Vectorial electron relay at ITO electrodes modified with self-assembled monolayers of ferrocene-porphyrin-fullerene triads and porphyrin-fullerene Dyads for molecular photovoltaic devices

Systematic series of indium tin oxide (ITO) electrodes modified covalently with self-assembled monolayers (SAMs) of ferrocene-porphyrin-fullerene triads and porphyrin-fullerene dyads were designed to gain valuable insight into the development of molecular photovoltaic devices. The structures of SAMs on ITO have been investigated by UV/Vis absorption spectroscopy, atomic force microscopy, and cyclic voltammetry. The photoelectrochemical and photophysical (fluorescence lifetime and time-resolved transient absorption) properties were also determined. The highest quantum yield of photocurrent generation (11 %) among donor-acceptor linked systems which are covalently attached to the surface of ITO electrodes was achieved with SAMs of ferrocene-zinc porphyrin-fullerene linked triad on ITO electrodes. The quantum yields of photocurrent generation correlate well with the charge-separation efficiency and the lifetime of the charge-separated state of the porphyrin-fullerene linked systems in solution. These results provide valuable information for the construction of photonic molecular devices and artificial photosynthetic systems on ITO electrodes.     

Photoinduced electron transfer in self-assembled monolayers of porphyrin-fullerene dyads on ITO

Two porphyrin-fullerene dyads were synthesized to form self-assembled monolayers (SAMs) on indium-tin oxide (ITO) electrode, with either ITO-porphyrin-fullerene or ITO-fullerene-porphyrin orientations. The dyads contain two linkers for connecting the porphyrin and fullerene moieties and enforcing them essentially to similar geometries of the donor-acceptor pair, and two linkers to ensure the attachment of the dyads to the ITO surface with two desired opposite orientations. The transient photovoltage responses (Maxwell displacement charge) were measured for the dyad films covered by insulating LB films, thus ensuring that the dyads interact only with the ITO electrode. The direction of the electron transfer was from the photoexcited dyad to ITO independent of the dyad orientation. The response amplitude for the ITO-fullerene-porphyrin structure, where the primary intramolecular electron-transfer direction coincides with the direction of the final electron transfer from the dyad to ITO, was 25 times stronger than that for the opposite ITO-porphyrin-fullerene orientation of the dyad. Static photocurrent measurements in a liquid electrochemical cell, however, show only a minor orientation effect, indicating that the photocurrent generation is controlled by the processes at the SAM-liquid interface.     

Efficient charge injection from the S2 photoexcited state of special-pair mimic porphyrin assemblies anchored on a titanium-modified ITO anode

A novel surface fabrication methodology has been accomplished, aimed at efficient anodic photocurrent generation by a photoexcited porphyrin on an ITO (indium-tin oxide) electrode. The ITO electrode was submitted to a surface sol-gel process with titanium n-butoxide in order to deposit a titanium monolayer. Subsequently, porphyrins were assembled as monolayers on the titanium-treated ITO surface via phosphonate, isophthalate, and thiolate groups. Slipped-cofacial porphyrin dimers, the so-called artificial special pair at the photoreaction center, were organized through imidazolyl-to-zinc complementary coordination of imidazolylporphyrinatozinc(II) units, which were covalently immobilized by ring-closing olefin metathesis of allyl side chains. The modified surfaces were analyzed by means of X-ray photoelectron spectroscopy. Photoirradiation of the porphyrin dimer generated a large anodic photocurrent in aqueous electrolyte solution containing hydroquinone as an electron sacrificer, due to the small reorganization energy of the dimer. The use of different linker groups led to significant differences in the efficiencies of anodic photocurrent generation. The apparent flat-band potentials evaluated from the photocurrent properties at various pH values and under biased conditions imply that the band structure of the ITO electrode is modified by the anchoring species. The quantum yield for the anodic photocurrent generation by photoexcitation at the Soret band is increased to 15 %, a surprisingly high value without a redox cascade structure on the ITO electrode surface, while excitation at the Q band is not so significant. Extensive exploration of the photocurrent properties has revealed that hot injection of the photoexcited electron from the S2 level into the conduction band of the ITO electrode takes place before internal conversion to the S1* state, through the strong electronic communication of the phosphonyl anchor with the sol-gel-modified ITO surface.     

Fine-tuning of a ferrocene[porphyrin]ITO redox cascade for efficient sequential electron transfer commenced by an S2 photoexcited special-pair mimic

A systematic series of ferrocene/porphyrin redox cascade architectures was assembled through a slipped-cofacial porphyrin dimer on ITO electrode in optimizing the anodic photocurrent generation to perform the highest quantum yield compared to reported values on ITO electrodes.     

Langmuir-Blodgett films of a cationic zinc porphyrin-imidazole-functionalized fullerene dyad: formation and photoelectrochemical studies

Electron donor-acceptor dyad ensembles of a water-soluble cationic zinc porphyrin (viz., zinc tetrakis(N-methylpyridinium)porphyrin tetrachloride, Zn(TMPyP)) and a C60 derivative that bears an imidazole ligand (viz., 2-(phenylimidazolyl)fulleropyrrolidine, C60im) were assembled during the formation of Langmuir and then Langmuir-Blodgett (LB) films. Surface pressure versus surface area isotherms and surface pressure time profiles, as well as Brewster angle microscopic images documented that the Langmuir films formed were remarkably stable. Subsequently, these Langmuir films were transferred onto different solid substrates, by using the LB technique, for spectroscopic and photoelectrochemical characterization. The UV-vis spectroscopic investigations confirmed that the water-soluble Zn(TMPyP) was, indeed, transferred together with C60im in the LB films. Upon visible light illumination of these LB films, deposited on the ITO transparent conductive supports, a photocurrent generated in the C60im-Zn(TMPyP) system is ascribed to an efficient photoinduced electron transfer from the electron donor, porphyrin singlet excited-state to the electron acceptor, C60. Overall, internal photon-to-current efficiency, IPCE, of the photoanodic current generation (with ascorbate as a sacrificial electron donor) in the ITO/C60im-Zn(TMPyP)/ascorbate/Pt construct is over 5x larger than that of the photocathodic system (with methyl viologen, MV2+, as a sacrificial electron acceptor) in the ITO/Zn(TMPyP)-C60im/MV2+/Pt construct. Highly ordered film stacking favors vectorial electron transfer within the dyad, giving rise to the highest IPCE values of 2.5% determined for a photoanode that was composed of around 20 monolayer films.     

含不同链长的三个卟啉LB膜修饰电极的光电响应研究

利用LB (Langmuir-Blodgett)技术将含不同链长的卟啉化合物(C4Py, C6Py和C8Py)单层膜转移到ITO (indium-tin oxide)导电玻璃上, 发现其具有良好的光电转换性质. 卟啉化合物修饰后的紫外吸收光谱与光电流工作谱重叠, 表明卟啉化合物起到了敏化光电流产生的效果; 而且电子给体、电子受体和偏压对其敏化效果的实验结果表明: 光诱导电子转移是产生光电响应的主要原因. 而且, 这三个卟啉化合物的光电响应性质与碳链长度相关, 其中含有六个碳链的C6Py表现出最佳的光电转化效果.     

A photoelectrochemical device with a nanostructured SnO2 electrode modified with composite clusters of porphyrin-modified silica nanoparticle and fullerene

A silica nanoparticle has been successfully employed as a nanoscaffold to self-organize porphyrin and C60 molecules on a nanostructured SnO2 electrode. The quenching of the porphyrin excited singlet state on the silica nanoparticle is suppressed significantly, showing that silica nanoparticles are promising scaffolds for organizing photoactive molecules three-dimensionally in nanometer scale. Marked enhancement of the photocurrent generation was achieved in the present system compared with the reference system, where a gold core was employed as a scaffold of porphyrins instead of a silica nanoparticle. The rather small incident photon-to-current efficiency relative to a similar photoelectrochemical device using a silica microparticle may result from poor electron and hole mobility in the composite film due to poor connection between the composite clusters of a porphyrin-modified silica nanoparticle and C60 in micrometer scale.     

Electrocatalytic reduction of oxygen at electrodes coated with a bimetallic cobalt(II)/platinum(II) porphyrin

Edge plane pyrolytic graphite (EPG) electrodes coated with 5-(4-pyridyl)-10,15,20-tris(3-methoxy-4-hydroxyphenyl)porphyrin and its Pt(II) and Co(II)/Pt(II) analogs undergo an electrochemical-chemical-electrochemical (ECE) reaction when anodically scanned in 1.0 M HClO4. The new redox couple formed from this anodic conditioning of the coated electrode is dependent on the pH of the solution. Roughened EPG electrodes coated with the Co(II)/Pt(II) bimetallic porphyrin show a catalytic shift of 500 mV for the reduction of O2 when compared to the reduction of O2 at a bare EPG electrode. An additional catalytic shift of ca. 100 mV is observed for O2 reduction at an EPG electrode coated with the Co(II)/Pt(II) porphyrin which has been oxidized in 1.0 M HClO4. In addition to the added electrocatalysis a significant percentage of O2 reduced at the oxidized Co(II)/Pt(II) EPG electrode is converted to H2O as determined by rotating disk electrode measurements.     

Unusually high performance photovoltaic cell based on a [60]fullerene metal cluster-porphyrin dyad SAM on an ITO electrode

A self-assembled monolayer (SAM) of a C60-triosmium cluster complex Os3(CO)7(CNR)(CNR')(mu3-eta2:eta2:eta2-C60) (ZnP-C60; R = (CH2)3Si(OEt)3, R' = ZnP) on an ITO surface exhibits ideal electrochemical responses as well as remarkable enhancement of the photocurrent generation. The diazabicyclooctane (DABCO) binding (ZnP)-C60/ITO/AsA/Pt cell shows the highest photocurrent generation quantum yield (19.5%) ever reported for the molecular photovoltaic cells based on the covalently linked donor-acceptor dyad structures. The high efficiency in photocurrent generation is ascribed to an efficient electron transfer from photoexcited porphyrin to fullerene, revealed by fluorescence lifetime measurements and transient absorption decay profiles. These results provide valuable information on the new strategy for the construction of molecular photonic devices and artificial photosynthetic systems on ITO electrodes.     

Hydrogen bonding effects on the surface structure and photoelectrochemical properties of nanostructured SnO2 electrodes modified with porphyrin and fullerene composites

Hydrogen bonding effects on surface structure, photophysical properties, and photoelectrochemistry have been examined in a mixed film of porphyrin and fullerene composites with and without hydrogen bonding on indium tin oxide and nanostructured SnO2 electrodes. The nanostructured SnO2 electrodes modified with the mixed films of porphyrin and fullerene composites with hydrogen bonding exhibited efficient photocurrent generation compared to the reference systems without hydrogen bonding. Atomic force microscopy, infrared reflection absorption, and ultraviolet-visible absorption spectroscopies and time-resolved fluorescence lifetime and transient absorption spectroscopic measurements disclosed the relationship between the surface structure and photophysical and photoelectrochemical properties relating to the formation of hydrogen bonding between the porphyrins and/or the C60 moieties in the films on the electrode surface. These results show that hydrogen bonding is a highly promising methodology for the fabrication of donor and acceptor composites on nanostructured semiconducting electrodes, which exhibit high photoelectrochemical properties.     

Photovoltaic and spectral properties of tetraphenyloporphyrin and metallotetraphenyloporphyrin dyes

Spectroscopical properties and photocurrent (or photovoltage) of tetraphenyloporphyrins and metallotetraphenyloporphyrins in nematic liquid crystal have been studied. Photoelectric response has been measured in an electrochemical cell made of the semitransparent semiconducting and golden electrodes with porphyrin dyes embedded in liquid crystal. Fluorescence, time-resolved luminescence in microsecond time scale and photoacoustic spectra have also been measured. The competition between radiative, non-radiative processes and charge transfer is discussed. It has been shown that effectivity of porphyrins for photocurrent generation depends on the presence/absence of central metal in the macrocycle of porphyrin skeleton and the kind of metal. The schematic model of the contributions of the dye molecule and semiconducting electrode in the electron transfer process is shown.     

Hydrogen bonding effect on photocurrent generation in porphyrin-fullerene photoelectrochemical devices

A hydrogen bonding effect on photocurrent generation has been evaluated successfully in a mixed film of porphyrin and fullerene with hydrogen bonding on an ITO electrode, which exhibits efficient cathodic photocurrent generation as compared to the reference system without hydrogen bonding.     

有机钌螯合物/TiO_2杂化膜修饰电极上Pt纳米团簇的光电流增强效应

利用LB膜技术可控制备了纳米单层和多层的二氧化钛-有机钌螯合物杂化膜,并研究了上述无机-有机杂化膜修饰电极在Pt纳米团簇敏化后的光电流增强效应.实验结果表明:(1)纳米单层TiO2/[Ru(phen)2(dC18bpy)]2+(简称为TiO2-Ru)杂化膜的平均厚度为(3.6±0.5)nm;(2)在光照条件下TiO2-Ru杂化膜能有效催化还原[Pt(NH3)6]4+形成粒径位于20～160nm之间的Pt纳米团簇;(3)Pt纳米团簇的引入消除了金属钌螯合物中配体对电子传递的阻碍作用,改变了电子传递途径,从而有效减少了电子空穴对的复合,提高了Pt纳米团簇敏化的n层杂化膜修饰电极(ITO/(TiO2-Ru)n/Pt)在支持电解质中的光电流.与纳米单层TiO2-Ru杂化膜修饰的ITO电极(ITO/TiO2-Ru)相比,当工作电压为900mV时,ITO/TiO2-Ru/Pt在0.1mol·L-1的NaClO4电解质溶液中和光照(λ360nm)条件下,单位面积的光电流提高了约5倍;(4)ITO/(TiO2-Ru)n/Pt电极光电流的大小与杂化膜的层数密切相关,当TiO2-Ru杂化膜的层数从一层、二层增加到四层时,光电流呈现先升高后下降行为,这表明ITO/(TiO2-Ru)n/Pt电极的电子传递过程直接通过非电活性的二氧化钛纳米单层进行.     

Effects of porphyrin substituents on film structure and photoelectrochemical properties of porphyrin/fullerene composite clusters electrophoretically deposited on nanostructured SnO2 electrodes

We have systematically examined the substituent effects of meso-tetraphenylporphyrins on film structures and the photoelectrochemical properties of the composite clusters of free-base porphyrin and C(60) electrophoretically deposited on nanostructured SnO(2) electrodes. The photocurrent generation efficiency was found to correlate with the complexation ability of the porphyrin for C(60). Basically, the incident photon-to-current efficiency (IPCE) value was increased with increasing relative amounts of the porphyrin versus C(60) in the films. The unique molecular arrangement of the porphyrin with the simple, specific substituents (i.e., methoxy groups at the meta-positions of the meso-phenyl rings of tetraphenylporphyrins (3,5-OMeTPP; TPP=tetraphenylporphyrin)) and C(60) on SnO(2) electrodes resulted in the largest IPCE value (ca. 60 %) among this type of photoelectrochemical device. The rapid formation of the composite clusters and microcrystals from the combination of 3,5-OMeTPP and C(60) in a mixed solvent is unique as the association is accelerated by intermolecular interactions (i.e., hydrogen-bonding and CH-pi interactions) between the methoxy groups of the porphyrins and the porphyrin/C(60), in addition to the pi-pi interactions between the porphyrins/C(60) and C(60) molecules. Both the films and single crystals composed of the porphyrin and C(60) exhibited remarkably high electron mobility (7x10(-2) and 0.4 cm(2) V(-1) s(-1)), which is comparable to the value for highly efficient bulk heterojunction solar cells. Our experimental results have successfully demonstrated the importance of nanostructured electron- and hole-transporting pathways in bulk heterojunction solar cells. Such a finding will provide basic and valuable information on the design of molecular photovoltaics at the molecular level.     

Self-Assembled Monolayers of Bi-Functionalized Porphyrins: A Novel Class of Hole-Layer-Coordinating Perovskites and Indium Tin Oxide in Inverted Solar Cells

Self-assembled monolayers (SAMs) offer the advantage of facile interfacial modification, leading to significant improvements in device performance. In this study, we report the design and synthesis of a new series of carboxylic acid-functionalized porphyrin derivatives, namely AC-1, AC-3, and AC-5, and present, for the first time, a strategy to exploit the large π-moiety of porphyrins as a backbone for interfacing the indium tin oxide (ITO) electrode and perovskite active layer in an inverted perovskite solar cell (PSC) configuration. The electron-rich nature of porphyrins facilitates hole transfer and the formation of SAMs, resulting in a dense surface that minimizes defects. Comprehensive spectroscopic and dynamic studies demonstrate that the double-anchored AC-3 and AC-5 enhance SAMs on ITO, passivate the perovskite layer, and function as conduits to facilitate hole transfer, thus significantly boosting the performance of PSCs. The champion inverted PSC employing AC-5 SAM achieves an impressive solar efficiency of 23.19 % with a high fill factor of 84.05 %. This work presents a novel molecular engineering strategy for functionalizing SAMs to tune the energy levels, molecular dipoles, packing orientations to achieve stable and efficient solar performance. Importantly, our comprehensive investigation has unraveled the associated mechanisms, offering valuable insights for future advancements in PSCs.     

Structure and photophysical properties of porphyrin-modified metal nanoclusters with different chain lengths

Three-dimensional porphyrin-monolayer-protected gold clusters with different chain lengths (MPCs) have been prepared to examine the structure and photophysical properties, in comparison with self-assembled monolayers (SAMs) of the porphyrins on a flat gold surface. The three-dimensional porphyrin MPCs exhibit electrochemical and photophysical properties that are much closer to those of a porphyrin reference compound in solution than those of two-dimensional porphyrin SAMs on the flat gold surface. The three-dimensional architectures of porphyrin MPCs with large surface area have improved the light-harvesting efficiency relative to the corresponding porphyrin SAM on the two-dimensional flat gold surface. Time-resolved single photon counting fluorescence and transient absorption spectroscopic studies have demonstrated that undesirable quenching of the porphyrin excited singlet state via energy transfer to the gold surface of the three-dimensional MPCs is much suppressed, as compared to the quenching of the porphyrin SAMs on the two-dimensional flat gold surface. Both the quenching rate constants of the porphyrin excited singlet state by the surfaces of bulk gold and gold nanoclusters reveal weak chain length dependence of the energy transfer quenching.     

Carboxyphenyl metalloporphyrins as photosensitizers of semiconductor film electrodes. A study of the effect of different central metals

Free-base (P), Zn(II) (P(Zn)), Cu(II) (P(Cu)), Pd(II) (P(Pd)), Ni(II) (P(Ni)), and Co(II) (P(Co)) 5-(4-carboxyphenyl)-10,15,20-tris(4-methylphenyl) porphyrins were designed and synthesized to be employed as spectral senzitizers in photoelectrochemical cells. The dyes were studied adsorbed on SnO(2) nanocrystalline semiconductor and also in Langmuir-Blodgett film ITO electrodes in order to disclose the effect of molecular packing on the studied properties. Electron injection yields were obtained by fluorescence quenching analysis comparing with the dyes adsorbed on a SiO(2) nanocrystalline insulator. Back electron-transfer kinetics were measured by using laser flash photolysis. The unmetallized and metallized molecules have different singlet state energies, fluorescence quantum yields, and redox properties. The quantum yields of sensitized photocurrent generation are shown to be highly dependent on the identity of the central metal. It is shown that P(Ni) and P(Co) do not present a photoelectric effect. The other porhyrins present reproducible photocurrent, P(Pd) being the one that gives the highest quantum yield even in closely packet ITO/LB films. Photocurrent quantum yields increase as the dye ground-state oxidation potential becomes more anodic, which is in agreement with the observation, obtained by laser flash photolysis, that back electron-transfer kinetics decrease with the increase in the driving force for the recombination process. This effect could be exploited as a design element in the development of new and better sensitizers for high-efficiency solar cells involving porphyrins and related dyes.     

Preparation and photophysical and photoelectrochemical properties of a covalently fixed porphyrin-chemically converted graphene composite

Chemically converted graphene (CCG) covalently linked with porphyrins has been prepared by a Suzuki coupling reaction between iodophenyl-functionalized CCG and porphyrin boronic ester. The covalently linked CCG-porphyrin composite was designed to possess a short, rigid phenylene spacer between the porphyrin and the CCG. The composite material formed stable dispersions in DMF and the structure was characterized by spectroscopic, thermal, and microscopic measurements. In steady-state photoluminescence spectra, the emission from the porphyrin linked to the CCG was quenched strongly relative to that of the porphyrin reference. Fluorescence lifetime and femtosecond transient absorption measurements of the porphyrin-linked CCG revealed a short-lived porphyrin singlet excited state (38 ps) without yielding the porphyrin radical cation, thereby substantiating the occurrence of energy transfer from the porphyrin excited state to the CCG and subsequent rapid decay of the CCG excited state to the ground state. Consistently, the photocurrent action spectrum of a photoelectrochemical device with a SnO(2) electrode coated with the porphyrin-linked CCG exhibited no photocurrent response from the porphyrin absorption. The results obtained here provide deep insight into the interaction between graphenes and π-conjugated systems in the excited and ground states.     

四种新型D-A化合物的合成与光电性能研究

合成了H2Po-C70, H2Pp-C70, ZnPo-C70和ZnPp-C70 4种新型的D-A化合物; 通过紫外-可见吸收光谱、红外光谱、质谱和元素分析等多种手段对其进行了表征. 在光电化学电池中, 在GaAs电极上测量了这4种D-A化合物的光伏效应(PVE). 研究结果表明, H2P-C70/GaAs和ZnP-C70/GaAs电极的光生电压(ΔV)和光生电流(ΔI)比单纯的GaAs电极大得多, 据此能够确定这4种D-A化合物具有优良的光电性能.     

Electrochemical properties of protoporphyrin IX zinc(II) films

The electrochemical properties of protoporphyrin IX zinc(II) (ZnPP) films on indium-tin oxide (ITO) substrate have been studied for three types of films with different arrangements, which were an adsorbed film of ZnPP and LB films of ZnPP and its hybrid with hexadecyltrimethylammonium bromide. Cyclic voltammetry (CV) measurement showed that, as the adsorbed amount of ZnPP increases, an irreversible oxidation peak of ZnPP film is intensified. This reveals that electrochemical properties depend on the adsorbed amount rather than the orientation of porphyrin molecules. It was also supported from CV measurement and ultraviolet-visible absorption spectroscopy that porphyrins adsorbed on ITO substrate were desorbed after the single scan of potential. Additionally, photoresponse of these ZnPP films was investigated by photocurrent measurement. The photocurrent generation is due to carboxylic acid moieties but not ZnPP macrocycles.