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[RuCp*(1,3,5-R 3 C 6 H 3 )] 2 {Cp* = η 5 -pentamethylcyclopentadienyl, R = Me, Et} have previously been found to be moderately air stable, yet highly reducing, with estimated D + /0.5D 2 (where D 2 and D + represent the dimer and the corresponding monomeric cation, respectively) redox potentials of ca. −2.0 V vs. FeCp 2 +/0 . These properties have led to their use as n-dopants for organic semiconductors. Use of arenes substituted with π-electron donors is anticipated to lead to even more strongly reducing dimers. [RuCp*(1-(Me 2 N)-3,5-Me 2 C 6 H 3 )] + PF 6 − and [RuCp*(1,4-(Me 2 N) 2 C 6 H 4 )] + PF 6 − have been synthesized and electrochemically and crystallographically characterized; both exhibit D + /D potentials slightly more cathodic than [RuCp*(1,3,5-R 3 C 6 H 3 )] + . Reduction of [RuCp*(1,4-(Me 2 N) 2 C 6 H 4 )] + PF 6 − using silica-supported sodium–potassium alloy leads to a mixture of isomers of [RuCp*(1,4-(Me 2 N) 2 C 6 H 4 )] 2 , two of which have been crystallographically characterized. One of these isomers has a similar molecular structure to [RuCp*(1,3,5-Et 3 C 6 H 3 )] 2 ; the central C–C bond is exo , exo , i.e. , on the opposite face of both six-membered rings from the metals. A D + /0.5D 2 potential of −2.4 V is estimated for this exo , exo dimer, more reducing than that of [RuCp*(1,3,5-R 3 C 6 H 3 )] 2 (−2.0 V). This isomer reacts much more rapidly with both air and electron acceptors than [RuCp*(1,3,5-R 3 C 6 H 3 )] 2 due to a much more cathodic D 2 ˙ + /D 2 potential. The other isomer to be crystallographically characterized, along with a third isomer, are both dimerized in an exo , endo fashion, representing the first examples of such dimers. Density functional theory calculations and reactivity studies indicate that the central bonds of these two isomers are weaker than those of the exo , exo isomer, or of [RuCp*(1,3,5-R 3 C 6 H 3 )] 2 , leading to estimated D + /0.5D 2 potentials of −2.5 and −2.6 V vs. FeCp 2 +/0 . At the same time the D 2 ˙ + /D 2 potentials for the exo , endo dimers are anodically shifted relative to those of [RuCp*(1,3,5-R 3 C 6 H 3 )] 2 , resulting in much greater air stability than for the exo , exo isomer. 

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. 

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%. 

In₂O₃, an n‐type semiconducting transparent transition metal oxide, possesses a surface electron accumulation layer (SEAL) resulting from downward surface band bending due to the presence of ubiquitous oxygen vacancies. Upon annealing In₂O₃in ultrahigh vacuum or in the presence of oxygen, the SEAL can be enhanced or depleted, as governed by the resulting density of oxygen vacancies at the surface. In this work, an alternative route to tune the SEAL by adsorption of strong molecular electron donors (specifically here ruthenium pentamethylcyclopentadienyl mesitylene dimer, [RuCp*mes]₂) and acceptors (here 2,2′‐(1,3,4,5,7,8‐hexafluoro‐2,6‐naphthalene‐diylidene)bis‐propanedinitrile, F₆TCNNQ) is demonstrated. Starting from an electron‐depleted In₂O₃surface after annealing in oxygen, the deposition of [RuCp*mes]₂restores the accumulation layer as a result of electron transfer from the donor molecules to In₂O₃, as evidenced by the observation of (partially) filled conduction sub‐bands near the Fermi level via angle‐resolved photoemission spectroscopy, indicating the formation of a 2D electron gas due to the SEAL. In contrast, when F₆TCNNQ is deposited on a surface annealed without oxygen, the electron accumulation layer vanishes and an upward band bending is generated at the In₂O₃surface due to electron depletion by the acceptor molecules. Hence, further opportunities to expand the application of In₂O₃in electronic devices are revealed.

 

The combination of inorganic and organic semiconductors in a heterojunction is considered a promising approach to overcome limitations of each individual material class. However, to date only few examples of improved (opto‐)electronic functionality have been realized with such hybrid heterojunctions. The key to unraveling the full potential offered by inorganic/organic semiconductor heterojunctions is the ability to deliberately control the interfacial electronic energy levels. Here, a universal approach to adjust the offset between the energy levels at inorganic/organic semiconductor interfaces is demonstrated: the interlayer method. A monolayer‐thick interlayer comprising strong electron donor or acceptor molecules is inserted between the two semiconductors and alters the energy level alignment due to charge transfer with the inorganic semiconductor. The general applicability of this method by tuning the energy levels of hydrogenated silicon relative to those of vacuum‐processed films of a molecular semiconductor as well as solution‐processed films of a polymer semiconductor is exemplified, and is shown that the energy level offset can be changed by up to 1.8 eV. This approach can be used to adjust the energy levels at the junction of a desired material pair at will, and thus paves the way for novel functionalities of optoelectronic devices.

 

n‐Doping electron‐transport layers (ETLs) increases their conductivity and improves electron injection into organic light‐emitting diodes (OLEDs). Because of the low electron affinity and large bandgaps of ETLs used in green and blue OLEDs, n‐doping has been notoriously more difficult for these materials. In this work, n‐doping of the polymer poly[(9,9‐dioctylfluorene‐2,7‐diyl)‐alt‐(benzo[2,1,3]thiadiazol‐4,7‐diyl)] (F8BT) is demonstrated via solution processing, using the air‐stable n‐dopant (pentamethylcyclopentadienyl)(1,3,5‐trimethylbenzene)ruthenium dimer [RuCp*Mes]₂. Undoped and doped F8BT films are characterized using ultraviolet and inverse photoelectron spectroscopy. The ionization energy and electron affinity of the undoped F8BT are found to be 5.8 and 2.8 eV, respectively. Upon doping F8BT with [RuCp*Mes]₂, the Fermi level shifts to within 0.25 eV of the F8BT lowest unoccupied molecular orbital, which is indicative of n‐doping. Conductivity measurements reveal a four orders of magnitude increase in the conductivity upon doping and irradiation with ultraviolet light. The [RuCp*Mes]₂‐doped F8BT films are incorporated as an ETL into phosphorescent green OLEDs, and the luminance is improved by three orders of magnitude when compared to identical devices with an undoped F8BT ETL.