The syntheses of 4,4′-bis(4-dimethylaminophenyl)-6,6′-dimethyl-2,2′-bipyridine (1), 4,4′-bis(4-dimethylaminophenylethynyl)-6,6′-dimethyl-2,2′-bipyridine (2), 4,4′-bis(4-diphenylaminophenyl)-6,6′-dimethyl-2,2′-bipyridine (3), and 4,4′-bis(4-diphenylaminophenylethynyl)-6,6′-dimethyl-2,2′-bipyridine (4) are reported along with the preparations and characterisations of their homoleptic copper(I) complexes [CuL2][PF6] (L = 1–4). The solution absorption spectra of the complexes exhibit ligand-centred absorptions in addition to absorptions in the visible region assigned to a combination of intra-ligand and metal-to-ligand charge-transfer. Heteroleptic [Cu(5)(Lancillary)]+ dyes in which 5 is the anchoring ligand ((6,6′-dimethyl-[2,2′-bipyridine]-4,4′-diyl)bis(4,1-phenylene))bis(phosphonic acid) and Lancillary = 1–4 have been assembled on fluorine-doped tin oxide (FTO)-TiO2 electrodes in dye-sensitized solar cells (DSCs). Performance parameters and external quantum efficiency (EQE) spectra of the DSCs (four fully-masked cells for each dye) reveal that the best performing dyes are [Cu(5)(1)]+ and [Cu(5)(3)]+. The alkynyl spacers are not beneficial, leading to a decrease in the short-circuit current density (JSC), confirmed by lower values of EQEmax. Addition of a co-absorbent (n-decylphosphonic acid) to [Cu(5)(1)]+ lead to no significant enhancement of performance for DSCs sensitized with [Cu(5)(1)]+. Electrochemical impedance spectroscopy (EIS) has been used to investigate the interfaces in DSCs; the analysis shows that more favourable electron injection into TiO2 is observed for sensitizers without the alkynyl spacer and confirms higher JSC values for [Cu(5)(1)]+.
Dye-sensitized solar cell (DSC) technology has been broadly investigated over the past few decades. The sandwich-type structure of the DSC makes the manufacturing undemanding under laboratory conditions but results in the need for reproducible measurements for acceptable DSC characterization. Electrochemical impedance spectroscopy (EIS) offers the possibility to study complex electronic systems and is commonly used for solar cells. There is a tendency in the literature to present impedance data only for one representative device. At the same time, as current density–voltage plots illustrate, measurements can vary within one set of DSCs with identical components. We present multiple DSC impedance measurements on “identical” devices prepared using two different dyes and present a statistical analysis regarding the reproducibility.
The effects of different I2 concentrations and different ionic liquids (ILs) in the electrolyte on the performances of dye-sensitized solar cells (DSCs) containing an iron(II) N-heterocyclic carbene dye and containing the I–/I3– redox shuttle have been investigated. Either no I2 was added to the electrolyte, or the initial I2 concentrations were 0.02, 0.05, 0.10, and 0.20 M. The short-circuit current density (JSC), open-circuit voltage (VOC), and the fill factor (ff) were influenced by changes in the I2 concentration for all the ILs. For 1-hexyl-3-methylimidazole iodide (HMII), low VOC and low ff values led to poor DSC performances. Electrochemical impedance spectroscopy (EIS) showed the causes to be increased electrolyte diffusion resistance and charge transfer resistance at the counter electrode. DSCs containing 1,3-dimethylimidazole iodide (DMII) and 1-ethyl-3-methylimidazole iodide (EMII) showed the highest JSC values when 0.10 M I2 was present initially. Short alkyl substituents (Me and Et) were more beneficial than longer chains. The lowest values of the transport resistance in the photoanode semiconductor were found for DMII, EMII, and 1-propyl-2,3-dimethylimidazole iodide (PDMII) when no I2 was added to the initial electrolyte, or when [I2] was less than 0.05 M. Higher [I2] led to decreases in the diffusion resistance in the electrolyte and the counter electrode resistance. The electron lifetime and diffusion length depended upon the [I2]. Overall, DMII was the most beneficial IL. A combination of DMII and 0.1 M I2 in the electrolyte produced the best performing DSCs with an average maximum photoconversion efficiency of 0.65% for a series of fully-masked cells.
DSC photoconversion efficiencies of up to 0.93–0.95% have been achieved for a new heteroleptic iron(ii) N-heterocyclic carbene sensitizer employing n-butyl chains.
Correct photoluminescence quantum yield (PLQY) determination in the solid state is vital for numerous application fields, such as photovoltaics, solid lighting or the development of phosphors. In order to increase the limited number of suitable standards for such determinations, two new Ln3+‐based complexes with 4′‐phenyl‐2,2′ : 6′,2“‐terpyridine γ‐[Ln4(OAc)12(ptpy)2] (1‐Eu with europium and 1‐Tb with terbium) are presented. The corresponding complexes show solid‐state QYs of 58(4) % and 46(3) %, respectively, exhibiting broadband absorption in the UV range from 380–200 nm. As Ln3+ ions in general exhibit narrow f‐f transitions, spectral regions with a broadness of 20–35 nm can be checked. Both complexes have suitable thermal stability, up to 270 °C, and are stable with respect to air and humidity, for 1‐Eu up to 75 % and for 1‐Tb up to 53 % relative humidity. These complexes are altogether suitable as standards to increase the reliability of PLQY determination and proposed to be used for a relative PLQY determination in the solid state.
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