Design Rule of Electron- and Hole-Selective Contacts for Polycrystalline Silicon-Based Passivating Contact Solar Cells.

A crystalline silicon (c-Si) solar cell with a polycrystalline silicon/SiOx (poly-Si/SiOx) structure, incorporating both electron and hole contacts, is an attractive choice for achieving ideal carrier selectivity and serving as a fundamental component in high-efficiency perovskite/Si tandem and interdigitated back-contact solar cells. However, our understanding of the carrier transport mechanism of hole contacts remains limited owing to insufficient studies dedicated to its investigation. There is also a lack of comparative studies on the poly-Si/SiOx electron and hole contacts for ideal carrier-selective solar cells. Therefore, this study aims to address these knowledge gaps by exploring the relationship among microstructural evolution, dopant in-diffusion, and the resulting carrier transport mechanism in both the electron and hole contacts of poly-Si/SiOx solar cells. Electron (n+ poly-Si/SiOx/substrate)- and hole (p+ poly-Si/SiOx/substrate)-selective passivating contacts are subjected to thermal annealing. Changes in the passivation properties and carrier transport mechanisms of these contacts are investigated during thermal annealing at various temperatures. Notably, the results demonstrate that the passivation properties and carrier transport mechanisms are strongly influenced by the microstructural evolution of the poly-Si/SiOx layer stack and dopant in-diffusion. Furthermore, electron and hole contacts exhibit common behaviors regarding microstructural evolution and dopant in-diffusion. However, the hole contacts exhibit relatively inferior electrical properties overall, mainly because both the SiOx interface and the p+ poly-Si are found to be highly defective. Moreover, boron in the hole contacts diffuses deeper than phosphorus in the electron contacts, resulting in deteriorated carrier collection. The experimental results are also supported by device simulation. Based on these findings, design rules are suggested for both electron and hole contacts, such as using thicker SiOx and/or annealing the solar cell at a temperature not exceeding the critical annealing temperature of the hole contacts.

Thermal annealing effects on tunnel oxide passivated hole contacts for high-efficiency crystalline silicon solar cells.

Tunnel oxide passivated contacts (TOPCon) embedding a thin oxide layer between polysilicon and base crystalline silicon have shown great potential in the development of solar cells with high conversion efficiency. In this study, we investigate the formation mechanism of hole-carrier selective contacts with TOPCon structure on n-type crystalline silicon wafers. We explore the thermal annealing effects on the passivation properties in terms of the stability of the thermally-formed silicon oxide layer and the deposition conditions of boron-doped polysilicon. To understand the underlying principle of the passivation properties, the active dopant in-diffusion profiles following the thermal annealing are investigated, combined with an analysis of the microscopic structure. Based on PC1D simulation, we find that shallow in-diffusion of boron across a robust tunnel oxide forms a p-n junction and improves the passivation properties. Our findings can provide a pathway to understanding and designing high-quality hole-selective contacts based on the TOPCon structure for the development of highly efficient crystalline silicon solar cells.

Optical Characterization and Prediction with Neural Network Modeling of Various Stoichiometries of Perovskite Materials Using a Hyperregression Method.

Quaternary perovskite solar cells are being extensively studied, with the goal of increasing solar cell efficiency and securing stability by changing the ratios of methylammonium, formamidinium, I3, and Br3. However, when the stoichiometric ratio is changed, the photoelectric properties reflect those of different materials, making it difficult to study the physical properties of the quaternary perovskite. In this study, the optical properties of perovskite materials with various stoichiometric ratios were measured using ellipsometry, and the results were analyzed using an optical simulation model. Because it is difficult to analyze the spectral pattern according to composition using the existing method of statistical regression analysis, an artificial neural network (ANN) structure was constructed to enable the hyperregression analysis of n-dimensional variables. Finally, by inputting the stoichiometric ratios used in the fabrication and the wavelength range to the trained artificial intelligence model, it was confirmed that the optical properties were similar to those measured with an ellipsometer. The refractive index and extinction coefficient extracted through the ellipsometry analysis show a tendency consistent with the color change of the specimen, and have a similar shape to that reported in the literature. When the optical properties of the unmodified perovskite are predicted using the verified artificial intelligence model, a very complex change in pattern is observed, which is impossible to analyze with a general regression method. It can be seen that this change in optical properties is well maintained, even during rapid variations in the pattern according to the change in composition. In conclusion, hyperregression analysis with n-dimensional variables can be performed for the spectral patterns of thin-film materials using a simple big data construction method.

Fully Bottom-Up Waste-Free Growth of Ultrathin Silicon Wafer via Self-Releasing Seed Layer.

The fabrication of ultrathin silicon wafers at low cost is crucial for advancing silicon electronics toward stretchability and flexibility. However, conventional fabrication techniques are inefficient because they sacrifice a large amount of substrate material. Thus, advanced silicon electronics that have been realized in laboratories cannot move forward to commercialization. Here, a fully bottom-up technique for producing a self-releasing ultrathin silicon wafer without sacrificing any of the substrate is presented. The key to this approach is a self-organized nanogap on the substrate fabricated by plasma-assisted epitaxial growth (plasma-epi) and subsequent hydrogen annealing. The wafer thickness can be independently controlled during the bulk growth after the formation of plasma-epi seed layer. In addition, semiconductor devices are realized using the ultrathin silicon wafer. Given the high scalability of plasma-epi and its compatibility with conventional semiconductor process, the proposed bottom-up wafer fabrication process will open a new route to developing advanced silicon electronics.

Formation and suppression of hydrogen blisters in tunnelling oxide passivating contact for crystalline silicon solar cells.

The formation of hydrogen blisters in the fabrication of tunnelling oxide passivating contact (TOPCon) solar cells critically degrades passivation. In this study, we investigated the formation mechanism of blisters during the fabrication of TOPCons for crystalline silicon solar cells and the suppression of such blisters. We tested the effects of annealing temperature and duration, surface roughness, and deposition temperature on the blister formation, which was suppressed in two ways. First, TOPCon fabrication on a rough surface enhanced adhesion force, resulting in reduced blister formation after thermal annealing. Second, deposition or annealing at higher temperatures resulted in the reduction of hydrogen in the film. A sample fabricated through low-pressure chemical vapor deposition at 580 °C was free from silicon-hydrogen bonds and blisters after the TOPCon structure was annealed. Remarkably, samples after plasma-enhanced chemical vapor deposition at 300, 370, and 450 °C were already blistered in the as-deposited state, despite low hydrogen contents. Analysis of the hydrogen incorporation, microstructure, and deposition mechanism indicate that in plasma-enhanced chemical vapor deposition (PECVD) deposition, although the increase of substrate temperature reduces the hydrogen content, it risks the increase of porosity and molecular-hydrogen trapping, resulting in even more severe blistering.

Performance of Hybrid Energy Devices Consisting of Photovoltaic Cells and Thermoelectric Generators.

The aim of our study on hybrid energy devices (HEDs) is to find out the prerequisites for enhancing the performance of the HEDs using solar energy. In this work, first of all, the performance of the HEDs composed of photovoltaic cells (PVCs) and thermoelectric generators (TEGs) is analyzed, and then the contribution of three different interfaces between the PVC and TEG components to HED performance is assessed under solar irradiance from 200 to 1000 W/m2. The significant result of the analysis emphasizes that the performance of HEDs is enhanced when short-circuit current in HEDs is comparable with the PVCs and the thermoelectric voltage generated by the TEG is large. Furthermore, interfaces with high solar-energy-absorption efficiencies and high thermal conductivity cause TEGs to generate large thermoelectric voltages. Thus, the design of the interfaces plays an important role in enhancing HED performance.

Structural evolution of tunneling oxide passivating contact upon thermal annealing.

We report on the structural evolution of tunneling oxide passivating contact (TOPCon) for high efficient solar cells upon thermal annealing. The evolution of doped hydrogenated amorphous silicon (a-Si:H) into polycrystalline-silicon (poly-Si) by thermal annealing was accompanied with significant structural changes. Annealing at 600 °C for one minute introduced an increase in the implied open circuit voltage (Voc) due to the hydrogen motion, but the implied Voc decreased again at 600 °C for five minutes. At annealing temperature above 800 °C, a-Si:H crystallized and formed poly-Si and thickness of tunneling oxide slightly decreased. The thickness of the interface tunneling oxide gradually decreased and the pinholes are formed through the tunneling oxide at a higher annealing temperature up to 1000 °C, which introduced the deteriorated carrier selectivity of the TOPCon structure. Our results indicate a correlation between the structural evolution of the TOPCon passivating contact and its passivation property at different stages of structural transition from the a-Si:H to the poly-Si as well as changes in the thickness profile of the tunneling oxide upon thermal annealing. Our result suggests that there is an optimum thickness of the tunneling oxide for passivating electron contact, in a range between 1.2 to 1.5 nm.

Characterizing microscale aluminum composite layer properties on silicon solar cells with hybrid 3D scanning force measurements.

This article presents a novel technique to estimate the mechanical properties of the aluminum composite layer on silicon solar cells by using a hybrid 3-dimensional laser scanning force measurement (3-D LSFM) system. The 3-D LSFM system measures the material properties of sub-layers constituting a solar cell. This measurement is critical for realizing high-efficient ultra-thin solar cells. The screen-printed aluminum layer, which significantly affects the bowing phenomenon, is separated from the complete solar cell by removing the silicon (Si) layer with deep reactive ion etching. An elastic modulus of ~15.1 GPa and a yield strength of ~35.0 MPa for the aluminum (Al) composite layer were obtained by the 3-D LSFM system. In experiments performed for 6-inch Si solar cells, the bowing distances decreased from 12.02 to 1.18 mm while the Si layer thicknesses increased from 90 to 190 µm. These results are in excellent agreement with the theoretical predictions for ultra-thin Si thickness (90 µm) based on the obtained Al composite layer properties.

Effects of Current-injection Firing with Ag Paste in a Boron Emitter.

A high contact resistance for screen-printed contacts was observed when a conventional Ag paste was used on a boron emitter. The results of this study suggest that electron injection during firing is one of the processes that contribute to a lower contact resistance. Larger quantities of Ag precipitates formed upon electron injection into the boron emitter, which was confirmed by observing Ag crystallite or dendrite structures on the boron and by measuring the contact resistance between the boron emitter and the Ag bulk. The electron-injected sample had approximately 10000 times lower contact resistance than an untreated sample. The contact resistance of the electron-injected sample was 0.021 mΩ âˆ™ cm(2) under optimal conditions, which is lower than that of conventional p-type silicon solar cells. Thus, electron injection can effectively lower contact resistance when using Ag paste in n-type silicon solar cells. During the cooling in the firing process, dissolved Ag ions in the glass layer are formed as dendrites or crystallites/particles. The dendrites are formed earlier than others via electrochemical migration under electron injection conditions. Then, crystallites and particles are formed via a silicon etching reaction. Thus, Ag ions that are not formed as dendrites will form as crystallites or particles.

Electrostatic-Force-Assisted Dispensing Printing to Construct High-Aspect-Ratio of 0.79 Electrodes on a Textured Surface with Improved Adhesion and Contact Resistivity.

As a novel route to construct fine and abnormally high-aspect-ratio electrodes with excellent adhesion and reduced contact resistivity on a textured surface, an electrostatic-force-assisted dispensing printing technique is reported and compared with conventional dispensing and electrohydrodynamic jet printing techniques. The electrostatic force applied between a silver paste and the textured surface of a crystalline silicon solar cell wafer significantly improves the physical adhesion of the electrodes, whereas those fabricated using a conventional dispensing printing technique peel off with a silver paste containing 2 wt% of a fluorosurfactant. Moreover, the contact resistivity and dimensionless deviation of total resistance are significantly reduced from 2.19 ± 1.53 mΩ · cm(2) to 0.98 ± 0.92 mΩ · cm(2) and from 0.10 to 0.03, respectively. By utilizing electrodes with an abnormally high-aspect-ratio of 0.79 (the measured thickness and width are 30.4 µm and 38.3 µm, respectively), the cell efficiency is 17.2% on a polycrystalline silicon solar cell with an emitter sheet resistance of 60 Ω/sq. This cell efficiency is considerably higher than previously reported values obtained using a conventional electrohydrodynamic jet printing technique, by +0.48-3.5%p.

Contact resistivity decrease at a metal/semiconductor interface by a solid-to-liquid phase transitional metallo-organic silver.

We present a new approach to ensure the low contact resistivity of a silver paste at a metal/semiconductor interface over a broad range of peak firing temperatures by using a solid-to-liquid phase transitional metallo-organic silver, that is, silver neodecanoate. Silver nanoclusters, thermally derived from silver neodecanoate, are readily dissolved into the melt of metal oxide glass frit even at low temperatures, at which point the molten metal oxide glass frit lacks the dissociation capability of bulk silver into Ag(+) ions. In the presence of O(2-) ions in the melt of metal oxide glass frit, the redox reaction from Ag(+) to Ag(0) augments the noble-metal-assisted etching capability to remove the passivation layer of silicon nitride. Moreover, during the cooling stage, the nucleated silver atoms enrich the content of silver nanocolloids in the solidified metal oxide glass layer. The resulting contact resistivity of silver paste with silver neodecanoate at the metal/semiconductor interface thus remains low-between 4.12 and 16.08 mΩ cm(2)-whereas without silver neodecanoate, the paste exhibits a contact resistivity between 2.61 and 72.38 mΩ cm(2) in the range of peak firing temperatures from 750 to 810 °C. The advantage of using silver neodecanoate in silver paste becomes evident in that contact resistivity remains low over the broad range of peak firing temperatures, thus providing greater flexibility with respect to the firing temperature required in silicon solar cell applications.

A hybrid solar cell fabricated using amorphous silicon and a fullerene derivative.

Hybrid solar cells, based on organic and inorganic semiconductors, are a promising way to enhance the efficiency of solar cells because they make better use of the solar spectrum and are straightforward to fabricate. We report on a new hybrid solar cell comprised of hydrogenated amorphous silicon (a-Si:H), [6,6]-phenyl-C71-butyric acid methyl ester ([71]PCBM), and poly-3,4-ethylenedioxythiophene poly styrenesulfonate (PEDOT:PSS). The properties of these PEDOT:PSS/a-Si:H/[71]PCBM devices were studied as a function of the thickness of the a-Si:H layer. It was observed that the open circuit voltage and the short circuit current density of the device depended on the thickness of the a-Si:H layer. Under simulated one sun AM 1.5 global illumination (100 mW cm(-2)), a power conversion efficiency of 2.84% was achieved in a device comprised of a 274 nm-thick layer of a-Si:H; this is the best performance achieved to date for a hybrid solar cell made of amorphous Si and organic materials.

Excited-state photodynamics of perylene-porphyrin dyads. 5. Tuning light-harvesting characteristics via perylene substituents, connection motif, and three-dimensional architecture.

Seven perylene-porphyrin dyads were examined with the goal of identifying those most suitable for components of light-harvesting systems. The ideal dyad should exhibit strong absorption by the perylene in the green, undergo rapid and efficient excited-state energy transfer from perylene to porphyrin, and avoid electron-transfer quenching of the porphyrin excited state by the perylene in the medium of interest. Four dyads have different perylenes at the p-position of the meso-aryl group on the zinc porphyrin. The most suitable perylene identified in that set was then incorporated at the m- or o-position of the zinc porphyrin, affording two other dyads. An analogue of the o-substituted architecture was prepared in which the zinc porphyrin was replaced with the free base porphyrin. The perylene in each dyad is a monoimide derivative; the perylenes differ in attachment of the linker (either via a diphenylethyne linker at the N-imide or an ethynylphenyl linker at the C9 position) and the number (0-3) of 4-tert-butylphenoxy groups (which increase solubility and slightly alter the electrochemical potentials). In the p-linked dyad, the monophenoxy perylene with an N-imide diphenylethyne linker is superior in providing rapid and essentially quantitative energy transfer from excited perylene to zinc porphyrin with minimal electron-transfer quenching in both toluene and benzonitrile. The dyads with the same perylene at the m- or o-position exhibited similar results except for one case, the o-linked dyad bearing the zinc porphyrin in benzonitrile, where significant excited-state quenching is observed; this phenomenon is facilitated by close spatial approach of the perylene and porphyrin and the associated thermodynamic/kinetic enhancement of the electron-transfer process. Such quenching does not occur with the free base porphyrin because electron transfer is thermodynamically unfavorable even in the polar medium. The p-linked dyad containing a zinc porphyrin attached to a bis(4-tert-butylphenoxy)perylene via an ethynylphenyl linker at the C9 position exhibits ultrafast and quantitative energy transfer in toluene; the same dyad in benzonitrile exhibits ultrafast (<0.5 ps) perylene-to-porphyrin energy transfer, rapid (∼5 ps) porphyrin-to-perylene electron transfer, and fast (∼25 ps) charge recombination to the ground state. Collectively, this study has identified suitable perylene-porphyrin constructs for use in light-harvesting applications.

Linker dependence of energy and hole transfer in neutral and oxidized multiporphyrin arrays.

The excited-state photodynamics of the neutral and one-electron-oxidized forms of five porphyrin dyads were studied in benzonitrile containing tetrabutylammonium hexafluorophosphate as the supporting electrolyte. Each dyad contains a zinc porphyrin (Zn) and a free base porphyrin (Fb) joined by a linear biphenylene (Phi(2)), terphenylene (Phi(3)), quaterphenylene (Phi(4)), diphenylbutadiyne (L), or phenylethyne (E) linker (ZnFbPhi(2), ZnFbPhi(3), ZnFbPhi(4), ZnFbL, ZnFbE). The findings along with recent results on the neutral and oxidized forms of ZnFb dyads containing a diphenylethyne or phenylene linker (ZnFbU, ZnFbPhi) and steric hindrance to porphyrin-linker internal rotation at one or both ends of a diarylethyne linker (ZnFbD, ZnFbP, ZnFbB) give insights into the effects of linker characteristics (length, orbital energies, orbital overlap with the porphyrins) on the rate constants for excited-state energy transfer, excited-state hole transfer, and ground-state hole transfer. Analysis of the results is aided by density functional theory molecular orbital calculations and Forster energy-transfer calculations. Although the rate constants for linker-mediated through-bond excited-state energy transfer can be modulated significantly using a number of molecular design criteria (e.g., linker characteristics, interplay between porphyrin orbital characteristics, and linker attachment site), ground-state hole transfer, which also occurs via a linker-mediated through-bond electron-exchange mechanism, is primarily affected by the free-energy driving force for the process as dictated by the redox characteristics of the interacting porphyrins. The insights gained from this study should aid in the design of next-generation multichromophore arrays for solar energy applications.

Excited-state energy flow in phenylene-linked multiporphyrin arrays.

The dynamics and pathways for excited-state energy transfer in three dyads and five triads composed of combinations of zinc, magnesium, and free base porphyrins (denoted Zn, Mg, Fb) connected by p-phenylene linkers have been investigated. The processes in the triads include energy transfer between adjacent nonequivalent porphyrins, between adjacent equivalent porphyrins, and between nonadjacent nonequivalent porphyrins using the intervening porphyrin as a superexchange mediator. In the case of the triad ZnZnFbPhi, excitation of the zinc porphyrin (to yield Zn) ultimately leads to production of the excited free base porphyrin (Fb) via the three processes with the derived rate constants as follows: (2.8 ps)(-1) for ZnZn Fb --> ZnZnFb, (4 ps)(-1) for Zn ZnFb left arrow over right arrow ZnZn Fb, and (14 ps)(-1) for Zn ZnFb --> ZnZnFb. These results and those obtained for the other four triads show that energy transfer between nonadjacent sites is significant and is only 5-7-fold slower than between adjacent sites. This same scaling was found previously for arrays joined via diphenylethyne linkers. Simulations of the energy-transfer properties of fictive dodecameric arrays based on the data reported herein show that nonadjacent transfer steps make a significant contribution to the observed performance of such larger molecular architectures. Collectively, these results indicate that energy transfer between nonadjacent sites has important implications for the design of multichromophore arrays for molecular-photonic and solar-energy applications.

Energy- and hole-transfer dynamics in oxidized porphyrin dyads.

The mechanisms and dynamics of quenching of a photoexcited free base porphyrin (Fb*) covalently linked to a nearby oxidized zinc porphyrin (Zn(+)) have been investigated in a set of five dyads using time-resolved absorption spectroscopy. The dyads include porphyrins joined at the meso-positions by a diphenylethyne linker or a diarylethyne linker with 2,6-dimethyl substitution on either one or both of the aryl rings. Another dyad is linked at the beta-pyrrole positions of the porphyrins via a diphenylethyne linker. The type of linker and attachment site modulate the interporphyrin through-bond electronic coupling via steric hindrance (porphyrin-linker orbital overlap) and attachment motif (porphyrin electron density at the connection site). For each ZnFb dyad, the zinc porphyrin is selectively electrochemically oxidized (to produce Zn(+)Fb), the free base porphyrin is selectively excited with a 130 fs flash (to produce Zn(+)Fb*), and the subsequent dynamics monitored. The Zn(+)Fb* excited state has a lifetime of approximately 3 to approximately 30 ps (depending on the linker steric hindrance and attachment site) and decays by parallel excited-state energy- and hole-transfer pathways. The relative yields of the two channels depend on a number of factors including the linker-mediated through-bond electronic coupling and a modest (< or =20%) Forster through-space contribution for the energy-transfer route. One product of Zn(+)Fb* decay is the metastable ground-state ZnFb(+), which decays to the Zn(+)Fb preflash state by ground-state hole transfer with a linker-dependent rate constant of (20 ps)(-1) to (150 ps)(-1). Collectively, these results provide a detailed understanding of the mechanism and dynamics of quenching of excited porphyrins by nearby oxidized sites, as well as the dynamics of ground-state hole transfer between nonequivalent porphyrins (Zn and Fb). The findings also lay the foundation for the study of ground-state hole transfer between identical porphyrins (e.g., Zn/Zn, Fb/Fb) in larger multiporphyrin arrays wherein a hole is selectively placed via electrochemical oxidation.

Probing ground-state hole transfer between equivalent, electrochemically inaccessible states in multiporphyrin arrays using time-resolved optical spectroscopy.

A new strategy is described and implemented for determining the rates of hole-transfer between equivalent porphyrins in multiporphyrin architectures. The approach allows access to these rates between sites that are not the most easily oxidized components of the array. The specific architectures investigated with this new strategy are triads consisting of one zinc porphyrin (Zn) and two free base porphyrins (Fb). The triads employ a diphenylethyne linker (ZnFbFbU) and a phenylene linker (ZnFbFbPhi). The zinc porphyrin is selectively oxidized to produce Zn(+)FbFb, the free base porphyrins are excited to produce the excited-state mixture Zn(+)Fb*Fb and Zn(+)FbFb*, and the subsequent dynamics are monitored by ultrafast absorption spectroscopy. The system evolves by a combination of energy- and hole-transfer processes involving (adjacent and nonadjacent) zinc and free base porphyrin constituents that are complete within 100 ps of excitation; the rate constants of many of these processes are derived from prior studies of the oxidized forms of the benchmark dyads (ZnFbU and ZnFbPhi). One of the excited-state decay channels produces the metastable state ZnFbFb(+) that decays to a second metastable state ZnFb(+)Fb by the target hole-transfer process, followed by rapid hole transfer to produce the Zn(+)FbFb thermodynamic ground state of the system. The rate constant for hole transfer between the free base porphyrins in the oxidized ZnFbFb triads is found to be (0.5 ns)(-1) and (0.6 ns)(-1) across phenylene and diphenylethyne linkers, respectively. These rate constants are comparable to those recently measured, using a related but distinct strategy, for ground-state hole transfer between zinc porphyrins in oxidized ZnZnFb triads. The two complementary strategies provide unique approaches for probing hole transfer between equivalent sites in multiporphyrin arrays, with the choice of method being guided by the particular target process and the ease of synthesis of the necessary architectures.

Determination of ground-state hole-transfer rates between equivalent sites in oxidized multiporphyrin arrays using time-resolved optical spectroscopy.

Excited-state charge separation in molecular architectures has been widely explored, yet ground-state hole (or electron) transfer, particularly involving equivalent pigments, has been far less studied, and direct quantitation of the rate of transfer often has proved difficult. Prior studies of ground-state hole transfer between equivalent zinc porphyrins using electron paramagnetic resonance techniques give a lower limit of approximately (50 ns)(-1) on the rates. Related transient optical studies of hole transfer between inequivalent sites [zinc porphyrin (Zn) and free base porphyrin (Fb)] give an upper limit of approximately (20 ps)(-1). Thus, a substantial window remains for the unknown rates of ground-state hole transfer between equivalent sites. Herein, the ground-state hole-transfer processes are probed in a series of oxidized porphyrin triads (ZnZnFb) with the focus being on determination of the rates between the nominally equivalent sites (Zn/Zn). The strategy builds upon recent time-resolved optical studies of the photodynamics of dyads wherein a zinc porphyrin is electrochemically oxidized and the attached free base porphyrin is photoexcited. The resulting energy- and hole-transfer processes in the oxidized ZnFb dyads are typically complete within 100 ps of excitation. Such processes are also present in the triads and serve as a starting point for determining the rates of ground-state hole transfer between equivalent sites in the triads. The rate constant of the Zn/Zn hole transfer is found to be (0.8 ns)(-1) for diphenylethyne-linked zinc porphyrins and increases only slightly to (0.6 ns)(-1) when a shorter phenylene linker is utilized. The rate decreases slightly to (1.1 ns)(-1) when steric constraints are introduced in the diarylethyne linker. In general, the rate constants for ground-state Zn/Zn hole transfer in oxidized arrays are a factor of 40 slower than those for Zn/Fb transfer. Collectively, the findings should aid the design of next-generation molecular architectures for applications in solar-energy conversion.

Photophysics of reduced silicon tetraphenylporphyrin.

The contrasting photophysical properties of two silicon (IV) tetraphenylporphyrins, Si(TPP)(py)2 and Si(TPP)Cl2, have been investigated using static absorption and fluorescence spectroscopy and ultrafast transient absorption measurements. The parent Si(TPP)Cl2, in which the porphyrin macrocycle has its normal 2- oxidation state, has a fluorescence yield of 0.027, and a lifetime of 1.8 ns for the lowest excited singlet state. In marked contrast, the reduced, anti-aromatic complex Si(TPP)(py)2, with the macrocycle in the 4- oxidation state, has an extremely low fluorescence yield (< or =0.0004) and a 750-fold shorter excited-state lifetime (2.4 ps) in the same solvent (pyridine). The rapid deactivation of photoexcited Si(TPP)(py)2 to the ground state is likely associated with its ruffled structure and the presence of low-energy excited states in its electronic manifold.