The synthesis, characterization, and incorporation of open-cage [60]fullerene derivatives as electron-transporting materials (ETMs) in perovskite solar cells (PSCs) with an inverted planar (p-i-n) structure is reported. Following optical and electrochemical characterization of the open-cage fullerenes 2a–c, p-i-n PSCs with a indium tin oxide (ITO)/poly(3,4-ethylenedioxythiophene)-polystyrene sulfonate (PEDOT:PSS)/perovskite/fullerene/Ag structure were prepared. The devices obtained from 2a–b exhibit competitive power conversion efficiencies (PCEs) and improved open-circuit voltage (Voc) values (>1.0 V) in comparison to a reference cell based on phenyl-C61-butyric-acid methyl-ester (PC61BM). These results are rationalized in terms of a) the higher passivation ability of the open-cage fullerenes with respect to the other fullerenes, and b) a good overlap between the highest occupied molecular orbital/lowest unoccupied molecular orbital (HOMO/LUMO) levels of 2a–b and the conduction band of the perovskite.
more »
« less
Ruthenium pentamethylcyclopentadienyl mesitylene dimer: a sublimable n-dopant and electron buffer layer for efficient n–i–p perovskite solar cells
Electron-transport materials such as fullerenes are widely used in perovskite solar cells to selectively transfer the photogenerated electrons to the electrodes. In order to minimize losses at the interface between the fullerene and the electrode, it is important to reduce the energy difference between the transport level of the two materials. A common approach to reduce such energy mismatch is to increase the charge carrier density in the semiconductor through doping. A variety of molecular dopants have been reported to reduce (n-dope) fullerenes. However, most of them are either difficult to process or extremely air sensitive, with most n-dopants leading to the formation of undesirable side products. Dimers formed by 19-electron organometallic sandwich compounds combine strong reducing ability, clean reactivity, and moderate air stability, while being processable both from solution and in vacuum. In this work, we have investigated the use of pentamethylcyclopentadienyl mesitylene ruthenium dimer, (RuCp*mes) 2 , as a dopant for C 60 in fully vacuum-deposited n–i–p perovskite solar cells. The (RuCp*mes) 2 was either co-evaporated with the fullerene or deposited as a pure thin film on top of the transparent electrode prior to the deposition of the fullerene. It was found that both the co-evaporated blends and the bilayers are effective electron-transport layers, leading to solar cells with efficiencies up to 18%.
more »
« less
- Award ID(s):
- 1807797
- PAR ID:
- 10156621
- Date Published:
- Journal Name:
- Journal of Materials Chemistry A
- Volume:
- 7
- Issue:
- 45
- ISSN:
- 2050-7488
- Page Range / eLocation ID:
- 25796 to 25801
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
null (Ed.)The synthesis, characterization and incorporation of fullerene derivatives bearing primary, secondary and tertiary nitrogen atoms, which possess different basicities, in perovskite solar cells (PSCs), is reported. In this work, we tested the compounds as conventional electron transporting materials (ETMs) in a single layer with phenyl-C 61 -butyric acid methyl ester (PC 61 BM) as control. Additionally, we tested the idea of separating the ETM into two different layers: a thin electron extracting layer (EEL) at the interface with the perovskite, and an electron transporting layer (ETL) to transport the electrons to the Ag electrode. The compounds in this work were also tested as EELs with C 60 as ETL on top. Our results show that the new fullerenes perform better as EELs than as ETMs. A maximum power conversion efficiency (PCE) value of 18.88% was obtained for a device where a thin layer (∼3 nm) of BPy-C 60 was used as EEL, a higher value than that of the control device (16.70%) with only pure C 60 . Increasing the layer thicknesses led to dramatically decreased PCE values, clearly proving that the compound is an excellent electron extractor from the perovskite layer but a poor transporter as a bulk material. The improved passivation ability and electron extraction capabilities of the BPy-C 60 derivative were demonstrated by steady state and time-resolved photoluminescence (SS-and TRPL) as well as electrochemical impedance spectroscopy (EIS) and X-Ray photoelectron spectroscopy (XPS) measurements; likely attributed to the enhanced basicity of the pyridine groups that contributes to a stronger interaction with the interfacial Pb 2+ .more » « less
-
Nam-Gyu Park (Ed.)With the rapid development of perovskite solar cells (PSCs), lowering fabrication costs for PSCs has become a prominent challenge for commercialization. At present, gold is commonly used as the back metal electrode in state-of-the-art n-i-p structured PSCs due to its compatible work function, chemical inertness, and high conductivity. However, the high cost of gold and the expensive and time-consuming vacuum-based thin-film coating facilities may impede large-scale industrialization of PSCs. Here, we report a bilayer back electrode configuration consisting of an Ni-doped natural graphite layer with a fusible Bi-In alloy. This back electrode can be deposited in a vacuum-free approach and enables PSCs with a power conversion efficiency of 21.0%. These inexpensive materials and facile ambient fabrication techniques provide an appealing disruptive solution to low-cost PSC industrialization.more » « less
-
null (Ed.)Chemical doping is a key process for controlling the electronic properties of molecular semiconductors, including their conductivity and work function. A common limitation of n-doped polymers is their instability under ambient conditions, which has imposed restrictions on the characterisation and device application of n-doped polymers. In this study, sequential n-doping with organometallic dopants was performed on thin films of polymeric semiconductors with naphthalene diimide and perylene diimide-based backbones. Moderate ambient stability was achieved with (RuCp*Mes) 2 , {Cp* = pentamethylcyclopentadienyl; Mes = 1,3,5-trimethylbenzene}, which is in striking contrast to the unstable, n-doped state obtained with cobaltocene, a simple one-electron reductant. The highly cathodic, effective redox potential of (RuCp*Mes) 2 , ca. −2.0 V vs. ferrocene, suppresses the back electron transfer reaction and the subsequent dopant loss in air, which gives rise to the observed air stability. It also allows a perylene diimide-based polymer to be reduced to a state in which the repeat units are largely dianionic. Photoelectron measurements show that the ionization potential of the heavily doped polymer is ca. 3.9 eV. Our findings show that chemical doping with (RuCp*Mes) 2 is an effective method to produce highly stable, n-doped conjugated polymers.more » « less
-
We present a series of new dopants based on a bicyclcic guanidine-type structure, 1,5,7-triazabicyclo[4.4.0]dec-5-ene ( TBD ), for organic semiconductors. A series of TBD derivatives that were alkylated at the 7-position were synthesized and their physical properties were determined. These stable dopants were shown to be effective n-type dopants for [6,6]-phenyl- C 61 -butyric acid methyl ester (PC 61 BM), poly{[ N , N ′-bis(2-octyldodecyl)naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]- alt -5,5′-(2,2′-bithiophene)} (P(NDI2OD-T2)) and 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3- d :2′,3′- d ′]- s -indaceno[1,2- b :5,6- b ′]dithiophene (ITIC). Films of PC 61 BM doped with 10 mol% of a dimeric derivative of TBD had electrical conductivities of 0.065 S cm −1 . The utility of the dopants was further shown by doping electron transport layers of PC 61 BM with 2TBD-C10 for methyl ammonium lead iodide (MAPbI 3 ) solar cells leading to improved fill factors and PCEs relative to undoped ETLs.more » « less
An official website of the United States government

