Ether‐Soluble Cu₅₃ Nanoclusters as an Effective Precursor of High‐Quality CuI Films for Optoelectronic Applications

Abstract

An effective strategy is developed to synthesize high‐nuclearity Cu clusters, [Cu53(RCOO)10(C≡CtBu)20Cl2H18]+ (Cu53), which is the largest CuI/Cu0 cluster reported to date. Cu powder and Ph2SiH2 are employed as the reducing agents in the synthesis. As revealed by single‐crystal diffraction, Cu53 is arranged as a four‐concentric‐shell Cu3@Cu10Cl2@Cu20@Cu20 structure, possessing an atomic arrangement of concentric M12 icosahedral and M20 dodecahedral shells which popularly occurs in Au/Ag nanoclusters. Surprisingly, Cu53 can be dissolved in diethyl ether and spin coated to form uniform nanoclusters film on organolead halide perovskite. The cluster film can subsequently be converted into high‐quality CuI film via in situ iodination at room temperature. The as‐fabricated CuI film is an excellent hole‐transport layer for fabricating highly stable CuI‐based perovskite solar cells (PSCs) with 14.3 % of efficiency.

Observation of Non‐FCC Copper in Alkynyl‐Protected Cu53Nanoclusters

“…Half of them are positioned between and bonded with the first AB layers, while the others are stapled to BC layers (Figure A, in blue). As mentioned, the recently reported Cu 0 NCs are characterized by their respective polyhedron kernels with one central 12‐fold coordinated Cu . In Cu 53 , there are 5 such atoms, shaping into a triangular bipyramid (Figure C).…”

“…As mentioned, the recently reported Cu 0 NCs are characterized by their respective polyhedron kernels with one central 12-fold coordinated Cu. [28][29][30][31][32] In Cu 53 ,t here are 5s uch atoms,s haping into at riangular bipyramid ( Figure 2C). They are the centers of 4a nticuboctahedrons (unit cut from HCP) and one cuboctahedron (Supporting Information, Figure S3).…”

“…A Cu 13 cuboctahedron and Cu 20 NCs were also captured very recently . We have noticed that during the preparation of this work, another Cu 53 NC bearing core–shell structure was reported . Unfortunately, none of them provide a clear image depicting the stacking of Cu atoms, either because they have only one or two Cu atoms mimicking the bonding mode of bulk Cu (that is, 12‐fold coordinated with Cu atoms) or because they are essentially copper hydrides.…”

“…[29][30][31] We have noticed that during the preparation of this work, another Cu 53 NC bearing core-shell structure was reported. [32] Unfortunately,n one of them provide ac lear image depicting the stacking of Cu atoms, either because they have only one or two Cu atoms mimicking the bonding mode of bulk Cu (that is,1 2-fold coordinated with Cu atoms) or because they are essentially copper hydrides.T hus,f reestanding Cu nanomaterial with non-FCC phase has yet to be discovered. [33] We report herein asolution-phase synthesis and structural characterization of three novel layer-structured Cu 0 NCs, namely,Cu 53 (C CPhPh) 9 (dppp) 6 Cl 3 (NO 3 ) 9 (denoted as Cu 53 ) and its two derivatives,C u 53 (C CPh) 9 (dppp) 6 Cl 3 (NO 3 ) 9 (Cu 53 -H)a nd Cu 53 (4-FPhC C) 9 (dppp) 6 Cl 6 (OAc) 6 (Cu 53 -F).…”

Self‐Assembly of Hybrid Oxidant POM@Cu‐BTC for Enhanced Efficiency and Long‐Term Stability of Perovskite Solar Cells

“…[3] Thestability of perovskite layer may be improved by reinforcing intrinsic stability,employing surface passivation, and using appropriate interlayers. [4] However,e ffectively improving and controlling the stability of the HTM layer are less studied which is also important for whole device.A mong the commonly used HTMs, [5] small organic molecule spiro-OMeTAD,h as wildly proven as the dominant HTM for highly efficient PSCs,mainly ascribing to high solubility and well-matched energy level. [6] However, many practical results testify that pristine spiro-OMeTAD has low conductivity,m oderate hole-mobility and long oxidation time in the order of days,restricting its functionality in highefficiency PSCs.…”