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Polyethylene oxide (PEO)-based polymers are commonly studied for use as a solid polymer electrolyte for rechargeable Li-ion batteries; however, simultaneously achieving sufficient mechanical integrity and ionic conductivity has been a challenge. To address this problem, a customized polymer architecture is demonstrated wherein PEO bottle-brush arms are hyperbranched into a star architecture and then functionalized with end-grafted, linear PEO chains. The hierarchical architecture is designed to minimize crystallinity and therefore enhance ion transport via hyperbranching, while simultaneously addressing the need for mechanical integrity via the grafting of long, PEO chains ( M n = 10,000). The polymers are doped with lithium bis(trifluoromethane) sulfonimide (LiTFSI), creating hierarchically hyperbranched (HB) solid polymer electrolytes. Compared to electrolytes prepared with linear PEO of equivalent molecular weight, the HB PEO electrolytes increase the room temperature ionic conductivity from ∼2.5 × 10 –6 to 2.5 × 10 −5  S/cm. The conductivity increases by an additional 50% by increasing the block length of the linear PEO in the bottle brush arms from M n = 1,000 to 2,000. The mechanical properties are improved by end-grafting linear PEO ( M n = 10,000) onto the terminal groups of the HB PEO bottle-brush. Specifically, the Young’s modulus increases by two orders of magnitude to a level comparable to commercial PEO films, while only reducing the conductivity by 50% below the HB electrolyte without grafted PEO. This study addresses the trade-off between ion conductivity and mechanical properties, and shows that while significant improvements can be made to the mechanical properties with hierarchical grafting of long, linear chains, only modest gains are made in the room temperature conductivity. 

Abstract Doping is a fundamental requirement for tuning and improving the properties of conventional semiconductors. Recent doping studies including niobium (Nb) doping of molybdenum disulfide (MoS₂) and tungsten (W) doping of molybdenum diselenide (MoSe₂) have suggested that substitutional doping may provide an efficient route to tune the doping type and suppress deep trap levels of 2D materials. To date, the impact of the doping on the structural, electronic, and photonic properties of in situ‐doped monolayers remains unanswered due to challenges including strong film substrate charge transfer, and difficulty achieving doping concentrations greater than 0.3 at%. Here, in situ rhenium (Re) doping of synthetic monolayer MoS₂with ≈1 at% Re is demonstrated. To limit substrate film charge transfer,r‐plane sapphire is used. Electronic measurements demonstrate that 1 at% Re doping achieves nearly degenerate n‐type doping, which agrees with density functional theory calculations. Moreover, low‐temperature photoluminescence indicates a significant quench of the defect‐bound emission when Re is introduced, which is attributed to the MoO bond and sulfur vacancies passivation and reduction in gap states due to the presence of Re. The work presented here demonstrates that Re doping of MoS₂is a promising route toward electronic and photonic engineering of 2D materials.