Enhanced performance of P3HT/TiO2 bilayer heterojunction photovoltaic device having gold nanoparticles in the donor layer

The photovoltaic effects of blending gold nanoparticles (AuNPs) into the donor layer of a poly(3-hexylthiophene) (P3HT)/TiO2 bilayer heterojunction device have been studied. P3HT was synthesized via the modified Gragnard metathesis method and AuNPs with sizes ranging from 12 to 15 nm were formed via a reduction of HAuCl4. The blending of AuNPs into P3HT caused a lower photoluminescence (PL) intensities and a decreased energy level of the highest occupied molecular orbital (HOMO) than the pristine P3HT owing to the good electron-accepting nature of AuNPs. Upon the use of P3HT-AuNPs as the donor layer, the decreased HOMO(donor) resulted in an increased open circuit voltage (V(OC)) and thus enabled the fabricated (P3HT-AuNPs)/TiO2 bilayer heterojunction photovoltaic device to have an improved power conversion efficiency of solar energy. V(OC) as well as the overall power conversion efficiency increased with an increase in the AuNP content as a result of additional interfaces which facilitated the charge separation of excitons and percolation pathways which enhanced the electron transfer to the TiO2 acceptor. Furthermore, unannealed P3HT-AuNPs exhibited nanoholes and provided photovoltaic devices a power conversion efficiency nearly two time higher than annealed P3HT-AuNPs.     

Ab initio simulation of Si-doped GaAs(110) cross-sectional surfaces

We study different configurations of the (110) cross-sectional surface of Si-doped GaAs, from the isolated Si donor up to an entire donor–acceptor Si bilayer embedded along the (001) growth direction. Electronic potentials, density of electronic states, cross-sectional scanning tunneling microscopy (XSTM) images are calculated using first-principles numerical simulations. Doping configurations with compensating Si impurities in cationic and anionic sites, such as the donor–acceptor bilayer, are characterized by XSTM images with bright signal at negative bias, strongly attenuated when the bias is reversed. These features are characteristic of real samples above the onset of self-compensation. The comparison of the experimental images with the numerical simulations allows to shed light on the microscopic picture of self compensation hitherto associated to a variety of mechanisms – including the formation of complexes of Si with native defects – and to uniquely attribute the observed experimental features to Si donor–acceptor configurations.     

Balanced Partnership between Donor and Acceptor Components in Nonfullerene Organic Solar Cells with >12% Efficiency

Relative to electron donors for bulk heterojunction organic solar cells (OSCs), electron acceptors that absorb strongly in the visible and even near‐infrared region are less well developed, which hinders the further development of OSCs. Fullerenes as traditional electron acceptors have relatively weak visible absorption and limited electronic tunability, which constrains the optical and electronic properties required of the donor. Here, high‐performance fullerene‐free OSCs based on a combination of a medium‐bandgap polymer donor (FTAZ) and a narrow‐bandgap nonfullerene acceptor (IDIC), which exhibit complementary absorption, matched energy levels, and blend with pure phases on the exciton diffusion length scale, are reported. The single‐junction OSCs based on the FTAZ:IDIC blend exhibit power conversion efficiencies up to 12.5% with a certified value of 12.14%. Transient absorption spectroscopy reveals that exciting either the donor or the acceptor component efficiently generates mobile charges, which do not suffer from recombination to triplet states. Balancing photocurrent generation between the donor and nonfullerene acceptor removes undesirable constraints on the donor imposed by fullerene derivatives, opening a new avenue toward even higher efficiency for OSCs.     

Simple indoline based donor–acceptor dye for high efficiency dye-sensitized solar cells

A simple metal-free donor–acceptor type sensitizer U01, bearing strong electron donor indoline-triphenylamine was synthesized for panchromatic sensitization of TiO₂ nanocrystalline film. Photovoltaic properties of U01 showed remarkably enhanced light harvesting due to the presence of strong electron donor and robust structure. The new U01 sensitized solar cell exhibited a photovoltaic performance: a short-circuit photocurrent density (J_sc) of 10.70 mA cm⁻², an open-circuit photovoltage (V_oc) of 0.758 V and a fill factor (FF) of 0.74, corresponding to an overall conversion efficiency of 6.01% under standard global AM 1.5 solar light condition. Our results suggest that indoline-triphenylamine based robust D–A molecular architecture is a highly promising class of panchromatic sensitizers for improvement of the performance of dye-sensitized solar cells (DSCs).     

Controlling molecular weight of naphthalenediimide-based polymer acceptor P(NDI2OD-T2) for high performance all-polymer solar cells

A widely-used naphthalenediimide(NDI) based electron acceptor P(NDI2OD-T2) with different numberaverage molecular weight(M_n) of 38(N2200_L), 56(N2200_M), 102(N2200_H) kD a were successfully prepared.The effect of molecular-weight on the performance of all-polymer solar cells based on Poly(5-(5-(4,8-bis(5-decylthiophen-2-yl)-6-methylbenzo[1,2-b:4,5-b']dithophen-2-yl)thiophen-2-yl)-6,7-difluoro-8-(5-methylthiophen-2-yl)-2,3-bis(3-(octyloxy)phenyl)quinoxaline)(P2F-DE):N2200 was systematically investigated. The results reveal that N2200 with increased Mn show enhanced intermolecular interactions, resulting in improved light absorption and electron mobility. However, the strong aggregation trend of N2200_H can cause unfavorable morphology for exciton dissociation and carrier transport. The blend film using N2200 with moderate Mn actually develops more ideal phase segregation for efficient charge separation and transport, leading to balanced electron/hole mobility and less carrier recombination. Consequently, all-polymer solar cells employing P2F-DE as the electron donor and N2200_M as the electron acceptor show the highest efficiency of 4.81%, outperforming those using N2200_L(3.07%)and N2200_H(3.92%). Thus, the Mn of the polymer acceptor plays an important role in all-polymer solar cells, which allows it to be an effective parameter for the adjustment of the device morphology and efficiency.     

The significance of fullerene electron acceptors in organic solar cell photo-oxidation

Stability of organic solar cells requires development before their commercialisation is possible. This review will give a brief overview of organic solar cells and their stability, before focussing on the photochemical stability of the active layer. The photo-oxidation of the donor polymers will be looked at first which has been studied quite extensively and then fullerene electron acceptors, such as widely used phenyl-C61-butyric acid methyl ester, which has been considerably less studied. It has been shown that oxidation of the fullerene cage on phenyl-C61-butyric acid methyl ester results in oxides with a deeper lowest unoccupied molecular orbital (LUMO) level than the fresh electron acceptor. These oxides act as electron traps, leading to deterioration of the blend photoconductivity. The significance of fullerene photo-oxidation on device stability has been indirectly shown via research on: photoconductivity; organic solar cells made with an oxidised fullerene derivative and organic field effect transistors. Techniques that could be developed to increase photochemical stability of fullerene electron acceptor resistance to photo-oxidation include: reducing its LUMO level; increasing its crystallinity or aggregation and changing its chemical structure. Improving the photochemical stability of organic solar cells would move us one step closer to a more accessible solar power.     

Influence of position of auxiliary acceptor in D–A–π–A photosensitizes on photovoltaic performances of dye-sensitized solar cells

Several novel indoline dyes configured with donor–acceptor–bridge–acceptor (D–A–π–A) structures were designed and applied to organic dye-sensitized solar cells. These D–A–π–A dye molecules are composed of indoline (electron donating group), benzothiadiazole (BDT) (auxiliary acceptor), two furan rings (π-conjugated group), and 2-cyanoacrylic acid (electron accepting group). The influence of position of auxiliary acceptor in D–A–π–A organic sensitizer on the performance of photosensitize is investigated in detail. Calculated results show that the sensitizer could achieve a red-shifted absorption in long-wavelength region and a stronger absorption in short-wavelength region when the position of auxiliary acceptor changes from the donor to the acceptor. Moreover, among these dyes, WS-12, whose auxiliary acceptor nearing the 2-cyanoacrylic acid, possesses the better performance in terms of the charge transfer characteristics, lifetime of excited state as well as the vertical dipole moment when compared with WS-1 and WS-11. We hope that the present results could provide theoretical guidance for designing photosensitizes with higher efficiencies.     

Electron transfer quenching of excited pyrene or Ru(II)(bpy)3 derivative in Langmuir-Blodgett films by donor or acceptor molecules with different redox potentials

By using nanosecond laser photolysis, the luminescence decay curves were recorded for a sensitizer such as pyrene and Ru(bpy)²⁺₃ derivatices (where bpy is bypyridine) confined in one monolayer in Langmuir-Blodgett (LB) films which also contained the other monolayer of an acceptor or a donor surfactant deposited apart from the sensitizer monolayer by a fixed distance. In addition to the distinct difference of 1.0 V in the oxidation potentials between the excited pyrene and the Ru(bpy)²⁺₃ derivatives, the redox potentials of four types of acceptor and one donor used in the present study ranged widely up to 1.8 V width. This enabled us to examine the dependence of the photoinduced electron transfer rates on the standard free energy difference δG° of the reaction.

The rate constants calculated from the analysis of the decay curves will be discussed also in terms of the structure of the LB films and the distance between the sensitizer and the acceptor (or donor) monolayer.     

Cover Picture: Novel Photoactive Single‐Walled Carbon Nanotube–Porphyrin Polymer Wraps: Efficient and Long‐Lived Intracomplex Charge Separation (Adv. Mater. 7/2005)

The figure on the cover portrays a novel donor–acceptor nanoassembly, based on a single‐walled carbon nanotube (SWNT) as the electron acceptor and poly(methyl methacrylate) (PMMA)‐carrying porphyrin units (H2P) as the excited‐state electron donors. In these supramolecular “polymer wraps”, reported on p. 871 by Guldi and co‐workers, SWNTs quench the photoexcited H2P chromophores, resulting in the creation of microsecond‐lived radical ion pairs.     

Diketopyrrolopyrrole-based π-bridged donor-acceptor polymer for photovoltaic applications

We report the synthesis, properties, and photovoltaic applications of a new conjugated copolymer (C12DPP-π-BT) containing a donor group (bithiophene) and an acceptor group (2,5-didodecylpyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione), bridged by a phenyl group. Using cyclic voltammetry, we found the energy levels of C12DPP-π-BT are intermediate to common electron donor and acceptor photovoltaic materials, poly (3-hexylthiophene-2,5-diyl) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM), respectively. Whereas P3HT and PCBM are exclusively electron donating or accepting, we predict C12DPP-π-BT may uniquely serve as either an electron donor or an acceptor when paired with PCBM or P3HT forming junctions with large built-in potentials. We confirmed the ambipolar nature of C12DPP-π-BT in space charge limited current measurements and in C12DPP-π-BT:PCBM and C12DPP-π-BT:P3HT bulk heterojunction solar cells, achieving power conversion efficiencies of 1.67% and 0.84%, respectively, under illumination of AM 1.5G (100 mW/cm(2)). Adding diiodooctane to C12DPP-π-BT:PCBM improved donor-acceptor inter-mixing and film uniformity, and therefore enhanced charge separation and overall device efficiency. Using higher-molecular-weight polymer C12DPP-π-BT in both C12DPP-π-BT:PCBM and C12DPP-π-BT:P3HT devices improved charge transport and hence the performance of the solar cells. In addition, we compared the structural and electronic properties of C12DPP-π-BT:PCBM and C12DPP-π-BT:P3HT blends, representing the materials classes of polymer:fullerene and polymer:polymer blends. In C12DPP-π-BT:PCBM blends, higher short circuit currents were obtained, consistent with faster charge transfer and balanced electron and hole transport, but lower open circuit voltages may be reduced by trap-assisted recombination and interfacial recombination losses. In contrast, C12DPP-π-BT:P3HT blends exhibit higher open circuit voltage, but short circuit currents were limited by charge transfer between the polymers. In conclusion, C12DPP-π-BT is a promising material with intrinsic ambipolar characteristics for organic photovoltaics and may operate as either a donor or acceptor in the design of bulk heterojunction solar cells.     

Design of a New Small‐Molecule Electron Acceptor Enables Efficient Polymer Solar Cells with High Fill Factor

Improving the fill factor (FF) is known as a challenging issue in organic solar cells (OSCs). Herein, a strategy of extending the conjugated area of end‐group is proposed for the molecular design of acceptor–donor–acceptor (A–D–A)‐type small molecule acceptor (SMA), and an indaceno[1,2‐b:5,6‐b′]dithiophene‐based SMA, namely IDTN, by end‐capping with the naphthyl fused 2‐(3‐oxocyclopentylidene)malononitrile is synthesized. Benefiting from the π‐conjugation extension by fusing two phenyls, IDTN shows stronger molecular aggregation, more ordered packing structure, thus over one order of magnitude higher electron mobility relative to its counterpart. By utilizing the fluorinated polymer (PBDB‐TF) as the electron donor, the corresponding device exhibits a high efficiency of 12.2% with a record‐high FF of 0.78, which is approaching the theoretical limit of OSCs. Compared with the reference molecule, such a high FF in the IDTN system can be mainly attributed to the more ordered π–π packing of acceptor aggregates, higher domain purity and symmetric carrier transport in the blend. Hence, enlarging the conjugated area of the terminal‐group in these A–D–A‐type SMAs is a promising approach not only for enhancing the electron mobility, but also for improving the blend morphology, and both of them are conducive to the fill‐factor breakthrough.     

Triphenylene‐Derived Electron Acceptors and Donors on Ag(111): Formation of Intermolecular Charge‐Transfer Complexes with Common Unoccupied Molecular States

Over the past years, ultrathin films consisting of electron donating and accepting molecules have attracted increasing attention due to their potential usage in optoelectronic devices. Key parameters for understanding and tuning their performance are intermolecular and molecule–substrate interactions. Here, the formation of a monolayer thick blend of triphenylene‐based organic donor and acceptor molecules from 2,3,6,7,10,11‐hexamethoxytriphenylene (HAT) and 1,4,5,8,9,12‐hexaazatriphenylenehexacarbonitrile (HATCN), respectively, on a silver (111) surface is reported. Scanning tunneling microscopy and spectroscopy, valence and core level photoelectron spectroscopy, as well as low‐energy electron diffraction measurements are used, complemented by density functional theory calculations, to investigate both the electronic and structural properties of the homomolecular as well as the intermixed layers. The donor molecules are weakly interacting with the Ag(111) surface, while the acceptor molecules show a strong interaction with the substrate leading to charge transfer and substantial buckling of the top silver layer and of the adsorbates. Upon mixing acceptor and donor molecules, strong hybridization occurs between the two different molecules leading to the emergence of a common unoccupied molecular orbital located at both the donor and acceptor molecules. The donor acceptor blend studied here is, therefore, a compelling candidate for organic electronics based on self‐assembled charge‐transfer complexes.     

Analytical transmission electron microscopy at organic interfaces

Organic materials are ubiquitous in all aspects of our daily lives. Increasingly there is a need to understand interactions between different organic phases, or between organic and inorganic materials (hybrid interfaces), in order to gain fundamental knowledge about the origin of their structural and functional properties. In order to understand the complex structure–property–processing relationships in (and between) these materials, we need tools that combine high chemical sensitivity with high spatial resolution to allow detailed interfacial characterisation. Analytical transmission electron microscopy (TEM) is a powerful and versatile technique that can fulfil both criteria. However, the application of analytical TEM to organic systems presents some unique challenges, such as low contrast between phases, and electron beam sensitivity. In this review recent analytical TEM approaches to the nanoscale characterisation of two systems will be discussed: the hybrid collagen/mineral interface in bone, and the all-organic donor/acceptor interface in OPV devices.     

Bioinspired detection of light using a porphyrin-sensitized single-wall nanotube field effect transistor

Single-wall carbon nanotube (SWNT) field effect transistors (FETs), functionalized noncovalently with a zinc porphyrin derivative, were used to directly detect a photoinduced electron transfer (PET) within a donor/acceptor (D/A) system. We report here that the SWNTs act as the electron donor and the porphyrin molecules as the electron acceptor. The magnitude of the PET was measured to be a function of both the wavelength and intensity of applied light, with a maximum value of 0.37 electrons per porphyrin for light at 420 nm and 100 W/m2. A complete understanding of the photophysics of this D/A system is necessary, as it may form the basis for applications in artificial photosynthesis and alternative energy sources such as solar cells.     

Crystal structure,nonlinear optical and photophysical properties of a novel chromophore constructed with terpyridine,triphenylamine and ethyl cyanocaetate functional moieties

A novel chromophore (Z)-ethyl-3-(4-((4-([2,2′:6′,2″-terpyridin]-4′-yl)phenyl) (phenyl) amino)phenyl)-2-cyanoacrylate(3), constructed with triphenylamine moiety as the electron donor (D), 2, 2: 6, 2-terpyridine moiety as an electron acceptor (A), and ethyl cyanocaetate group as an auxiliary electron acceptor (A′), has been designed and synthesized. The crystal structures of 3 and its mediator 2 (4″-(4′-(4-(Diphenylamino) phenyl) aldehyde)-2,2′:6′,2″-Terpyridine), have been determined by single crystal X-ray diffraction analysis. The linear and nonlinear spectra of these chromophores were investigated on the basis of experimental and calculation methods. The two-photon absorption (TPA) cross-sections of 1–3 were determined by a femtosecond open-aperture Z-scan technique. The maximum value of the TPA cross-section (σ) for 3 is 7938.3 GM in DMF solution. However, much weaker two-photon absorption responses were observed at the same condition for chromophore 1 and 2, respectively. The results of the work indicate that, the photophysical properties of the D–A configuration group are influenced largely by the auxiliary moiety (A′) attached.     

BaTiO3基PTCR陶瓷中Bi2O3蒸汽掺杂和Mn的协同作用

BaTiO3基陶瓷材料的PTCR效应与施受主掺杂密切相关。通过BaTiO3、Sb2O3等蒸汽掺杂，材料的PTCR效应可以得到提高。然而，蒸汽掺杂之后，PTCR效应提高的幅度在含受主Mn的材料中比纯施主掺杂的材料中要大得多。这与BaTiO3蒸汽掺杂和Mn协同作用密切相关。这种协同作用可能进一步形成三阶Mn或中性钡缺位相关的更为稳定的复合缺陷，从而增大了电子捕获中心的浓度，使材料PTCR效应大幅提高。     

Intramolecular Electron Transfers in Donor/Acceptor Linked Molecules Based on Endohedral Lanthanide Metallofullerenes

Chemical syntheses and intramolecular electron transferring behaviors in the electron donor/acceptor conjugates based on endohedral metallofullerenes, La₂@C₈₀ and La@C₈₂, are overviewed. A study on the photo-induced excited states of a La₂@C₈₀ derivative connected with an electron donor revealed the formation of a distinct radical ion pair state. A La@C₈₂ derivative linked with an electron donor demonstrated an unprecedented ion/anion pair state, and La₂@C₈₀ tethered with an acceptor showed a fullerene donor system, in which the fullerene acts as an electron donor. Using endohedral lanthanide metallofullerenes for intramolecular electron transferring systems opens a new door for developing novel molecular materials.     

An organic donor/acceptor lateral superlattice at the nanoscale

A precise control of the nanometer-scale morphology in systems containing mixtures of donor/acceptor molecules is a key factor to improve the efficiency of organic photovoltaic devices. Here we report on a scanning tunneling microscopy study of the first stages of growth of 2-[9-(1,3-dithiol-2-ylidene)anthracen-10(9H)-ylidene]-1,3-dithiole, as electron donor, and phenyl-C61-butyric acid methyl ester, as electron acceptor, on a Au(111) substrate under ultrahigh vacuum conditions. Due to differences in bonding strength with the substrate and different interactions with the Au(111) herringbone surface reconstruction, mixed thin films spontaneously segregate into a lateral superlattice of interdigitated nanoscale stripes with a characteristic width of about 10-20 nm, a morphology that has been predicted to optimize the efficiency of organic solar cells.     

Enhanced light harvesting from Först-type resonance energy transfer in the quasi-solid state dye-sensitized solar cells

The demonstrated F?rst-type resonance energy transfer (FRET) is demonstrated in quasi-solid type dye-sensitized solar cells between organic fluorescence materials as an energy donor doped in polymeric gel electrolyte and a ruthenium complex as an energy acceptor on the surface of TiO2. Strong spectral overlap of emission/absorption of the energy donor and acceptor is required to obtain high FRET efficiency. The judicious choice of the energy donor allows the enhancement of the light harvesting characters of the energy acceptor (N3) in quasi-solid dye sensitized solar cells which increases the power conversion efficiency by 25% compare to that of a pristine cell. The optimized cell architecture fabricated with the quasi-solid type electrolyte containing fluorescence materials shows a maximum efficiency of 5.08% with a short-circuit current density (J(sc)) of 12.63 mA/cm2, and an open-circuit voltage (V(oc)) of 0.70 V under illumination of simulated solar light (AM 1.5, 100 mW/cm2).     

Surface plasmon enhanced energy transfer between donor and acceptor CdTe nanocrystal quantum dot monolayers

Surface plasmon enhanced Fo?rster resonant energy transfer (FRET) between CdTe nanocrystal quantum dots (QDs) has been observed in a multilayer acceptor QD-gold nanoparticle-donor QD sandwich structure. Compared to a donor-acceptor QD bilayer structure without gold nanoparticles, the FRET rate is enhanced by a factor of 80 and the Fo?rster radius increases by 103%. Furthermore, a strong impact of the donor QD properties on the surface plasmon mediated FRET is reported.