Modulating thermal conductance at ligand/nanocrystal interfaces via oxygen-coordinated ligands

Wong, Kae-Lin; Diroll, Benjamin T.; Schaller, Richard D.; Shao, Cheng; Ong, Wee-Liat

doi:10.1039/d5nr02509e

Modulating thermal conductance at ligand/nanocrystal interfaces via oxygen-coordinated ligands

Journal Article · Wed Aug 27 00:00:00 EDT 2025 · Nanoscale

DOI:https://doi.org/10.1039/d5nr02509e· OSTI ID:2588949

^[1]; ^[2]; Schaller, Richard D. ^[2]; Shao, Cheng ^[3]; ^[1]

Zhejiang Univ., Hangzhou (China)
Argonne National Laboratory (ANL), Argonne, IL (United States). Center for Nanoscale Materials (CNM)
Shandong Institute of Advanced Technology, Jinan (China)

Here, the interfacial thermal conductance (h_lig–NC) between a cadmium selenide (CdSe) nanocrystal (NC) and three related organic ligands—olealdehyde, oleyl alcohol, and oleic acid—was investigated computationally. These ligands have the same carbon backbone but differ in the number and type of oxygen-coordinated headgroups (carbonyl and/or hydroxyl), leading to distinct bonding geometries involving monodentate and bidentate bonds. For a fully encapsulated NC, h_lig–NC increases in the order of olealdehyde, oleic acid, and oleyl alcohol ligands. To isolate the contributions of h_lig–NC from each headgroup type, the distinct bonding geometries were analyzed. Aldehyde and alcohol ligands, each featuring a single oxygen headgroup (carbonyl or hydroxyl), exhibit similar O–Cd separations and nearly identical h_lig–NC per ligand at full surface coverage. However, the hydroxyl group in the alcohol ligand enables a higher ligand grafting density on the NC surface, resulting in a greater overall h_lig–NC than the aldehyde-grafted NCs. In contrast, the oleic acid ligand forms multidentate bonds with the NC, leading to a shorter average O–Cd separation and a higher h_lig–NC per ligand compared to monodentate bonds. Nevertheless, steric hindrance from the acid ligand's larger headgroup reduces its grafting density relative to alcohol ligands, ultimately resulting in a lower overall h_lig–NC.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: National Natural Science Foundation of China (NSFC); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 2588949

Journal Information:: Nanoscale, Journal Name: Nanoscale Journal Issue: 36 Vol. 17; ISSN 2040-3364; ISSN 2040-3372

Publisher:: Royal Society of Chemistry (RSC)Copyright Statement

Country of Publication:: United States

Language:: English

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