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Programmable synthesis of atomically precise semiconductor artificial atoms

Nature Synthesis volume 4, pages 1258–1269 (2025)Cite this article

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Abstract

Precision engineering of semiconductor nanomaterials remains difficult. Here we present a programmable approach to synthesizing a library of atomically precise semiconductor nanoclusters via cation exchange. Using a universal metal–ligand coordination complex to program cations and surface ligands, and a Cu26Se13 template cluster to control the anion lattice, we synthesize a homologous series of Zn14Se13, Cd14Se13 and Hg14Se13 clusters, all featuring a pair of prominent absorption peaks. The shared A14B13 framework with icosahedral anion packing and tetrahedral cation bonding serves as a blueprint for constructing chiral semiconductor nanostructures. Theoretical calculations reveal atom-like frontier orbitals, including triply degenerate P-type orbitals for holes and singlet S-type orbitals for electrons. The doublet absorptions originate from the spin–orbit splitting of the P → S transition. The precise and programmable synthesis is expected to enable atomic-level control over the optical, electronic and spin properties of semiconductor artificial atoms and their assemblies.

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Fig. 1: Programming cations in II14VI13 artificial atoms (II = Zn, Cd, Hg; VI = Se).
Fig. 2: Crystal structures of Cu26Se13(PEt2Ph)14 template cluster and product clusters [Zn14Se13(tmeda)6]2+ (1), Cd14Se13(tmeda)6I2 (2) and Hg14Se13(tmeda)6I2 (3).
Fig. 3: Programming surface ligands of II14VI13 clusters.
Fig. 4: Zincblende artificial solid assembled from chiral Cd14Se13 artificial atoms.
Fig. 5: Comparison of A14B13 cluster skeleton with zincblende and wurtzite phases of bulk semiconductors.
Fig. 6: Periodicity in optical properties of II14VI13 artificial atoms.
Fig. 7: Electronic structures of II14VI13 artificial atoms and the origin of their doublet excitonic transitions.

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Data availability

Crystallographic data for the structures reported in this article have been deposited at the Cambridge Crystallographic Data Centre, under deposition numbers CCDC 2345658 (1), 2345659 (2), 2345655 (3), 2345652 (4), 2345653 (5), 2345657 (6), 2345656 (7) and 2345654 (8). Copies of the data can be obtained free of charge at https://www.ccdc.cam.ac.uk/structures/. All other relevant data generated and analysed during this study, which include experimental, spectroscopic, crystallographic and computational data, are included in this article and its Supplementary Information.

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Acknowledgements

We thank the University of Florida start-up research fund for supporting the experimental work. We thank the National Science Foundation for funding the X-ray diffractometer through grant number CHE-1828064. Theoretical work was performed, in part, at the Center for Integrated Nanotechnologies, an Office of Science User Facility operated for the US Department of Energy (DOE) Office of Science and Los Alamos National Laboratory Institutional Computing Program. Los Alamos National Laboratory, an affirmative action equal opportunity employer, is managed by Triad National Security, LLC for the US Department of Energy’s NNSA, under contract 89233218CNA000001.

Author information

Authors and Affiliations

  1. Department of Chemistry, University of Florida, Gainesville, FL, USA

    Fuyan Ma, Lukasz M. Dobrzycki & Chenjie Zeng

  2. Center for Integrated Nanotechnologies, Materials Physics and Applications Division, Los Alamos National Laboratory, Los Alamos, NM, USA

    Sergei A. Ivanov

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  1. Fuyan Ma
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Contributions

F.M., S.A.I. and C.Z. conceived of the idea. F.M. performed the synthesis and characterization. F.M. and L.M.D. solved the crystal structures. S.A.I. performed theoretical analysis involving the synthesized structures and ESI-MS characterization. F.M., S.A.I. and C.Z. wrote the paper. C.Z. supervised the project.

Corresponding author

Correspondence to Chenjie Zeng.

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Competing interests

C.Z. and F.M. declare a pending patent application on the precision synthesis of semiconductor nanoclusters via cation exchange (US2430202). S.A.I. and L.M.D. declare no competing interests.

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Nature Synthesis thanks Paul Raithby, Tao Wu and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Peter Seavill, in collaboration with the Nature Synthesis team.

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Extended data

Extended Data Fig. 1 Characterization of three MI2(tmeda) complexes (M = Zn, Cd, Hg).

a, 1H NMR of the free tmeda ligand and three complexes in CDCl3. The satellite peaks in CdI2(tmeda) correspond to the coupling between 1H and 113Cd (J = 4 Hz). b, TGA measurements of the complexes.

Source data

Extended Data Fig. 2 Synthesis of II–VI nanoclusters from Cu26Se13 template cluster and MI2(tmeda) cation carriers (M = Zn, Cd, Hg).

a, Reaction with ZnI2(tmeda). b, Reaction with CdI2(tmeda). Excess PPr3 was added to increase complex solubility in toluene. c, Reaction with HgI2. Excess tmeda was added to stabilize the HgSe cluster. Left: Photos showing initial colour changes upon injection of the Cu26Se13 cluster solution (0.1 mL) into the cation solution (0.9 mL). Right: In situ UV-Vis spectroscopy monitoring of the diluted reaction mixture. The absorption spectra were recorded every 10 minutes in the first two hours and every hour for the next 14 hours. The first scan was measured around two minutes after mixing the reagents.

Source data

Extended Data Fig. 3 Crystal structures of resulting II–VI clusters and their packing in unit cells.

a, [Zn14Se13(tmeda)6]2+ cluster with co-crystallized [BPh4]‒ counterions and CH2Cl2 solvent molecules. Each unit cell contains two clusters and four counterions with balanced charges. b, Cd14Se13(tmeda)6I2 cluster co-crystallized with one CdI2(tmeda) complex and several toluene molecules. c, Hg14Se13(tmeda)6I2 cluster. Top: individual cluster; middle: top view of unit cell; bottom: side view of unit cell. The cations are drawn in space-filling mode to highlight the orientation of clusters in unit cells. The dark and light green colours in (b) indicate the left and right Cd14Se13 isomers.

Extended Data Fig. 4 Comparison of Se13 anion lattices of the template cluster and three product clusters.

Top: peripheral Se–Se distances in the icosahedron; middle: radial Se–Se distances in the icosahedron; bottom: tabulated Se–Se distances in clusters and bulk lattices.

Extended Data Fig. 5 Average metal-selenium and metal–ligand distances in the product clusters 1-3.

Top: Scheme for cation positions in A14B13 skeleton; bottom: tabulated M–Se and M–L distances of clusters and bulk lattices. The distance between non-bonded atoms is shown in grey.

Extended Data Fig. 6 Solvent-induced structural variations of Cd14Se13 and Zn14Se13 clusters and their UV-vis spectra comparison.

a, Crystal structures of [Zn14Se13(tmeda)6(CH3CN)]2+ (7) crystallized from CH3CN. b, Crystal structures of Cd14Se13(tmeda)6I2 cluster (8) synthesized from CH2Cl2. c–e, Comparison of absorption spectra of Zn14Se13 (c), Cd14Se13 (d), and Hg14Se13 (e) clusters.

Source data

Extended Data Fig. 7 A14B13 skeleton as a blueprint for constructing semiconductor nanoclusters.

a, Packing of anions in the bulk face-centred cubic (FCC) lattice and in the icosahedral cluster lattice. b, Bonding of cations in the zincblende lattice and in the A14B13 cluster. c, A14B13 skeleton identified in reported structures. Top: inorganic core oriented along a Cn rotation axis. Middle: B13 icosahedral anion framework highlighted with shading; Bottom: A14 cation coordination shown in space-filling mode. The clusters are reoriented to visualize similar cation positions. Redrawn from the CIF files of the references24,25,26,32.

Extended Data Fig. 8 Visualizing the wavefunctions of II14VI13 artificial atoms via Kohn–Sham orbital analysis.

a, [Zn14Se13(tmeda)6]2+. b, Hg14Se13I2(tmeda)6.

Extended Data Fig. 9 Comparison of calculated TDDFT spectra of clusters 1-3.

a, Without spin–orbit coupling. b, With spin–orbit coupling.

Source data

Extended Data Fig. 10 TDDFT structures and spectra.

Comparison of TDDFT structures and spectra of a series of CdSe clusters modified based on Cd14Se13(tmeda)6I2.

Source data

Supplementary information

Supplementary Information

Supplementary Video 1

Kohn–Sham orbitals of [Zn14Se13(tmeda)6]2+ (1).

Supplementary Video 2

Kohn–Sham orbitals of Cd14Se13(tmeda)6I2 (2).

Supplementary Video 3

Kohn–Sham orbitals of Hg14Se13(tmeda)6I2 (3).

Supplementary Data 1

[Zn14Se13(tmeda)6][BPh4]2 (1).

Supplementary Data 2

Cd14Se13(tmeda)6I2 (2).

Supplementary Data 3

Hg14Se13(tmeda)6I2 (3).

Supplementary Data 4

Zn14Se13(tmeda)6Cl2 (4).

Supplementary Data 5

[Cd14Se13(tmeda)6Cl2]n (5).

Supplementary Data 6

[Hg14Se13(tmeda)6Cl2]n (6).

Supplementary Data 7

[Zn14Se13(tmeda)6(CH3CN)][BPh4]2 (7).

Supplementary Data 8

Cd14Se13(tmeda)6I8×0.25 (8).

Source data

Source Data Fig. 1

Source data for UV-vis spectra of clusters in reaction mixture and crystal solution.

Source Data Fig. 6

Source data for energy plots.

Source Data Fig. 7

Source data for energy levels and theoretical spectra.

Source Data Extended Data Fig./Table 1

Source data for NMR and TGA of MI2(tmeda) complexes.

Source Data Extended Data Fig./Table 2

Source data for in situ UV-vis spectra of cation exchange.

Source Data Extended Data Fig./Table 6

Source data for UV-vis spectra of eight clusters.

Source Data Extended Data Fig./Table 9

Source data for theoretical spectrum comparison.

Source Data Extended Data Fig./Table 10

Source data for theoretical spectra of various CdSe clusters.

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Ma, F., Ivanov, S.A., Dobrzycki, L.M. et al. Programmable synthesis of atomically precise semiconductor artificial atoms. Nat. Synth 4, 1258–1269 (2025). https://doi.org/10.1038/s44160-025-00823-6

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