Role of $p$-$d$ Hybridization on Optical Properties of Chalcopyrite Semiconductors

Harang Kim; Minjae Kim; Neunghee Han; Woonhyuk Baek

REVIEW 4 major objections 4 minor 35 references

Role of $p$-$d$ Hybridization on Optical Properties of Chalcopyrite Semiconductors

T0 review · 4 major / 4 minor · reviewed 2026-08-01 · deepseek-v4-flash

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Pith's one-line read Strong copper–sulfur orbital mixing makes photodoped holes incoherent in chalcopyrite quantum dots, washing out band-edge emission.

desk verdict Plausible p–d hybridization design rule for chalcopyrite QD coherence, but the decoherence mechanism is inferred from static DFT and ensemble PL, not computed. read the letter →

arxiv 2607.22992 v1 pith:ROVWUPIE submitted 2026-07-25 cond-mat.mtrl-sci cond-mat.str-el

Neunghee Han , Harang Kim , Minjae Kim , Woonhyuk Baek This is my paper · ORCID

classification cond-mat.mtrl-scicond-mat.str-el PACS 78.67.Hc71.20.Nr

keywords p-dhybridizationchalcopyritequantumdotsopticalcoherenceCoulombscatteringCuInS2Agphotodopedholes

verification ladder T0 review T1 audit T2 compute T3 formal

The pith

A machine-rendered reading of the paper's core claim, the machinery that carries it, and where it could break.

The reading

The paper argues that the coherence of a chalcopyrite quantum dot's optical spectrum is set by the orbital character of the valence-band top. When transition-metal d and sulfur p orbitals hybridize strongly, as in CuInS2, the photoexcited hole takes on Cu(d) character and decoheres via a Coulomb scattering channel, suppressing band-edge spectral features. When hybridization is weak, as in AgInS2, the hole stays delocalized on sulfur p orbitals and the spectrum remains coherent. Photoluminescence and lifetime data on Cu-doped AgInS2 quantum dots support this picture: adding Cu first introduces a broadened defect side peak that merges with the main band-edge peak, then the spectrum collapses as the Cu ratio rises. The paper's design rule: to keep a coherent optical spectrum, avoid p–d-hybridized orbital character in the photodoped carrier.

What carries the argument

The valence-band-top (VBT) Bloch wavefunction and its orbital character—specifically the degree of p–d hybridization between transition-metal d and sulfur p states—is the central object. The paper computes the density of states, band structures, and VBT charge densities for CuInS2 and AgInS2, plus supercells with anti-site Cu–In or Ag–In swaps and transition-metal vacancies, using first-principles DFT+U+V with self-consistently determined on-site and intersite Hubbard parameters. The key mechanism is the 'Coulomb scattering channel' of the transition-metal d electrons: when p–d hybridization is strong, the photodoped hole acquires d character and scatters incoherently; when weak, the hole re

What would settle it

Measure the orbital character of the photodoped hole in CuInS2 quantum dots directly—for example, via X-ray absorption at the Cu L-edge or optically detected magnetic resonance of the hole: if the band-edge hole is not predominantly Cu(d)-hybridized, the mechanism fails. Alternatively, compute the exciton spectrum in a realistic finite quantum dot model both with and without the Cu(d) Coulomb scattering term; if removing the term does not restore a coherent band-edge line, the causal link asserted in the paper is unsupported.

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Extended reading notes

Core claim

The central claim is that p–d hybridization—the mixing between transition-metal d and ligand p orbitals at the valence-band top—controls whether a photodoped hole in a chalcopyrite semiconductor stays coherent. In CuInS2, the Cu(d) and S(p) levels sit close, so the valence-band-top Bloch state is strongly hybridized; the authors identify this as activating a Cu(d) Coulomb scattering channel that decoheres the exciton spectrum. In AgInS2, the Ag(d) level lies well below S(p), the valence-band top retains predominantly S(p) character, and the hole is delocalized; anti-site disorder and metal-vacancy defects are computed to remain weakly screened, so the optical response stays coherent. The PL

Load-bearing premise

The load-bearing premise is that the orbital character calculated for the valence-band top of a perfect bulk crystal at zero temperature also describes the photo-created hole in a disordered, nanometer-sized quantum dot, and that the computed Coulomb scattering channel is what destroys spectral coherence rather than some other broadening or recombination mechanism.

Editorial extensions

If this is right

If the p–d hybridization picture is correct, the long-standing absence of band-edge emission in CuInS2-based quantum dots is not primarily a surface or shell problem but an intrinsic orbital-coherence property of the valence band.
Alloying Cu into AgInS2 quantum dots is predicted to first create screened, hybridized Cu defect states and then, at higher Cu ratios, trigger the Coulomb scattering that collapses the band-edge spectrum; the observed PL merging at x≈0.007 matches this threshold behavior.
The design rule 'avoid p–d-hybridized orbital character in the photodoped carrier' gives a concrete criterion for selecting or engineering coherent quantum dot materials: keep the valence-band top ligand-p-like rather than transition-metal-d-like.
Computational screening of chalcopyrite and related I–III–VI2 compounds can use the computed VBT orbital character and the U/V parameters as a proxy for optical coherence, before growing dots.
The lifetime behavior in time-resolved PL—an initial drop then a rise and merging—follows from the impurity-screening picture and provides a spectroscopic fingerprint for the onset of the Cu(d) scattering channel.

Reading between the lines

Editorial extensions of the paper, not claims the author makes directly.

The paper's design rule generalizes naturally to other I–III–VI2 and related quantum dots (e.g., CuInSe2, AgInSe2, alloys with Ga); one could predict coherence by computing the VBT d-character fraction and the position of the TM(d) level relative to the anion p level.
A sharper version of the claim would separate homogeneous decoherence (dephasing due to the Cu(d) scattering channel) from inhomogeneous broadening (static disorder); the paper's PL data do not obviously distinguish these, so a single-dot linewidth or photon-echo measurement on individual AIGS dots with different Cu ratios would isolate the mechanism.
If the Cu(d) scattering channel is truly the cause, CuInS2-based dots should show a strongly temperature- or magnetic-field-dependent hole coherence, whereas AgInS2 dots should be comparatively immune—testable predictions via magneto-optical spectroscopy.
The reasoning could be extended to design 'coherent-by-construction' quantum dots by choosing cations whose d-levels sit far below the anion p-levels, keeping the valence-band top S(p)-like and thereby avoiding the decoherence channel entirely.

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Editorial analysis

A structured set of objections, weighed in public.

Desk editor's note, referee report, and a circularity audit.

Desk Editor's Note

read the letter

First thing to know: the paper's core claim—that strong p–d hybridization in CuInS2 creates a Cu(d) Coulomb-scattering channel that decoheres the photodoped hole, while weak hybridization in AgInS2 keeps it coherent—is plausible, practically relevant, and entirely undemonstrated as a dynamical mechanism. What is genuinely new here is the translation of the textbook Cu/Ag hybridization difference into a design rule for quantum-dot optical coherence: avoid p–d hybridized character in the photodoped carrier. That is a useful synthesis, and the paper states it clearly.

The DFT+U+V calculations are solid: eACBN0 gives parameter-free U and V, the U(V) trends (smaller U, larger V for CuInS2) are consistent with the hybridization picture, and the charge-density plots make the orbital character vivid. The experimental side is also competent: the PL red shift, side-peak emergence, and lifetime changes with Cu ratio are cleanly reported. The qualitative consistency between the calculated defect-state broadening and the observed spectral broadening is suggestive.

Now the soft spots. The central mechanistic clause—Coulomb scattering from Cu(d) electrons causing decoherence—is never computed. There is no scattering rate, self-energy, coherence time, or exciton spectral function anywhere. The evidence is static DOS and band structures, so the 'scattering channel' is an interpretation of a broadened defect band, not a calculated quantity. And the measurement is ensemble PL, which cannot separate decoherence from nonradiative recombination, alloy disorder, or size broadening. The non-monotonic lifetime trend (drop then rise with Cu ratio) is waved away with 'enhancement of screening' and no model. The bulk-to-QD mapping is a jump: a 2×2×1 supercell with one antisite is not a disordered, confined dot. The CuInS2 DFT gap (0.88 eV) is far from experiment (1.55 eV), which tempers confidence in the quantitative orbital character at the VBT.

None of this kills the paper. The DFT is not fitted to the PL, so there is no circularity in the traditional sense. The hypothesis is testable, and the paper is honest about what it has and hasn't shown. It reads like a strong Letter that has overinterpreted its own data.

Who should read it: anyone working on chalcopyrite QDs, and people who care about orbital-character design rules for photonic materials. It deserves a serious referee—send it to review—and the referee should ask for a quantitative scattering calculation or single-QD linewidth data, and a softening of the causal language.

Referee Report

4 major / 4 minor

Summary. The manuscript combines DFT+U+V calculations with eACBN0-derived on-site and intersite Hubbard parameters for CuInS2 and AgInS2, including pristine bulks and 2×2×1 supercells with a single antisite defect or metal vacancy, with ensemble photoluminescence and time-resolved photoluminescence measurements on Ag1−xCuxIn1−yGayS2 quantum dots. The authors argue that strong S(p)–Cu(d) hybridization in CuInS2 activates a Cu(d) Coulomb-scattering channel that decoheres the photodoped hole, whereas the weak S(p)–Ag(d) hybridization in AgInS2 preserves a delocalized, mostly S(p)-like hole. They conclude that designing coherent optical spectra in chalcopyrite quantum dots requires avoiding p–d-hybridized character in the photo-doped carrier.

Significance. If the central mechanistic claim were substantiated, this would provide a useful design rule for chalcopyrite quantum dots and would offer a first-principles rationale for the longstanding absence of sharp band-edge emission in CuInS2-based dots. Strengths of the paper include the use of the eACBN0 framework, which determines U and V self-consistently without fitting to the experimental PL data, and the DFT+U+V results improve upon PBE gaps (e.g., AgInS2 gap 1.75 eV vs experimental 1.87 eV; CuInS2 gap 0.88 eV vs 1.55 eV). The experimental PL/TRPL trends are presented clearly and are qualitatively consistent with the proposed picture. However, the distinctive claim—that p–d hybridization causes hole decoherence through a Cu(d) Coulomb-scattering channel—is not directly computed, and the currently available evidence does not uniquely support decoherence over alternative explanations such as nonradiative recombination or inhomogeneous broadening.

major comments (4)

[Abstract; Fig. 3(b) and surrounding text] The central claim is that strong p–d hybridization 'induces the Cu(d) Coulomb scattering channel' and that this 'Coulomb scattering gives rise to the decoherence in the optical spectrum.' In the entire manuscript, no scattering rate, self-energy, spectral function, coherence time, or exciton linewidth is computed. The evidence in Fig. 3(b) is a broadened defect band in a static DFT+U+V DOS, which the text interprets as 'Coulomb scattering.' A broadened or hybridized DOS is not equivalent to quantum decoherence of a photodoped hole; static disorder, lifetime broadening, or a simple resonance could produce the same DOS feature. To make the central claim load-bearing, the authors should compute a dynamical quantity—for example, the hole spectral function with a self-energy from GW/cumulant theory or a real-time propagation of the photodoped hole—and show that the Cu(d) channel produces an i
[Fig. 5 and the paragraph following it] The experimental evidence is ensemble PL and TRPL on Ag1−xCuxIn1−yGayS2 quantum dots. Broadening, merging, and the non-monotonic lifetime trend can all be produced by nonradiative recombination at traps or surfaces, increased alloy disorder, size/shape distribution, or composition-dependent radiative rates. The manuscript attributes the observations to 'Coulomb scattering-induced incoherence' without providing a control that distinguishes homogeneous decoherence from inhomogeneous broadening or nonradiative decay. Single-dot PL linewidths, temperature-dependent PL, or excitation-density-dependent decays would be natural discriminators. As it stands, Fig. 5 is consistent with the proposed mechanism but does not establish it.
[Figs. 1–4 versus Fig. 5; supercell setup] The calculations describe perfect, ordered bulk crystals and a single antisite or single vacancy in a 2×2×1 supercell, while the experiments concern disordered, confined quantum dots. The paper assumes that the zero-temperature bulk VBT Bloch orbital character is also the character of the photodoped hole in a disordered, finite-size quantum dot. This is an assumption, not a result. The authors should at least discuss or test the finite-size and disorder dependence, e.g., by performing calculations for a QD-like supercell or for multiple disorder configurations, and should address the significant gap underestimate for CuInS2 (0.88 eV vs 1.55 eV) as it may affect the predicted VBT orbital character.
[Paragraph after Fig. 5(b)] The non-monotonic lifetime trend (decrease then increase with increasing Cu ratio) is explained qualitatively by 'restoration of lifetime due to the enhancement of screening at Cu defect sites,' but no screening model, timescale, or calculation is provided. This is an important part of the experimental story, and the current explanation is ad hoc. A minimal quantitative model—for example, extracting defect-hole coupling from the DFT wavefunctions and feeding it into a master-equation or golden-rule estimate of the hole dephasing rate—would make the proposed mechanism testable. Without such a model, the causal chain from hybridization to coherence is incomplete.

minor comments (4)

[Fig. 3 and Fig. 4 captions] Typo: 'anti-stie disorder' should be 'anti-site disorder.'
[Table I and text near it] The text states that the intersite V for TM(d)–S(p) is larger in CuInS2 than in AgInS2. Table I shows V(Cu-d,S-p)=2.36 eV > V(Ag-d,S-p)=2.13 eV, but V(Cu-d,S-s)=1.03 eV < V(Ag-d,S-s)=1.17 eV. Please clarify whether the argument relies only on the d–S(p) coupling or on all d–S channels; the current wording is ambiguous.
[Experimental methods] The manuscript reports synthesis of AIGS quantum dots but does not state the actual Cu ratios (x values) used or measured. The PL figure is described as a function of Cu composition, but the numerical composition values are not provided in the main text; they should appear in the Supplemental Material at minimum.
[Conclusion] The conclusion says 'we demonstrate that the p–d hybridization is a key factor,' while the text around Fig. 3 says 'We suggest that this defect-environment hybridization is the origin.' The language should be aligned with the level of evidence actually provided.

Circularity Check

0 steps flagged · score 0.0 of 10

No significant circularity: the DFT+U+V inputs are not fitted to the PL outcome and the central orbital-character comparison has independent content.

full rationale

Score 0. The derivation chain does not contain a step in which a predicted quantity is equal by construction to an input quantity. The Hubbard U and V parameters are determined self-consistently via eACBN0 from the electron density (Table I), not fitted to the PL spectra of Fig. 5. The central comparison is between static DFT+U+V electronic structures of bulk/supercell CuInS2 and AgInS2 and PL/TRPL spectra of AIGS QDs; the orbital-character difference (Cu(d)-S(p) hybridized valence-band top versus S(p)-dominant VBT) is computed from the crystal structures and is not parameterized by the experimental data. The 'Coulomb scattering channel' is an interpretive label attached to a broadened defect band (Fig. 3b) rather than a calculated scattering rate, and the experimental-to-theory link is asserted post hoc ('fingerprint of the present theoretical proposal'). That is an inference-strength / underdetermination concern, not circularity. The only author self-citation (Ref. [17]) is one of several method citations and is not load-bearing for the central claim. No equation in the paper reduces the conclusion to the input.

Assumptions & free parameters 2 free parameters · 4 assumptions · 0 invented entities

No new particles or forces are introduced. The 'Coulomb scattering channel' is a physical mechanism, not a new entity. The main ledger items are the orbital-character-to-coherence link and the bulk-to-QD mapping, both of which are assumed rather than derived.

free parameters (2)

eACBN0 Hubbard U and V values for Cu/Ag d and S p orbitals = U(Cu-d)=5.12 eV, U(Ag-d)=6.68 eV, V(Cu-d,S-p)=2.36 eV, V(Ag-d,S-p)=2.13 eV (Table I)
These are computed self-consistently from the electronic structure, not fitted to the PL data, but they set the hybridization energy scale on which the entire decoherence argument depends. The central claim relies on their relative values between Cu and Ag compounds.
Supercell size and defect geometry (2×2×1; nearest-neighbor anti-site)
The choice of a single anti-site configuration and a single metal-vacancy configuration is a modeling choice that affects the DOS and the inferred screening behavior.

assumptions (4)

domain assumption DFT+U+V with eACBN0-extracted Hubbard parameters gives quantitatively reliable band characters and orbital ordering for CuInS2 and AgInS2.
The paper's own band gap for CuInS2 is 0.88 eV versus 1.55 eV experimental, and the 0.88 eV value is further from experiment than a cited earlier result (1.24 eV). Yet the orbital character data from the same calculation are used as the basis of the mechanism.
ad hoc to paper The zero-temperature bulk VBT Bloch orbital character determines the orbital character (and hence the decoherence) of the photodoped hole carrier in a disordered, confined quantum dot.
This is the central link between bulk DFT and the QD PL data. It is stated qualitatively around Fig. 2 but is never tested with a QD-level or exciton-level calculation.
domain assumption Anti-site disorder and metal deficiency in a bulk 2×2×1 supercell capture the structural and compositional inhomogeneity of the quantum dots.
The paper states 'This anti-site disorder and Cu defect could be inherited by the spatial inhomogeneity in the quantum dot,' but no surface, confinement, or finite-size effects are modeled.
ad hoc to paper The observed PL broadening, merging, and lifetime changes in Fig. 5 are direct signatures of hole-carrier decoherence rather than nonradiative trapping, surface states, or inhomogeneous size broadening.
The paper interprets all spectral changes through the Coulomb-scattering channel, but does not measure or subtract inhomogeneous broadening, nor does it compute a linewidth from the proposed mechanism.

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Pith. "Pith review of Role of $p$-$d$ Hybridization on Optical Properties of Chalcopyrite Semiconductors." pith.science (2026). https://pith.science/paper/ROVWUPIE

@misc{pith2026260722992,
  author       = {Pith},
  title        = {Pith review of: Role of $p$-$d$ Hybridization on Optical Properties of Chalcopyrite Semiconductors},
  year         = {2026},
  howpublished = {\url{https://pith.science/paper/ROVWUPIE}},
  note         = {Machine review of arXiv:2607.22992}
}

abstract

Designing quantum materials for coherent optical properties is a central agenda in quantum technology. Semiconductor quantum dots are an emerging approach for controlling coherent optical properties via confinement effects, tunable band gaps, and exciton binding energies, yet their inherent structural and compositional inhomogeneity degrades the coherence of the optical spectra, posing a major obstacle. We show that, for chalcopyrite semiconductors, hybridization between transition-metal $d$ and ligand $p$ electrons in the valence band is key to the coherence of the quantum dot optical spectrum. We demonstrate this using first-principles electronic-structure calculations and optical spectroscopy. The strong $p$-$d$ hybridization in CuInS$_{2}$ induces the Cu($d$) Coulomb scattering channel, giving rise to the incoherent photodoped hole carrier, while the weak $p$-$d$ hybridization in AgInS$_{2}$ induces the delocalized photodoped hole carrier having a predominant S($p$) orbital character. Our experimental results on optical spectra suggest that when the Cu ratio is enhanced in the Ag$_{1-x}$Cu$_{x}$In$_{1-y}$Ga$_{y}$S$_{2}$ quantum dot, Cu atoms at both Ag sites and defect sites experience enhanced $p$-$d$ hybridization, and a coupling begins to develop between the electrons in the quantum dot and the defect electrons at a small Cu ratio. This coupling activates Cu($d$) Coulomb scattering for photodoped holes traversing the defect sites, producing an incoherent optical response that naturally explains the long-standing absence of band-edge spectral signatures in CuIn$_{1-y}$Ga$_y$S$_2$ quantum dots. These results serve as a guideline for designing semiconductor quantum dots. To achieve a coherent optical spectrum, avoid $p$-$d$-hybridized orbital character in the photo-doped carrier.

Figures

Figures reproduced from arXiv: 2607.22992 by the authors.

**Figure 1.** (a) Density of states of CuInS2 bulk. The bar with a color gradient presents the energy for the Cu(d)-S(p) hybridized peak structure in the density of states. (b) Density of states of AgInS2 bulk. The red and orange colored bars present the energies for the Ag(d) and the S(p) dominant density of states, respectively, having a smaller p-d hybridization compared to the case of CuInS2. The total density of states are… view at source ↗

**Figure 2.** (a) The band structure of CuInS2 bulk. The direct band gap (Eg) at k = Γ is 0.88 eV. (b, c) The charge densities for the wave function of (b) the conduction band (CB) bottom and (c) the valence band (VB) top at k = Γ are presented, indicated by blue and red arrows in (a), respectively. (d) The band structure of AgInS2 bulk. The direct band gap (Eg) at k = Γ is 1.75 eV. (e, f) The charge densities for the wave functi… view at source ↗

**Figure 3.** (a, b, c) The electronic structures of CuInS [PITH_FULL_IMAGE:figures/full_fig_p003_3.png] view at source ↗

Figures from the paper (2 more)

**Figure 4.** Figure 4: (a, b, c) The electronic structures of AgInS [PITH_FULL_IMAGE:figures/full_fig_p004_4.png]

**Figure 5.** Figure 5: (a) Band-edge photoluminescence (PL) spectra of [PITH_FULL_IMAGE:figures/full_fig_p005_5.png]

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Works this paper leans on

35 extracted references

[1]

S. W. Koch, M. Kira, G. Khitrova, and H. M. Gibbs, Semiconductor excitons in new light, Nature materials 5, 523 (2006)

2006
[2]

F. P. García de Arquer, D. V. Talapin, V. I. Klimov, Y.Arakawa, M.Bayer,andE.H.Sargent,Semiconductor quantum dots: Technological progress and future chal- lenges, Science373, eaaz8541 (2021)

2021
[3]

W. Baek, M. S. Bootharaju, K. M. Walsh, S. Lee, D. R. Gamelin, and T. Hyeon, Highly luminescent and catalyti- callyactivesuprastructuresofmagic-sizedsemiconductor nanoclusters, Nature materials20, 650 (2021)

2021
[4]

J.-Y. Kim, J. Yang, J. H. Yu, W. Baek, C.-H. Lee, H. J. Son, T. Hyeon, and M. J. Ko, Highly efficient copper– indium–selenide quantum dot solar cells: suppression of carrier recombination by controlledZnSoverlayers, ACS nano9, 11286 (2015)

2015
[5]

J.-Y. Kim, W. Baek, S. Kim, G. Kang, I. K. Han, T. Hyeon, and M. Park, Moisture proof hole transport layers based onCISequantum dots for highly stable and large active area perovskite solar cells, Applied Surface Science496, 143610 (2019)

2019
[6]

S. M. Park, Y. Kim, Y. Kong, S. Ryu, Y.-H. Kim, C. Lee, B. Kim, K. Park, and H. Yang, RedAg-based i–iii–vi quantum dots as competitive alternatives toInPemit- ters, ACS Energy Letters10, 3005 (2025)

2025
[7]

K. Liu, T. Li, S. Zhang, Y. Liu, X. Zhou, D. Yu, X. Xie, L. Hou, J. Qin, B. Dong,et al., Core-localized cu dopants pin red emission in multinaryAg-based quantum dots, Nano Letters (2026)

2026
[8]

Jiang, M

C. Jiang, M. Tozawa, K. Akiyoshi, T. Kameyama, T. Yamamoto, G. Motomura, Y. Fujisaki, T. Uematsu, S. Kuwabata, and T. Torimoto, Development ofCu–In– Ga–Squantum dots with a narrow emission peak for red electroluminescence, The Journal of Chemical Physics 158(2023)

2023

Show all 35 references

[9]

Sundstrom, A

J. Sundstrom, A. Chemmangat, and P. V. Kamat, Engi- neering excited-state dynamics inAgInS2 quantum dots by gallium incorporation andGaS y shell passivation, Chemistry of Materials (2026)

2026
[10]

J. G. Mann, E. Kostyurina, M. Döblinger, B. Nickel, J. Feldmann, and S. Ghimire, Diminishing surface defects in silver indium sulfide quantum dots enables bandgap- excitonic characteristics, Advanced Optical Materials13, e00434 (2025)

2025
[11]

Motomura, T

G. Motomura, T. Uematsu, S. Kuwabata, T. Kameyama, T. Torimoto, and T. Tsuzuki, Quantum-dot light- emitting diodes exhibiting narrow-spectrum green elec- troluminescence by usingAg–In–Ga–S/GaS x quantum dots, ACS Applied Materials & Interfaces15, 8336 (2023)

2023
[12]

B.-G. Chae, M. Lim, J. Lee, N. Won, S. K. Kwon, A. Jo, D. J. Yun, S. Lee, J.-M. Nam, S. Sul,et al., 3d map- ping of compositional gradients of core-shell structures inAgIn xGa1−xS2 quantum dots by atom probe tomog- raphy, Nature Communications (2026)

2026
[13]

J.H.Kim, J.Song, Y.Park, H.Lim,andJ.Bang,Design- ing band-edge emissiveAgInS2 nanocrystals via compo- sition and structure control, Advanced Optical Materials 13, 2500331 (2025)

2025
[14]

L. A. Agapito, S. Curtarolo, and M. Buongiorno Nardelli, Reformulation ofDFT +Uas a pseudohybrid hubbard density functional for accelerated materials discovery, Phys. Rev. X5, 011006 (2015)

2015
[15]

Lee and Y.-W

S.-H. Lee and Y.-W. Son, First-principles approach with a pseudohybrid density functional for extended hubbard interactions, Physical Review Research2, 043410 (2020)

2020
[16]

Tancogne-Dejean and A

N. Tancogne-Dejean and A. Rubio, Parameter-free hy- bridlike functional based on an extended hubbard model: DFT +U+V, Physical Review B102, 155117 (2020)

2020
[17]

B. G. Jang, M. Kim, S.-H. Lee, W. Yang, S.-H. Jhi, and Y.-W. Son, Intersite coulomb interactions in charge- ordered systems, Physical Review Letters130, 136401 (2023)

2023
[18]

Kohn, Inhomogeneouselectron gas, Physical review136, B864 (1964)

P.Hohenberg andW. Kohn, Inhomogeneouselectron gas, Physical review136, B864 (1964)

1964
[19]

Kohn and L

W. Kohn and L. J. Sham, Self-consistent equations in- cluding exchange and correlation effects, Physical review 140, A1133 (1965)

1965
[20]

Leiria Campo Jr and M

V. Leiria Campo Jr and M. Cococcioni, ExtendedDFT+ U+Vmethod with on-site and inter-site electronic in- teractions, Journal of Physics: Condensed Matter22, 055602 (2010)

2010
[21]

Giannozzi, S

P. Giannozzi, S. Baroni, N. Bonini, M. Calandra, R. Car, C. Cavazzoni, D. Ceresoli, G. L. Chiarotti, M. Cococ- cioni, I. Dabo,et al., Quantum espresso: a modular and open-source software project for quantum simula- tions of materials, Journal of physics: Condensed matter 21, 3...

2009
[22]

H. W. Spiess, U. Haeberlen, G. Brandt, A. Räu- ber, and J. Schneider, Nuclear magnetic resonance in IB− −III− −VI 2 semiconductors, physica status solidi (b)62, 183 (1974)

1974
[23]

G.Delgado, A.J.Mora, C.Pineda,andT.Tinoco,Simul- taneous rietveld refinement of three phases in theAg–In– Ssemiconducting system from x-ray powder diffraction, Materials Research Bulletin36, 2507 (2001)

2001
[24]

See supplementary materials for the computational de- tails and experimental method
[25]

K. E. Hughes, S. R. Ostheller, H. D. Nelson, and D. R. Gamelin, Copper’s role in the photoluminescence of Ag1−xCuxInS2 nanocrystals, from copper-dopedAgInS2 (x∼0) toCuInS 2 (x= 1), Nano letters19, 1318 (2018)

2018
[26]

Shabaev, M

A. Shabaev, M. Mehl, and A. L. Efros, Energy band structure ofCuInS 2 and optical spectra ofCuInS 2 nanocrystals, Physical Review B92, 035431 (2015)

2015
[27]

J.JaffeandA.Zunger,Electronicstructureoftheternary chalcopyrite semiconductorsCuAlS 2,CuGaS 2,CuInS 2, CuAlSe2,CuGaSe 2, andCuInSe2, Physical Review B28, 5822 (1983)

1983
[28]

Liu and E

J. Liu and E. Hua, Electronic structure and absolute band edge position of tetragonalAgInS2 photocatalyst: A hybrid density functional study, Materials Science in Semiconductor Processing40, 446 (2015)

2015
[29]

M. A. Aguilera, J. A. Hernández, M. G. Trujillo, M. O. López, and G. C. Puente, Photoluminescence studies of chalcopyrite and orthorhombicAgInS2 thin films de- posited by spray pyrolysis technique, Thin Solid Films 515, 6272 (2007)

2007
[30]

B. Tell, J. Shay, and H. Kasper, Electrical properties, optical properties, and band structure ofCuGaS 2 and CuInS2, Physical review B4, 2463 (1971)

1971
[31]

P. W. Anderson, Localized magnetic states in metals, Physical Review124, 41 (1961)

1961
[32]

A. C. Hewson,The Kondo Problem to Heavy Fermions (Cambridge University Press, 1993)

1993
[33]

Doniach and E

S. Doniach and E. H. Sondheimer,Green ’s Functions for Solid State Physicists(Imperial College Press, 1998)

1998
[34]

P. W. Anderson, Absence of diffusion in certain random lattices, Physical Review109, 1492 (1958)

1958
[35]

Evers and A

F. Evers and A. D. Mirlin, Anderson transitions, Reviews of Modern Physics80, 1355 (2008). 8 SUPPLEMENT AL MA TERIAL COMPUT A TIONAL DET AILS We performed first-principles calculation using self-consistent extended Hubbard interactions called as density functional theory plusU...

2008

Pith tools

Reviewed August 1, 2026 · model on record in the stance chip above.

[1] [1]

S. W. Koch, M. Kira, G. Khitrova, and H. M. Gibbs, Semiconductor excitons in new light, Nature materials 5, 523 (2006)

2006

[2] [2]

F. P. García de Arquer, D. V. Talapin, V. I. Klimov, Y.Arakawa, M.Bayer,andE.H.Sargent,Semiconductor quantum dots: Technological progress and future chal- lenges, Science373, eaaz8541 (2021)

2021

[3] [3]

W. Baek, M. S. Bootharaju, K. M. Walsh, S. Lee, D. R. Gamelin, and T. Hyeon, Highly luminescent and catalyti- callyactivesuprastructuresofmagic-sizedsemiconductor nanoclusters, Nature materials20, 650 (2021)

2021

[4] [4]

J.-Y. Kim, J. Yang, J. H. Yu, W. Baek, C.-H. Lee, H. J. Son, T. Hyeon, and M. J. Ko, Highly efficient copper– indium–selenide quantum dot solar cells: suppression of carrier recombination by controlledZnSoverlayers, ACS nano9, 11286 (2015)

2015

[5] [5]

J.-Y. Kim, W. Baek, S. Kim, G. Kang, I. K. Han, T. Hyeon, and M. Park, Moisture proof hole transport layers based onCISequantum dots for highly stable and large active area perovskite solar cells, Applied Surface Science496, 143610 (2019)

2019

[6] [6]

S. M. Park, Y. Kim, Y. Kong, S. Ryu, Y.-H. Kim, C. Lee, B. Kim, K. Park, and H. Yang, RedAg-based i–iii–vi quantum dots as competitive alternatives toInPemit- ters, ACS Energy Letters10, 3005 (2025)

2025

[7] [7]

K. Liu, T. Li, S. Zhang, Y. Liu, X. Zhou, D. Yu, X. Xie, L. Hou, J. Qin, B. Dong,et al., Core-localized cu dopants pin red emission in multinaryAg-based quantum dots, Nano Letters (2026)

2026

[8] [8]

Jiang, M

C. Jiang, M. Tozawa, K. Akiyoshi, T. Kameyama, T. Yamamoto, G. Motomura, Y. Fujisaki, T. Uematsu, S. Kuwabata, and T. Torimoto, Development ofCu–In– Ga–Squantum dots with a narrow emission peak for red electroluminescence, The Journal of Chemical Physics 158(2023)

2023