。BaTiO3陶瓷晶粒的"核-壳结构"模型能较好地解释这一现象。     

Recent Developments of Polymer Solar Cells with Photovoltaic Performance over 17%

With the emergence of ADA'DA-type (Y-series) non-fullerene acceptors (NFAs), the power conversion efficiencies (PCEs) of organic photovoltaic devices have been constantly refreshed and gradually reached 20% in recent years (19% for single junction and 20% for tandem device). The acceptors possess specific design concept, which greatly enrich the NFA types and have excellent compatibility with many donor materials. It is gratifying to note that the previously underperforming donor materials combine with these regulated acceptors to shine again. Nowadays, the concept of modular design is widely used in the research of acceptors and donors, injecting new vitality into the field of organic photovoltaics. Furthermore, these acceptors also promote the research of multicomponent devices, tandem devices, bilayer devices, processing solvent engineering, and additive engineering. Herein, the latest progresses of polymer solar cells with efficiency over 17% are briefly reviewed from the aspects of active material design, interface material development, and device technology. At last, the opportunities and challenges of organic photovoltaic commercialization in the future are discussed.     

Enhancing the Photovoltaic Performance of Ladder-Type Heteroheptacene-based Nonfullerene Acceptors by Incorporating Halogen Atoms on Their Ending Groups

Ending group halogenation is an effective strategy for modulating the energy levels, bandgaps, and intermolecular interactions of nonfullerene acceptors. Understanding the influence of different halogen atoms on the acceptor properties is of great importance for designing high-performance nonfullerene acceptors. Here, three acceptor–donor–acceptor (A-D-A) type nonfullerene acceptors (M5, M6, and M7), which are constructed by using a ladder-type heteroheptacene core without the traditional sp³ carbon-bonded side chains as the electron-rich core, and 2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile without or with halogen atoms as the ending groups. The nonfullerene acceptors with chlorinated (M6) and brominated (M7) ending groups exhibit broadened absorption spectra, down-shifted energy levels, and enhanced molecular ordering compared to the counterpart without any halogenated ending groups (M5). Among the nonfullerene acceptors, M6 has the strongest intermolecular π π interaction with its shortest π π interaction distance and the longest coherent length which are beneficial for enhancing the charge transport and therefore boosting the photovoltaic performance. An excellent power conversion efficiency of 15.45% is achieved for the best-performing polymer solar cell based on M6. These results suggest that the halogenated ending groups are essential for high-performance heteroheptacene-based nonfullerene acceptors considering their simultaneous enhancements in both the light-harvesting and the charge transport.     

Optical and electrical properties of CdGeAs2

Large-grained ingots of CdGeAs₂ have been grown from near-stoichiometric melts. Resistivity and Hall coefficient (R_H) measurements were made on a large number of samples at 77 and 300 K and in some cases up to 450 K. Good fits to the log R_H vs 1/T plots are obtained by using a model that assumes three kinds of electronic levels within the energy gap: donors, shallow acceptors, and acceptors with an ionization energy of 0. 30 eV. The deep acceptors are probably native defects, since their concentration varies by nearly four orders of magnitude from ingot to ingot with little change in impurity concentration. Between the intrinsic absorption edge at about 2. 5 Μm and the two-phonon absorption band at 18 Μm, the optical absorption increases with increasing deep acceptor concentration. By using oriented single-crystal samples ∼ 1 cm on a side, conversion efficiencies as high as 27% have been achieved for second-harmonic generation with single-mode pulses from a CO₂ TEA laser.     

The Hall conductivity of graphene

Sensitivity of the Hall conductivity of graphene plane to gas molecule adsorption is investigated within the coherent potential approximation for the tight-binding model Hamiltonian. The results show that the Hall conductivity of system have a limit change when finite triatomic and tetratomic gas molecules adsorb and act as acceptors or donors.     

The investigations of two conjugated polymers that show distinctly different photovoltaic properties in polymer solar cells

In fullerene-free polymer solar cells (PSC), the non-fullerene small molecular acceptors (NF-SM) demonstrates quite different film morphology in comparison with the conventional fullerene acceptors when blended with the same conjugated polymer donor. In this work, a NF-SM acceptor, ITIC, was introduced into two efficient binary PSCs based on fullerene to fabricate ternary solar cells. It is found that the addition of ITIC led fundamentally different results. After carefully investigated the difference on film morphology and charge carriers' mobility, the results showed that the good miscibility between ITIC and the polymer may deteriorate the favorable film morphology with appropriate phase separation and suppress the formation of continues charge transport channel. This work offered a useful consideration to produce high-performance ternary PSCs by rational selecting the donors and acceptors.     

The substituents on the intermediate electron-deficient groups in small molecular acceptors result appropriate morphologies for organic solar cells

The small molecule acceptors with the structure of acceptor-donor acceptor' donor-acceptor (A−DA'D−A) boost the power conversion efficiency of organic solar cells. Compared with multifused DA'D core with an electron-deficient unit at the center, the unfused core emerges low cost and high yield. Herein, we designed and synthesized three small molecule acceptors named as TR2F-IC4F, BTOC8-IC4F and, BTOC6C8-IC4F, with an unfused core containing one benzothiadiazole (BT) or triazole (TR) unit and two cyclopentadithiophene (CPDT) units. The nearly planar geometry is realized through noncovalent F⋯H, F⋯S and S⋯O interactions. These acceptors have broad near-infrared absorption. For devices with BTOC8-IC4F, TR2F-IC4F and BTOC6C8-IC4F, the highest PCEs are only 5.81%, 5.89% and 7.55%, respectively. For devices with BTOC6C8-IC4F, the PCEs are further improved to 10.01% for ternary cells, which add PC₇₁BM into devices. In this work, we found with the increase of the substituents on the intermediate electron-donating groups, the planarity of the molecules become weaken, but can obtain more compatible with the donor molecules, which could result in the different film-forming properties and morphologies in blending films. This work provides a typical example of introducing unfused core into small molecule acceptors, which is important to design new solution-processable small molecule acceptors in the future.     

An analysis of the shape of a luminescence band induced by transitions of free electrons to carbon atoms in semi-insulating undoped GaAs crystals

The shape of a photoluminescence band observed due to recombination of free electrons at shallow-level acceptors (carbon atoms) in semi-insulating undoped GaAs crystals was analyzed at various temperatures (T=4.8–77 K). It is shown that at low temperatures the shape observed essentially differs from the theoretical one, while at high temperatures theory and experiment agree closely for radiative transitions of free electrons to isolated shallow-level acceptors. The difference between the experimental and theoretical shapes of the photoluminescence band is associated with the broadening of carbon-induced acceptor levels (i.e., with the formation of the acceptor impurity band), resulting from the effect of electric fields of randomly distributed ionized acceptors and donors on “isolated” carbon atoms. Coincidence of the shapes is associated with a considerable increase in the energy of free carriers (to values up to and above the width of the acceptor impurity band).     

Thermal diffusion of lithium acceptors into ZnO crystals

Electron paramagnetic resonance (EPR) has been used to monitor the diffusion of lithium ions into single crystals of ZnO. The in-diffusion occurs when a crystal is embedded in LiF powder and then held in air at temperatures near 750°C for periods of time ranging up to 22 h. These added lithium ions occupy zinc sites and become singly ionized acceptors (because the material is initially n type). A corresponding reduction in the number of neutral shallow donors is observed with EPR. To monitor the lithium acceptors, we temporarily convert them to the EPR-active neutral acceptor state by exposure to laser light (325 nm or 442 nm) at low temperatures. Also, after each diffusion treatment, we monitor the EPR signal of singly ionized copper acceptors and the photo-induced EPR signal of neutral nitrogen acceptors. These nitrogen and copper impurities are initially present in the crystal, at trace levels, and are made observable by the thermal anneals. Infrared-absorption measurements at room temperature in the 2–10 μm region show that the concentration of free carriers decreases as lithium is added to the crystal. After 22 h at 750°C in the LiF powder, the free-carrier absorption is no longer present, and the crystal is semi-insulating.     

Enhancing the performance of non-fullerene solar cells with polymer acceptors containing large-sized aromatic units

In this work, we develop four diketopyrrolopyrrole-based polymer acceptors for application in polymer-polymer solar cells. The polymer acceptors contain different-sized aromatic units, from small thiophene to benzodithiophene and large alkylthio-benzodithiophene units. Although the polymer acceptor with large-sized groups shows small LUMO offset and low energy loss when blended with the donor polymer PTB7-Th, the corresponding solar cells can achieve a high power conversion efficiency (PCE) of 3.1% due to high photocurrent. In contrast, the polymer acceptor with small thiophene units only provides a low PCE of 0.14% in solar cells. These results indicate that polymer acceptors with large-sized aromatic units can be potentially used into high performance non-fullerene solar cells.     

Temperature dependence of the atomic structure and electrical activity of defects in ZnSb thermoelectric lightly doped with copper

A model for describing the temperature dependence of the defect microstructure in high-efficiency ZnSb thermoelectric with a copper content of 0.1 at % is chosen. The temperature dependences of the chargecarrier density and mobility for thermal cycle I (300–700–300 K) are analyzed taking into account the features of the crystal structure and covalent chemical bond in ZnSb. The basic defect structure (at temperatures of T = 560–605 K) is the state when all Cu atoms are equally distributed between sites of both sublattices and behave as acceptors, and the number of intrinsic donor and acceptor defects is much smaller. The effect of the latter becomes noticeable when the temperature goes beyond the above-mentioned range. At T > 605 K, extra acceptors (antisite Zn_Sb) occur; upon cooling below 560 K, Cu₂ dimers arise and the electrical activity of the impurity lowers. Dimer decay upon heating leads to growth in the concentration with temperature up to saturation in the above-mentioned range. Additional thermal cycles II–VIII are performed; the observed changes in the temperature dependences of the hole concentration and mobility are discussed in the context of the investigated model.     

Tuning the optical absorption of potential blue emitters

The quest for more efficient blue emitters to be applied in organic light-emitting diodes is one of the challenging tasks of contemporary nanotechnologies. An approach to enhance substantially the intrinsic efficiency of luminescent organic molecules is the so-called thermally activated delayed fluorescence. A prerequisite for its occurrence is a vanishing energy separation between the first singlet and triplet excited states. A series of donor–acceptor molecules is investigated theoretically within this study in order to validate a molecular model for design of efficient organic blue emitters with closely spaced singlet and triplet excited states. The model is based on meta-linkage of the donor and acceptor residues to a spacer ensuring frontier molecular orbitals partitioning. The optimal geometries of the molecules are obtained with density functional theory (B3LYP/6-31G^*) and the singlet and triplet absorption spectra are simulated within the time-dependent density functional framework. The excited singlet-triplet energy gap is estimated and correlated to structural and energetic characteristics of the donors and acceptors. Several requirements for achieving high-energy triplet states at the molecular level in such donor–acceptor systems are outlined, the main being disjoint character of the molecular orbitals on the spacer and sufficient energy separation of the two topmost occupied orbitals. It is shown that by variation of the acceptor moiety the optical absorption transitions of the compounds can be fine-tuned in a systematic fashion. Molecules with degenerate singlet and triplet first excited states are proposed, combining bisdimethylaminotriphenylamine or phenoxazine as donors with diphenyloxadiazole or diphenyl-2,2′-bipyridine as acceptors. Bipolar molecules derived from this model could be used as prospective building blocks for efficient emissive materials in blue organic light-emitting diodes.     

Poly(2,2’-(2,5-difluoro-1,4-phenylene)dithiophene-alt-naphthalene diimide) synthesized by direct (hetero)arylation reaction for all-polymer solar cells

The weak donor-strong acceptor polymer acceptors for all-polymer solar cells (all-PSCs) have gained much less attention compared with the typical donor-strong acceptor counterparts. Direct (hetero)arylation polymerization reaction is a rising synthetic method, although most of the naphthalene diimide polymer photovoltaic acceptors have been prepared by classic Stille polymerization. A weak donor-strong acceptor polymer acceptor PNB2F has been successfully designed and synthesized by the two-step direct (hetero)arylation reaction and further applied in all-PSCs. The all-PSC device based on PNB2F and electron-donating polymer PBDB-T gained a PCE of 4.49%. The results demonstrate that direct (hetero)arylation reaction is a promising tool for building efficient polymer acceptors with convenient and low-cost synthesis ideas.     

Relaxation of a defect subsystem in silicon irradiated with high-energy heavy ions

The relaxation of a silicon defect subsystem modified by the implantation of high-energy heavy ions was studied by varying the electrical properties of irradiated Si crystal annealed at a temperature of 450°C. It is shown that quenched-in acceptors are introduced into Si crystals as a result of irradiation with comparatively low doses of Bi ions and subsequent relatively short annealing (no longer than 5 h); the distribution of these quenched-in acceptors has two peaks located at a depth of about 10 μm and at a depth corresponding approximately to the ions’ projected range (43.5 μm). The peaks in the distribution of quenched-in acceptors correspond to the regions enriched with vacancy-containing defects. As the heat-treatment duration increases, the acceptor centers are transformed into donor centers with the centers’ spatial distribution remaining intact. Simultaneously, an almost uniform introduction of quenched-in donors occurs in the entire crystal beyond the depth corresponding to the projected range of ions. __________ Translated from Fizika i Tekhnika Poluprovodnikov, Vol. 37, No. 5, 2003, pp. 565–569. Original Russian Text Copyright ? 2003 by Smagulova, Antonova, Neustroev, Skuratov.     

p-to-n type-conversion mechanisms for HgCdTe exposed to H2/CH4 plasmas

The role of hydrogen incorporation in H₂/CH₄ reactive ion etching (RIE) induced type-conversion of p-type HgCdTe is investigated. A model is proposed in which hydrogen is incorporated into the HgCdTe crystal lattice in at least three different forms. It is proposed that the junction formation mechanism is a mixture of RIE-induced damage and Hg interstitial formation to which hydrogen forms strong bonds, and hydrogen-induced neutralization of acceptors. Confirmation of the model is presented based on experimental secondary ion mass spectroscopy of RIE-induced junctions, transport measurements reported previously, and initial diode bake stability testing.     

High-Efficiency Organic Solar Cells Based on a Low-Cost Fully Non-Fused Electron Acceptor

A series of tetrathiophene-based fully non-fused ring acceptors (4T-1, 4T-2, 4T-3, and 4T-4), which can be paired with the star donor polymer PBDB-T to fabricate highly efficient organic solar cells are developed. Tailoring the size of lateral chains can tune the solubility and packing mode of acceptor molecules in neat and blend films. It is found that the incorporation of 2-ethylhexyl chains can effectively change the compatibility with the donor polymer PBDB-T, and an encouraging power conversion efficiency of 10.15% is accomplished by 4T-3-based organic solar cells. It also presents good compatibility with the other polymer donor and an even higher power conversion efficiency (PCE) of 12.04% is achieved based on D18:4T-3 blend, which is the champion PCE for the fully non-fused acceptors. Importantly, these inexpensive tetrathiophene fully non-fused ring acceptors provide cost-effective photovoltaic performance. The results demonstrate a high photovoltaic performance from synthetically inexpensive materials could be achieved by the rational design of non-fused ring acceptor molecules.