Photogeneration Quantum Yield Research Articles

New Theoretical Model to Describe Carrier Multiplication in Semiconductors: Explanation of Disparate Efficiency in MoTe2 versus PbS and PbSe.

We present a theoretical model to compute the efficiency of the generation of two or more electron-hole pairs in a semiconductor by the absorption of one photon via the process of carrier multiplication (CM). The photogeneration quantum yield of electron-hole pairs is calculated from the number of possible CM decay pathways of the electron and the hole. We apply our model to investigate the underlying cause of the high efficiency of CM in bulk 2H-MoTe2, as compared to bulk PbS and PbSe. Electronic band structures were calculated with density functional theory, from which the number of possible CM decay pathways was calculated for all initial electron and hole states that can be produced at a given photon energy. The variation of the number of CM pathways with photon energy reflects the dependence of experimental CM quantum yields on the photon energy and material composition. We quantitatively reproduce experimental CM quantum yields for MoTe2, PbS, and PbSe from the calculated number of CM pathways and one adjustable fit parameter. This parameter is related to the ratio of Coulomb coupling matrix elements and the cooling rate of the electrons and holes. Large variations of this fit parameter result in small changes in the modeled quantum yield for MoTe2, which confirms that its high CM efficiency can be mainly attributed to its extraordinary large number of CM pathways. The methodology of this work can be applied to analyze or predict the CM efficiency of other materials.

Disorder and Photogeneration Efficiency in Organic Semiconductors.

An analytical description of the separation probability of a geminate pair in organic semiconductors is given. The initial diffusion of "hot" twins is anomalously strong due to energy disorder. This circumstance significantly increases the photogeneration quantum yield at low temperatures and weakens its temperature dependence relative to predictions of the Onsager model, in agreement with Monte Carlo and experimental results.

Benzo[A]Pyrene and Benzo[E]Pyrene: Photoreactivity and Phototoxicity toward Human Keratinocytes.

Polycyclic aromatic hydrocarbons (PAHs) are a group of organic compounds derived mostly from the incomplete combustion of fossil fuels and biomass. Human skin can absorb PAHs and the uptake increases with their molar mass and lipophilicity. Benzopyrene is high molecular weight PAH frequently appearing in ambient pollution. It exists in two isomeric forms: benzo[a]pyrene (BaP) and benzo[e]pyrene (BeP), which exhibit different biological activity. Although certain properties of benzopyrenes suggested photoreactivity of the compounds, no direct measurements were previously conducted to characterize their photochemical activity. In this study, quantum yield and action spectra of singlet oxygen photogeneration by BaP and BeP were measured by time-resolved near-infrared phosphorescence, and the ability of both compounds to photogenerate superoxide anion was assessed by electron paramagnetic resonance (EPR) spin-trapping. The measurements revealed high efficiency of benzopyrenes to photogenerate singlet oxygen and their ability to photogenerate superoxide anion. Using HaCaT cells as single-layer skin model, we demonstrated concentration-dependent and light-dependent cytotoxicity of BaP and BeP. The compounds induced damage to the cell mitochondria and elevated the levels of intracellular reactive oxygen species.

Determination of Photoinduced Radical Generation Quantum Efficiencies by Combining Chemical Actinometry and 19F NMR Spectroscopy.

We introduce a general and relatively straightforward protocol aimed at determining the absolute photoinduced radical generation efficiency via NMR monitoring. This approach relies on the use of a radical scavenger probe that combines a nitroxide moiety that specifically reacts with radicals and a trifluoromethyl group used as a 19F NMR signaling unit. Using an LED source, whose fluence is precisely determined by a chemical actinometry procedure also described herein, the method is used to determine the radical photogeneration quantum yields of three well-known polymerization initiators: azobisisobutyronitrile (AIBN), 4,4'-bis(N,N-diethylamino)benzophenone (BDEBP, a derivative of Michler's ethyl ketone), and 2,4,6-trimethylbenzoyl diphenylphosphine oxide (MAPO). The overall good agreement with values previously reported in the literature proves the robustness of this new method. We then extended the study to the precise measurement of the quantum yield of free-radical photogeneration on a newly synthesized photoinitiator used for two-photon direct laser writing. This study highlights the potential of this methodology for the quantitative determination of photoinduced radical generation efficiency used in many fields of applications.

Photogeneration Quantum Yield and Character of Free Charges and Excitons in PbSe Nanorods

Lead selenide (PbSe) nanorods are of interest for applications in infrared LEDs, lasers, and photovoltaics due to the possibility of tuning their band gap from the far- to the near-infrared by decr...

Applications of Photoswitches in the Storage of Solar Energy

AbstractPhotoswitches are organic or organometallic chromophores that undergo a reversible chemical transformation upon absorption of light. Among the most commonly studied photoswitches are stilbenes and azobenzenes, capable of efficient interconversion between cis and trans isomers. When one isomer is significantly less thermodynamically stable than the other, photoisomerization of the stable to the metastable isomer converts a fraction of the absorbed photon energy into excess free energy (chemical potential). If the metastable isomer is sufficiently inert at room temperature, its photoconversion provides a means of storing solar energy, which is recovered by triggering heat‐releasing thermal conversion of the metastable to the stable isomer. In other words, such a photoswitch acts as a battery that captures solar energy, stores it as chemical potential and releases it on demand as heat. This process is known as molecular solar thermal energy storage or a molecular solar thermal battery. Unlike the more established conventional solar thermal storage, which uses sunlight to heat, melt or vaporize material, molecular solar thermal energy storage does not require thermal insulation to prevent discharge but relies on the kinetic activation barrier separating the two isomers. Unlike solar‐to‐chemical energy conversion by photosplitting of H2O or photoreduction of CO2, which comprise open‐system cycles, photoswitches are thermodynamically closed storage media. Successful deployment of molecular solar thermal energy storage requires new photoswitches that combine a seemingly contradictory set of molecular parameters: a large difference in the free energies of the two isomers separated by a large kinetic barrier; a high quantum yield of photogeneration of the metastable isomer that itself is either photochemically inactive or transparent to sunlight; highly selective isomerizations that allow many charge/discharge cycles without accumulation of side‐products even at high discharge temperatures. While the optimal photoswitch for molecular solar thermal energy storage remains to be invented, a large body of empirical observations acquired in the past decade provides several potentially valuable starting points for such a search.

Diphosphine-induced chiral propeller arrangement of gold nanoclusters for singlet oxygen photogeneration

In this study, 1,2-bis(diphenylphosphino)ethane (dppe) ligands are used to synthesize gold nanoclusters with an icosahedral Au13 core. The nanoclusters are characterized and formulated as [Au13(dppe)5Cl2]Cl3 using synchrotron radiation X-ray diffraction, UV/Vis absorption spectroscopy, electrospray ionization mass spectrometry, and density functional theory (DFT) calculations. The bidentate feature of dppe ligands and the positions of coordinating surface gold atoms induce a helical arrangement that forms a propeller-like structure, which reduces the symmetry of the gold nanocluster to C1. Therefore, dppe ligands perform as a directing agent to create chiral an ansa metallamacrocycle [Au13(dppe)5Cl2]3+ nanocluster, as confirmed by simulated electronic circular dichroism spectrum. The highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) gap of the [Au13(dppe)5Cl2]3+ cluster is determined as approx. 1.9 eV, and further confirmed by ultraviolet photoemission spectroscopy analysis and DFT simulation. Furthermore, the photoactivity of [Au13(dppe)5Cl2]3+ is investigated, with the nanocluster shown to possess near-infrared photoluminescence properties, which can be employed for 1O2 photogeneration. The quantum yield of 1O2 photogeneration using the [Au13(dppe)5Cl2]3+ nanocluster is up to 0.71, which is considerably higher than those of anthracene (an organic dye), and Au25 and Au38 nanoclusters.

Magnetic Spin Effects in Photoprocesses inside Polymeric Photoconductors

Magnetic spin effects are detected and studied in the processes of sensitized current-carrier photogeneration and luminescence inside polymer photoconductor films based on polyimides and composites of polymers with carbazole moieties combined with electron acceptors (chemical sensitization) and dyes (spectral sensitization). The effect an electric field has on the quantum yield of photogeneration and the luminescence of excited charge-transfer complexes (reversible and irreversible effects) at spectral sensitization is studied in the presence of O2.

Shell Thickness Engineering Significantly Boosts the Photocatalytic H2 Evolution Efficiency of CdS/CdSe Core/Shell Quantum Dots.

Colloidal semiconductor quantum dots (QDs) have recently emerged as a good candidate for photocatalytic hydrogen (H2) evolution in water. A further understanding of the factors that can affect and boost the catalytic activity of the QD-based H2-generating system is of great importance for the future design of such systems for practical use. Here, we report on the fine shell thickness engineering of colloidal CdS/CdSe core/shell QDs and its effect on the photocatalytic H2 production in water. Our results show that, with the proper shell thickness, the H2 photogeneration quantum yield (ΦH2) of CdS/CdSe core/shell QDs could reach 30.9% under the illumination of 420 nm light, which is 49% larger than that of the CdS core. Furthermore, the underlying mechanism has also been tentatively proposed and discussed.

On the mechanisms of photogeneration of charge carriers in PEPC-C60 composites

Photogeneration of electric charge carriers at high strengths of the external electric field and the temperature of transition to the viscous-flow state (T visc) of thin PEPC-C60 composite films obtained by casting from a toluene solution have been studied. The rheology of the composite films has been investigated by the nondestructive optical method. The consistent correlated change in the values of T visc and the effective temperature in the expression for the photogeneration quantum yield (T 0) in the Meltz representation with variations in the C60 concentration has been established. The difference between T visc and T 0 in thin composite films does not exceed 2–3% of T visc (T 0).

Influence of bimolecular recombination on the photogeneration yield values determined by xerographic method

Xerographic method consists in monitoring of decay of the surface potential of the photoconducting layer under illumination. The charge carrier photogeneration quantum yield is determined basing on the initial potential decay rate. In this work the photogeneration quantum yield for theoretically simulated initial surface potential decay is analyzed for a case when simultaneous photogeneration and recombination occur. A model disordered organic photoconductor is considered in which the photogeneration probability is described by the Onsager model of geminate recombination and the cross-section for recombination exhibits power dependence on the electric field. Photogeneration yields calculated in the classical way and the yields calculated with assumed bimolecular recombination are compared. It is shown that for high bimolecular recombination probability correctly determining the classical xerographic method of photogeneration quantum yield is difficult.

Carbazole-containing polyphenylquinolines as a basis for optoelectronic materials with white luminescence

The photophysical properties of poly-2,2′-(1-dodecyl carbazole-4,7-yl)-6,6′-(oxy)-bis-(4-phenylquinoline) in a solution, as a film, and in a poly(methyl methacrylate) or poly-N-vinylcarbazole host matrix have been studied. Considerable positive solvatochromism in the photoluminescence spectra, compared with solvatochromism in the absorption spectra, indicates that the dipole moment of the donor-acceptor complex increases in the excited state. Calculations show that the dipole moments of the complex in the ground and excited states differ by more than an order of magnitude. Upon transition to films, photoluminescence is observed in the entire visible spectral range (white luminescence). The intensity of the white luminescence grows by an order of magnitude when the polymer is dispersed in a poly(methyl methacrylate) matrix. The integrated photosensitivity and parameters of the photogeneration process (quantum yield of carrier photogeneration, quantum yield of free carrier formation, and thermalization radii) have been determined.

Photophysical and electrical properties of polyphenylquinolines containing carbazole or indolo[3,2-b]carbazole fragments as new optoelectronic materials

Photophysical and electrical properties of new synthesized 2,6-polyphenylquinolines (PPQs) containing an oxygen or phenylamine bridging group between quinoline cycles and, as an arylene radical, alkylated derivatives of carbazole or indolo[3,2-b]carbazole are studied. It is shown that the photosensitivity for new PPQs is 104–105 cm2/J and the photogeneration quantum yield of free carriers is as high as 0.15. Photophysical parameters increase with the phenylamine bridging group in place of the oxygen one and when using indolocarbazole instead of carbazole. It is found that a film of polyphenylquinoline containing an oxygen bridging group and an alkylcarbazole fragment in the polymer repeat unit exhibits “white” luminescence. Both electron and hole transport with a mobility of ∼10−6 cm2/(V s) are detected in films of all studied polymers. The conductivity value and type can be controlled by varying the chemical structure of the (oxygen or phenylamine) bridging group between PPQ cycles and by choosing carbazole or indolo[3,2-b]carbazole derivatives as an arylene radical.

Photophysical properties of indolo[3,2-b]carbazoles as a promising class of optoelectronic materials

The photophysical properties of new synthesized indolocarbazoles, i.e., indolo[3,2-b]carbazole and its derivatives, have been comparatively analyzed. It is shown that their photosensitivity (total photosensitivity to (5–8) × 10−2 (lx s)−1, spectral photosensitivity ∼105 cm2 J−1, and free carrier photogeneration quantum yield of 0.1) and transport (effective mobility in 5,11-dioctyl indolo[3,2-b]carbazole is more than 10−5 cm2/(V s)) parameters significantly exceed those of pentacene, which, among molecular media (organic crystals), exhibits the highest carrier photogeneration quantum yields. The high photoluminescence intensity of synthesized indolo[3,2-b]carbazole derivatives shows promise for their applicability in electroluminescent devices.

Structural features of the photogeneration mechanism of free charge carriers in element-containing polydisalicylidene azomethine series

Photophysical properties of new polytetra- and polydisalicylidene azomethines (PSAMs) with chains containing Si, Ge, Sn, or transition metal atoms and atoms of a number of other divalent metals are studied. Based on data on ultraviolet and infrared spectra, it was found that the noncovalent transannular donor-acceptor interaction N M (M is semimetal or metal) occurs in polymers, which leads to the formation of a polymer chain of six-membered cycles. As a result, polyconjugations arise in PSAMs by a “non-classical” mechanism. Due to multiple donor-acceptor interactions of unshared electron pairs of azomethine groups with vacant d-orbitals in metals, polymers feature conductive, photosensitive, and photoconductive properties. The photosensitivity and quantum yield of photogeneration of free charge carriers for PSAMs are close to the values characteristic of classical conducting polymers. It was shown that the PSAM properties are controlled by the azomethine fragment structure and acceptor properties of metal. A mechanism of free carrier photogeneration was suggested.

Temperature-Independent Charge Carrier Photogeneration in P3HT−PCBM Blends with Different Morphology

The effect of temperature on the quantum yield for charge carrier photogeneration in P3HT−PCBM blend films was studied using ultrafast transient absorption and microwave photoconductance techniques. The quantum yield was found to be virtually independent of temperature for time scales up to tens of nanoseconds after photoexcitation of P3HT. Implications of this observation for the mechanism of free charge carrier generation are discussed. The decay of charges due to recombination and/or trapping on longer times becomes faster at higher temperature, as a result of thermally activated electron and hole mobilities. The magnitude of the quantum yield depends on the morphology of the blend film, which is determined by the spin-coating solvent and annealing conditions.

Supercrystals of CdSe Quantum Dots with High Charge Mobility and Efficient Electron Transfer to TiO2

Thermal annealing of thin films of CdSe/CdS core/shell quantum dots induces superordering of the nanocrystals and a significant reduction of the interparticle spacing. This results in a drastic enhancement of the quantum yield for charge carrier photogeneration and the charge carrier mobility. The mobile electrons have a mobility as high as 0.1 cm(2)/(V x s), which represents an increase of 4 orders of magnitude over non-annealed QD films and exceeds existing literature data on the electron mobility in CdSe quantum dot films. The lifetime of mobile electrons is longer than that of the exciton. A fraction of the mobile electrons gets trapped at levels below the conduction band of the CdSe nanocrystals. These electrons slowly diffuse over 50-300 nm on longer times up to 20 micros and undergo transfer to a TiO2 substrate. The yield for electron injection in TiO2 from both mobile and trapped electrons is found to be >16%.

Cage Effect Dynamics under Photolysis of Photoinitiators

The efficiency of photoinitiators depends upon the quantum yield of photogeneration of reactive free radicals and the cage effect value. Only radicals that escape the cage can initiate free radical polymerization. The modern concept of the cage effect is presented. Dependencies of the cage effect upon increasing of solvent viscosity in the course of polymerization are discussed. Cage effect dynamics or kinetics of geminate recombination is of special interest. Results of a kinetic study on the cage effect using ns laser flash photolysis are described.

Photogeneration and Ultrafast Dynamics of Excitons and Charges in P3HT/PCBM Blends

The photogeneration quantum yield and dynamics of charge carriers and excitons in thin films of neat regioregular poly(3-hexylthiophene) (P3HT) and blends with [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) were studied with ultrafast optical pump−probe spectroscopy. In neat P3HT the quantum yield for direct photogeneration of charge carriers amounts to 0.15 per absorbed photon. The remaining fraction of absorbed photons leads to formation of excitons. Recombination of charges reduces the quantum yield to about 25% of its initial value on a time scale of 100 ps followed by decay to a no longer observable yield after 1 ns. Addition of 50% PCBM by weight leads to ultrafast (<200 fs) formation of charge pairs with a total quantum yield of 0.5. The presence of 50% PCBM causes exciton decay to be about an order of magnitude faster than in neat P3HT, which is expected to be at least in part due to interfacial exciton dissociation into charge carriers. The yield of charges in the blend has decayed to about ha...

Photoelectric and electrical properties of soluble polyphenylquinolines containing an oxygen or phenylamine bridge group between quinoline moieties

Photoelectric and electrical properties of polyphenylquinolines differing in the structure of donor bridge groups between quinoline moieties have been studied. It is demonstrated that films of the polymers synthesized exhibit a photosensitivity at the level of 105 cm2 J−1 (integrated sensitivity 5 × 10−4 lx−1 · s−1), with a quantum yield of carrier photogeneration of 0.07 and a carrier drift mobility on the order of 10−6 cm2 V−1 s−1. The fact that the electron and hole drift mobilities in polyphenylquinoline with a phenylamine bridge group are balanced makes the polymer promising for development of film-type devices based on the bipolar conductivity of a material (e.g., single-layer light-emitting diode).