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[Kazuhiro Nemoto](https://orcid.org/0000-0001-5228-1826), Cong Zhang, Daiki Kido, [Daniel Limouchi](https://orcid.org/0009-0005-0205-447X), [Masaki Takeguchi](https://orcid.org/0000-0002-0282-6020), [Hong-Tao Sun](https://orcid.org/0000-0002-0003-7941), [Naoto Shirahata](https://orcid.org/0000-0002-1217-7589)

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[Tailored Pnictogen Precursor Chemistry Enables Metal-Hydride-Free Selective Synthesis of InP                    <sub>                      1–                      <i>x</i>                    </sub>                    Sb                    <sub>                      <i>x</i>                    </sub>                    Quantum Dots](https://mdr.nims.go.jp/datasets/f1f4cdd6-68dd-4892-8017-d509cfbc2553)

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Tailored Pnictogen Precursor Chemistry Enables Metal-Hydride-Free Selective Synthesis of InP1–xSbx Quantum DotsTailored Pnictogen Precursor Chemistry Enables Metal-Hydride-FreeSelective Synthesis of InP1−xSbx Quantum DotsKazuhiro Nemoto,* Cong Zhang, Daiki Kido, Daniel Limouchi, Masaki Takeguchi, Hong-Tao Sun,and Naoto Shirahata*Cite This: Chem. Mater. 2026, 38, 3486−3495 Read OnlineACCESS Metrics & More Article Recommendations *sı Supporting InformationABSTRACT: Controlling precursor reactivity through liganddesign remains a central challenge in the colloidal synthesis ofIII−V quantum dots (QDs). In particular, InSb QDs have beendifficult to access due to hazardous metal-hydride reductants andlimited precursor availability. Here, we report a metal-reductant-free route employing tris(dimethylamino)phosphine [P(NMe2)3],whose function as a reductant or a P(−III) source is determined bythe coordination environment of SbCl3. When Sb−oleylamine(OlNH2) complexes are used, P(NMe2)3 reduces both Sb and Inprecursors, producing phase-pure InSb QDs. In contrast, Sb−trioctylphosphine (TOP) complexes undergo partial Sb(+III)reduction via electrons released from TOP oxidation, whileP(NMe2)3 simultaneously reduces In and generates P(−III)species, enabling controlled formation of alloyed InP1−xSbx QDs (0.6 ≤ x < 1). 31P NMR and EXAFS analyses reveal that theSb−TOP complex exists in a dynamic chloride−phosphine equilibrium, which governs P(−III) availability and reaction selectivity.This mechanistic insight demonstrates that ligand coordination can be leveraged to modulate precursor reactivity, selectively directreduction pathways, and achieve controlled alloying in colloidal III−V QDs. The resulting QDs exhibit sharp excitonic absorptionand band-edge emission in the short-wavelength infrared (SWIR) region, bridging the previously inaccessible spectral gap betweenInP and InSb. Beyond InSb and InP1−xSbx, these findings establish a general design principle: dynamic ligand environments can beexploited to tune reactivity, composition, and alloy formation in colloidal semiconductors. This work thus provides a safe, high-yielding, mechanistically rational strategy for Sb-based III−V QDs and lays the foundation for extending optoelectronic functionalitythrough precise precursor engineering.■ INTRODUCTIONGroup III−V semiconductors are a class of RoHS-compliantmaterials distinguished by high carrier mobility, low electroneffective mass and composition-tunable bandgaps achievedthrough alloying.1 When processed as colloidal quantum dots(QDs), these materials exhibit strong quantum confinementeffects, enabling a wide range of optoelectronic applications,including solar cells,2,3 photodetectors,4−6 light-emittingdiodes,7,8 and biomedical imaging.9−11The colloidal synthesis of III−V QDs was pioneered in 1989by Wells and co-workers,12 who employed tris(trimethylsilyl)-arsenide as a pnictide precursor to generate InAs and GaAsQDs via dehalosilylation.12,13 This highly reactive precursorchemistry was later extended to InP14,15 and InSb QDs,16,17enabling fast nucleation and brief growth, narrow sizedistributions, and highly crystalline nanocrystals whilegenerating volatile Si-containing byproducts that are readilyremoved after reaction.8,18,19 Indeed, tris(trimethylsilyl)-phosphine (TMS−P) has long been the benchmark for InPQDs and enables near-unity photoluminescence quantum yield(PLQY) after shelling.8 However, its rapid consumptionduring nucleation limits control over growth, hindering theformation of larger nanocrystals, and its pyrophoric, airsensitive nature poses significant safety concerns.20 Theselimitations have stimulated efforts toward alternative precursorsystems.Aminophosphines have emerged as cost-effective andsynthetically accessible pnictogen precursors suitable for QDsynthesis.21−23 In oleylamine, transamination generates tris-(oleylamino)phosphine in situ, which undergoes disproportio-nation to form both P(+V) and reactive P(−III) species.21,22The latter reacts with In(+III) to deliver InP units, enablinghigh-quality InP QDs with visible PLQYs exceeding 95% afterReceived: December 4, 2025Revised: March 24, 2026Accepted: March 27, 2026Published: April 2, 2026Articlepubs.acs.org/cm© 2026 The Authors. Published byAmerican Chemical Society3486https://doi.org/10.1021/acs.chemmater.5c03273Chem. Mater. 2026, 38, 3486−3495This article is licensed under CC-BY 4.0Downloaded via 113.33.250.99 on April 16, 2026 at 10:48:23 (UTC).See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.https://pubs.acs.org/action/doSearch?field1=Contrib&text1="Kazuhiro+Nemoto"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Cong+Zhang"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Daiki+Kido"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Daniel+Limouchi"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Masaki+Takeguchi"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Hong-Tao+Sun"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Naoto+Shirahata"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Naoto+Shirahata"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/showCitFormats?doi=10.1021/acs.chemmater.5c03273&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.chemmater.5c03273?ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.chemmater.5c03273?goto=articleMetrics&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.chemmater.5c03273?goto=recommendations&?ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.chemmater.5c03273?goto=supporting-info&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.chemmater.5c03273?fig=tgr1&ref=pdfhttps://pubs.acs.org/toc/cmatex/38/7?ref=pdfhttps://pubs.acs.org/toc/cmatex/38/7?ref=pdfhttps://pubs.acs.org/toc/cmatex/38/7?ref=pdfhttps://pubs.acs.org/toc/cmatex/38/7?ref=pdfpubs.acs.org/cm?ref=pdfhttps://pubs.acs.org?ref=pdfhttps://pubs.acs.org?ref=pdfhttps://doi.org/10.1021/acs.chemmater.5c03273?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://pubs.acs.org/cm?ref=pdfhttps://pubs.acs.org/cm?ref=pdfhttps://creativecommons.org/licenses/by/4.0/shelling.24−26 Extending this strategy to aminoarsines revealedlimited reactivity: tris(oleylamino)arsine cannot undergodisproportionation to form As(−III) species.27 This challengewas addressed by introducing aminophosphine, which reducesAs(+V) to As(−III), as shown in equation27:+ [ ] + [ ] ++ + [ ]InCl As NMe 3P NMe 12RNHInAs 12HNMe 3 P(NHR) Cl3 2 3 2 3 22 4 (1)In contrast, synthesizing colloidal InSb QDs remainsparticularly challenging due to lack of Sb(−III) such as stibine(SbH3).28 Reiss et al. reported that Sb(+III) can be reduced toSb(−III) by In(+I),29 but most successful syntheses rely onstrong metal hydrides such as lithium triethylborohydride(LiEt3BH)30−39 These reagents coreduce Sb(+III) and In-(+III) to zerovalent species that nucleate InSb, as shown inequation:+In(0) Sb(0) InSb (2)However, their high hydride donor ability (ΔG°h = 26 kcalmol−1)34 often leads to uncontrolled reduction and metallicbyproducts, compromising control over nucleation and growth.Recent efforts have turned to milder hydrides,35 such as AlaneN,N-dimethylethylamine (AlH3·DMEDA) with a weakerreducing ability of ΔG°h = 37 kcal mol−1,36,37 yet a metal-hydride-free synthesis of InSb QDs has not been demon-strated. Although P(NMe2)3 is much weaker reductant,34 itsability to form InSb under QD synthesis conditions hasremained unexplored.Here, we report a metal-reductant-free route to phase-pureInSb QDs. As outlined in Scheme 1, P(NMe2)3 acts as aselective reductant that enables high-yield formation of InSbfrom indium palmitate [In(Palm)3] and an SbCln−oleylaminecomplex (Sb−OlNH). Remarkably, replacing Sb−OlNH withan SbCln−trioctylphosphine complex (Sb−TOP) allows P-(NMe2)3 to serve dually as both a reductant and a phosphorussource, yielding anion-alloyed InP1−xSbx QDs (0.6 ≤ x < 1).The resulting QDs exhibit well-defined first excitonicabsorption peaks and corresponding band-edge PL, demon-strating the effectiveness of this metal-reductant-free strategy.■ RESULTSInP1−xSbx QDs (0.6 ≤ x ≤ 1) were synthesized using amodified hot-injection procedure adapted from established InPQD syntheses.21,27,38 A schematic overview of the method isprovided in Figure S1 (see Supporting Information). Buildingupon our preliminary findings (Section S1, Figure S2,Supporting Information), In(Palm)3 served as the indiumprecursor and 1-octadecene (ODE) as the reaction solvent. Wefound that the coordination environment of the antimonyprecursor strongly affected the reducing ability of P(NMe2)3,leading to distinct final chemical composition of the QDs(Scheme 1). To identify suitable antimony precursors, weevaluated the solubility of several SbCln−L Lewis acid−baseadducts in ODE�where L = trioctylphosphine (TOP),diphenylphosphine (DPP), or OlNH2�and confirmed thatboth TOP and OlNH2 form stable complexes with SbCl3(Section S2, Figures S3 and S4, Table S1, SupportingInformation). Following the procedure outlined in Figure S1,In(Palm)3 was heated with either Sb−OlNH or Sb−TOP at190 °C in ODE under Ar atmosphere. A mixture of P(NMe2)3and excess OlNH2 (>3 equiv) was then swiftly injected toinitiate nucleation. The resulting mixture was subsequentlyheated to 280 °C, maintained for 2 min, and cooled to roomtemperature. After the reaction, the crude solution was purifieddirectly by centrifugation, yielding a supernatant (Mothersample) and an insoluble fraction (Precipitate). Precipitateconsisted of macroscopic InSb crystals in both the OlNH- andTOP-based systems (Figure S5, Supporting Information). Incontrast, Mother sample was separated into Samples A, B, andC via stepwise ethanol-induced fractionation (Section S3,Figures S6 and S7, Supporting Information).Optimization of the synthetic conditions confirmed theformation of QDs in the mother sample (Section S4,Supporting Information). Specifically, the injection temper-ature of the Sb and P precursors was investigated. Attemperatures below 140 °C, the balance between nucleationand growth could not be controlled, and almost no QDs wereformed. In contrast, at temperatures above 240 °C, low-boilingP(NMe2)3 evaporated, leading to the preferential formation ofreadily reducible metallic Sb and a decrease in the yield of InSbQDs. Injection at 190 °C enabled the recovery of QDs withoutgenerating metallic impurities (Figure S8b, SupportingInformation). Furthermore, as shown in Scheme 1, thesimultaneous addition of a Zn source with In(Palm)3 improvedthe size distribution (Figure S8b, Supporting Information).XRD and TEM analyses were performed to elucidate thestructural characteristics of Samples A−C prepared using theSb−OlNH and Sb−TOP precursor systems. As shown inFigure 1a, Sample A from the Sb−OlNH route exhibits threediffraction peaks (green) corresponding to the (111), (220),and (311) planes of zinc-blende InSb. In contrast, Samples Afrom the Sb−TOP system show diffraction features positionedbetween those of InSb and InP, shifting systematically to lower2θ values with increasing Sb/In feed ratio. This behavior isconsistent with the formation of InP0.4Sb0.6 QDs (blue) andInP0.2Sb0.8 QDs (orange), matching theoretical predic-tions.39,40 TEM analysis (Figures 1b and S9) revealed thatthe resulting InP1−xSbx QDs (x = 0.6−0.8) have meandiameters of 4.1 ± 1.6 and 4.2 ± 1.3 nm, respectively,indicating that variations in phosphorus content do notScheme 1. Schematic Illustration of the PrecursorChemistry and Reaction Concept Leading to the SelectiveFormation of InP1−xSbx QDsaaIndium acetate (In(Ac)3) is first converted into In(Palm)3 throughligand exchange with palmitic acid in octadecene (ODE). Thereaction mixture is then heated under an argon atmosphere, and theSb precursor, the P(NMe2)3, and a small amount of OlNH2 are addedto generate either InSb or InP1−xSbx QDs. The final product can beselectively controlled by tuning the coordination environment ofSbCl3. When SbCl3 is mixed with OlNH2, InSb QDs are formed,whereas mixing SbCl3 with TOP leads to the selective formation ofInP1−xSbx QDs.Chemistry of Materials pubs.acs.org/cm Articlehttps://doi.org/10.1021/acs.chemmater.5c03273Chem. Mater. 2026, 38, 3486−34953487https://pubs.acs.org/doi/suppl/10.1021/acs.chemmater.5c03273/suppl_file/cm5c03273_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acs.chemmater.5c03273/suppl_file/cm5c03273_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acs.chemmater.5c03273/suppl_file/cm5c03273_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acs.chemmater.5c03273/suppl_file/cm5c03273_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acs.chemmater.5c03273/suppl_file/cm5c03273_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acs.chemmater.5c03273/suppl_file/cm5c03273_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acs.chemmater.5c03273/suppl_file/cm5c03273_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acs.chemmater.5c03273/suppl_file/cm5c03273_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acs.chemmater.5c03273/suppl_file/cm5c03273_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acs.chemmater.5c03273/suppl_file/cm5c03273_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acs.chemmater.5c03273/suppl_file/cm5c03273_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acs.chemmater.5c03273/suppl_file/cm5c03273_si_001.pdfhttps://pubs.acs.org/doi/10.1021/acs.chemmater.5c03273?fig=sch1&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.chemmater.5c03273?fig=sch1&ref=pdfpubs.acs.org/cm?ref=pdfhttps://doi.org/10.1021/acs.chemmater.5c03273?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-assignificantly affect particle size within experimental error. Ashighlighted in Figure 1c, high-resolution imaging shows well-defined facets composed of low-index planes such as {111} and{110}, confirming the absence of amorphous domains. Themeasured lattice spacing (∼0.62 nm) lies between those ofbulk InSb (∼0.65 nm) and InP (∼0.59 nm) and agrees wellwith values extracted from XRD.STEM-EDX elemental mapping demonstrates homogeneousdistributions of In, P, and Sb within individual particles,verifying the formation of genuine anion-alloyed InP1−xSbxQDs rather than physical mixtures of InP and InSb (Figure1d−g). In addition, a EDX line profile acquired across singleparticles do not exhibit core−shell-like elemental distributionsor abrupt compositional transitions (Figure 1h,i).For comparison, the Sb−OlNH system produced phase-pureInSb QDs (x = 1) with a mean diameter of 4.1 ± 0.9 nm. Tofurther substantiate alloy formation, XPS was conducted onInP1−xSbx QDs (x = 0.8−0.6) (see Figure S10, SupportingInformation). The In 3d5/2 binding energies of bulk InSb andInP are 443.5−444.0 eV16,31 and 444.6−444.7 eV41,42respectively. As shown in Panels (b)−(c), the In 3d5/2 peakshifts progressively from 444.0 to 444.5 eV as the Sb/In feedratio decreases (x = 0.8 → 0.6), consistent with the higherelectronegativity of phosphorus.The continuous shift of the In 3d5/2 binding energy withcomposition indicates a gradual change in the chemicalenvironment surrounding the indium atoms, supporting theformation of an alloy structure. Indeed, Pietra et al. reported acontinuous shift of the In 3d peak with increasing Zn contentin InxZnyP QDs,43 which they interpreted, in combination withXRD analysis, as evidence of alloy formation. The systematicshift of the In 3d peak observed in this study similarly providesstrong support for the formation of an anion-alloyed QDstructure.Figure 2a−c shows the SWIR absorption and PL spectra ofInP1−xSbx QDs with x = 0.6, 0.8, and 1.0, each exhibiting thecharacteristic band-edge emission expected for direct bandgapIII−V QDs. The asymmetry of the PL spectrum was revealedby time-resolved PL measurements to originate from the sizedistribution (Figure S11, Supporting Information). When thecomposition was varied from x = 0.6 to 0.8 while maintaining acomparable particle size of ∼4.2 nm (Figure S9, SupportingInformation), the PL peak red-shifted from 1125 to 1220 nm,reflecting increased Sb incorporation within the alloyed lattice.These results demonstrate that the optical response of the QDscan be systematically tuned through precise control of theanion composition. Although QDs with x ≤ 0.6 were alsoaccessible and emitted near 650 nm, their separation from InPFigure 1. (a) XRD patterns of InP1−xSbx QDs synthesized from Sb−TOP system (blue: Sb/In = 0.3 feed ratio, orange: Sb/In = 0.5 feed ratio) andSb−OlNH system (green). The lattice constants calculated from the diffraction peaks were 0.635 (orange) and 0.623 nm (blue). (b) HAADF-STEM and (c) HR-TEM images of the InP0.4Sb0.6 QDs. (d−f) Absorption and PL spectra of InP1−xSbx QDs with chemical composition X = 0.6.(d) STEM-EDX overlay image of elemental maps in panels (e), (f), and (g), identifying colocalization of In (green), Sb (blue), and P (red) intypical QDs. (h) Image cropped from the area within the white frame in panel (d). (i) Corresponding line profile of P, In, and Sb EDX signalintensities acquired along the orange line in panel (h).Figure 2. (a−c) Absorption and PL spectra of InP1−xSbx QDs with chemical composition X = 0.6−1.0.Chemistry of Materials pubs.acs.org/cm Articlehttps://doi.org/10.1021/acs.chemmater.5c03273Chem. Mater. 2026, 38, 3486−34953488https://pubs.acs.org/doi/suppl/10.1021/acs.chemmater.5c03273/suppl_file/cm5c03273_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acs.chemmater.5c03273/suppl_file/cm5c03273_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acs.chemmater.5c03273/suppl_file/cm5c03273_si_001.pdfhttps://pubs.acs.org/doi/10.1021/acs.chemmater.5c03273?fig=fig1&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.chemmater.5c03273?fig=fig1&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.chemmater.5c03273?fig=fig1&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.chemmater.5c03273?fig=fig1&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.chemmater.5c03273?fig=fig2&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.chemmater.5c03273?fig=fig2&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.chemmater.5c03273?fig=fig2&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.chemmater.5c03273?fig=fig2&ref=pdfpubs.acs.org/cm?ref=pdfhttps://doi.org/10.1021/acs.chemmater.5c03273?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asQDs was challenging, resulting in broadened PL features(Figure S12, Supporting Information). InSb QDs (x = 1.0)with an average diameter of 3.5 nm (Figure S9c, SupportingInformation) displayed a PL peak at 1161 nm (1.07 eV),consistent with the established size-bandgap relationship forInSb QDs.44 The corresponding absorption spectrum ex-hibited a well-defined excitonic peak with a pronounced valleydepth of 0.16.The size-dependent PL tunability of InP1−xSbx QDs isshown in Figure S13. Size control can be achieved by varyingthe type of saturated fatty acid used during synthesis, andreplacing palmitic acid with lauric acid resulted in anapproximately 70 nm redshift of the PL emission. In addition,in syntheses employing metal halide-based additives, atendency toward the formation of relatively larger particleshas been reported compared to saturated fatty acid−basedsystems; accordingly, the addition of ZnCl2 during synthesisenabled a further redshift of the emission wavelength up to1380 nm (see Figure S13c). Furthermore, as shown in FigureS14, the PL emission wavelength was tuned over a broadspectral window ranging from 860 to 1380 nm by controllingthe composition and particle size. Notably, PL peaks emergingin the 800−970 nm region bridge the photon energy gapbetween the tunable spectral ranges of InP and InSb QDs. Atrend toward narrower fwhm values was also observed as theemission wavelength red-shifted. This behavior can beexplained by the effective mass approximation (EMA), whichdescribes the size dependence of the bandgap in semi-conductor QDs. As particle size increases, the bandgapbecomes less sensitive to size variations, leading to a narroweremission energy distribution even with a similar sizedispersion.The absolute PLQYs of the InP1−xSbx QDs, measured bystandardized integrated method, ranged from 0.1 to 1.3%(Figure S15, Supporting Information), comparable to valuesreported for unshelled III−V QDs, such as InP,15 InAs,45 andInSb.32 No significant variation in PLQY was observed forcompositions of x = 0.6, 0.8, and 1.0. Considering theuniformly low emission efficiencies, nonradiative recombina-tion pathways�most likely associated with surface states�appear to dominate over compositional effects within thisrange (Table S3, Supporting Information). These resultsindicate that improving surface passivation is essential toenhance the emission efficiency, and the development of atype-I core−shell structure will therefore be required toachieve bright luminescence.To the best of our knowledge, no previous study hasreported the synthetic yield of colloidal InSb QDs. Wetherefore benchmarked the yield obtained here against that ofour previously reported coreduction method (see Table 1).4,46Under the conventional protocol, substantial formation ofcoarse InSb crystalline precipitates led to modest yield of only13%. In striking contrast, the yield increased to 40% for theInSb QDs synthesized using the Sb−OlNH system and to 36%for the alloyed InP1−xSbx QDs produced using the Sb−TOPsystem�values that are notably high for III−V QDs. Theimproved yield is attributed to the suppression of insolubleprecipitate formation, and it is considered that saturated fattyacids such as PA, employed as ligands in this study, suppressedparticle coarsening. Importantly, both synthetic routes avoidhazardous metal-hydride reductants, providing safer and morescalable pathway toward high-throughput production.■ DISCUSSIONTo date, all attempts to use P(NMe2)3 as a reducing agent inODE have consistently failed in the synthesis of III−V QDs.For example, introducing P(NMe2)3 into indium acetate-basedInP QD syntheses resulted in no QDs formation.47 This lack ofreactivity can reasonably be attributed to the inability of theintermediate P(OlNH)3�generated via transamination be-tween P(NMe2)3 and primary amines (see eq 3)�21,38participate in the reaction network.+ +P(NMe ) 3OlnH 3P(OlnH) 3Me NH2 3 2 3 2 (3)In the present study, the reaction was conducted in ODEusing In(Palm)3 and Sb−L (L = OlNH2 or TOP) as precursors(see Sections S1 and S2, Supporting Information)), whileP(OlNH)3 was supplied through the prereaction of OlNH2with P(NMe2)3. To confirm the reducing ability of P(OlNH)3,a mixture of SbCl3, TOP, and P(OlNH)3 was heated at 190°C, and the resulting solution was analyzed by 31P NMRspectroscopy (see Figure S16). The peak observed around 100ppm is attributed to unreacted transaminated species, whereasthe peak at approximately 30 ppm corresponds to P-(NHOl)4Cl formed by oxidation of P(OlNH)3. These resultsindicate that the overall transformation of the reaction can beexplained by the pathway shown in Scheme 2. In this scheme,the oxidation of three equivalents of phosphorus from P(+III)to P(+V) provides the reducing equivalents required toconvert both In(+III) and Sb(+III) to their zerovalent states,thereby initiating InSb nucleation. Experimentally, decreasingOlNH2:P(NMe2)3 molar ratio below 3 reduced the formationof P(OlNH)3, resulting in insufficient reduction of the trivalentcations and, consequently, a markedly lower synthetic yield ofInSb QDs. These observations strongly support the reactionpathway proposed in Scheme 2.Table 1. Comparison of Reactants for QD Synthesis and Synthetic Yields of the Resultant Mother SampleaIn source Sb source reductant solvent mother sample synthetic yieldprevious work InSb QDs InCl3 SbCl3 SH OlNH2 InSb 13%this work InSb QDs In(Palm)3 Sb−OlNH2 P(NMe2)3 ODE InSb 40%this work InP1−xSbx QDs In(Palm)3 Sb−TOP P(NMe2)3 ODE InP1−xSbx 36%aThe synthetic yields were calculated based on the Sb content in the QDs.Scheme 2. Reaction Scheme for InSb FormationaaIn(RCOO)3 and SbCln−L are reduced by three equivalents of P(NHOl)3 to form InSb and oxidized P(V) species. Here, L representscoordinating ligands (OlNH or TOP) bound to SbCln.Chemistry of Materials pubs.acs.org/cm Articlehttps://doi.org/10.1021/acs.chemmater.5c03273Chem. Mater. 2026, 38, 3486−34953489https://pubs.acs.org/doi/suppl/10.1021/acs.chemmater.5c03273/suppl_file/cm5c03273_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acs.chemmater.5c03273/suppl_file/cm5c03273_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acs.chemmater.5c03273/suppl_file/cm5c03273_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acs.chemmater.5c03273/suppl_file/cm5c03273_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acs.chemmater.5c03273/suppl_file/cm5c03273_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acs.chemmater.5c03273/suppl_file/cm5c03273_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acs.chemmater.5c03273/suppl_file/cm5c03273_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acs.chemmater.5c03273/suppl_file/cm5c03273_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acs.chemmater.5c03273/suppl_file/cm5c03273_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acs.chemmater.5c03273/suppl_file/cm5c03273_si_001.pdfhttps://pubs.acs.org/doi/10.1021/acs.chemmater.5c03273?fig=sch2&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.chemmater.5c03273?fig=sch2&ref=pdfpubs.acs.org/cm?ref=pdfhttps://doi.org/10.1021/acs.chemmater.5c03273?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asThe Sb−TOP complex was found to be stable at roomtemperature and served as a soluble antimony precursor. Uponheating above 130 °C, however, the solution graduallydarkened, indicating the onset of elemental antimonyformation. This reduction proceeded more slowly than thatobserved for the analogous Sb−DPP complex. To elucidate thecoordination environment of the Sb−TOP adduct and its rolein nucleation, we began by analyzing it using 31P NMR. FigureS17 shows the 31P NMR spectra of free TOP and of theantimony complex formed by heating a 1:3 mixture of SbCl3and TOP at 190 °C for 2 min. Free TOP exhibits a resonanceat −31 ppm (orange). After heating, the reaction mixturedisplays four distinct peaks at −16, 11, 39, and 106 ppm, withno detectable signal from unbound TOP, indicating completecoordination of TOP to SbCl3. The resonances at 11, 39, and106 ppm are consistent with the stepwise oxidation ofphosphorus from the +III to the +V oxidation state, inagreement with previous report.38 The broad feature at −16ppm is assigned to the Sb−TOP complex, as discussed below.Importantly, these results suggest that TOP coordinated toSbCl3 undergoes gradual oxidation from P(+III) to P(+V),concomitantly donating electrons that are likely accepted bySb(+III), thereby facilitating its reduction to elemental Sb(0).In the previous studies, chalcogenide anions such as sulfur,selenium, and tellurium were shown to readily form complexeswith TOP, which have been widely employed as anionprecursors in the synthesis of compound semiconductorQDs.48,49 In contrast, to our knowledge, no reports havedescribed the formation of cationic complexes between SbCl3and TOP, nor has the structural nature of such species beenelucidated. Considering possible coordination modes, SbCl3−TOP species may adopt either a neutral SbCl3−TOPxformulation or a cationic [SbCl3−x−TOPx]x+ structurefeaturing partial chloride dissociation. If the former structurewere operative, Sb−Cl bond cleavage at 130 °C would beunlikely; the latter appears more plausible. Under thisassumption, chloride dissociation occurs, yet the Sb−TOPinteraction remains weak and thermally labile. Collectively, ourresults indicate that the Sb−TOP complex represents apreviously unrecognized class of cationic Sb(+III) precursors.To elucidate the mechanisms underlying the suppression ofInSb formation and the selective generation of alloyedInP1−xSbx QDs, we investigated the coordination environmentof Sb−TOP. TOP solutions with stepwise additions of SbCl3were compared with InCl3−TOP system as a reference (seeFigure S18, Supporting Information). Unlike InCl3, which ispoorly soluble in TOP, SbCl3 dissolves readily, forminghomogeneous solutions. 31P NMR spectra (see Figure 3) ofthese solutions reveal a single resonance across the entire Sb/TOP molar ratio range, in contrast to the multiple speciesobserved for InCl3−TOP. As the Sb/TOP ratio increases, thepeak shifts downfield, reflecting stronger Sb(+III)−P inter-actions and reduced electronic shielding. The single resonanceand its compositional dependence indicate rapid exchangebetween free and coordinated TOP, supporting a model inwhich chloride dissociation occurs concomitantly withcoordination of phosphorus lone pairs to antimony.While the 31P NMR results clearly demonstrate the dynamiccoordination of TOP to Sb(+III), they do not provide directinformation regarding the behavior of the chloride ligands. Toaddress this, EXAFS measurements were performed to provethe local coordination environment of antimony in thepresence of TOP. The analysis reveals substantial changes inantimony coordination upon complex formation. In theXANES region (Figure 4a), the unaltered absorption edgeconfirms that the oxidation state of antimony remains +III.However, the dampened oscillations and reduced white-lineintensity for the SbCl3: TOP samples indicate a perturbation ofthe original coordination geometry. In Figure 4b, the EXAFSoscillation amplitude of the Sb−TOP complex is markedlylower than that of crystalline SbCl3, suggesting significantalterations in both coordination number and Sb−Cl bonddistances. These results indicate the existence of a dynamicequilibrium in which chloride ligands are partially andreversibly substituted by TOP molecules. Under theseconditions, chloride anions remain in solution, and the rapidexchange between Sb−Cl and Sb−TOP interactions result inan averaged, structurally disordered local environment. Thecorresponding R-space spectra (Figure 4c) show a pronouncedSb−Cl peak (∼2.1 Å) in crystalline SbCl3 that diminishes andbroadens with increasing TOP content, while a shoulder at∼2.4 Å (red arrow) grows, consistent with Sb−P coordination.These observations corroborate the NMR-derived inference ofdynamic ligand exchange and partial chloride dissociation(Figure 3). Based on EXAFS fitting (Figures S19 and S20,Supporting Information), a plausible coordination model forthe SbCl3:TOP = 1:3 system involves one chloride ligand andthree TOP molecules arranged around the Sb(+III) center,forming a distorted tetrahedral geometry. The Sb−Pcoordination number was determined to be 2.9, reflectingthe nominal stoichiometry of the precursor mixture, while theresidual Sb−Cl coordination number of 0.7 supports theretention of a single chloride ligand. These results areconsistent with the formation of a [SbCl(TOP)3]2+-typecomplex.50 The steric bulk of the TOP ligands likely limitsthe coordination number to four. The EXAFS-derived bondlengths of 2.41 ± 0.01 Å for Sb−Cl and 2.59 ± 0.01 Å for Sb−P agree with reported values for these ligand types, supportingthe coexistence of both interactions.51 The slightly elongatedSb−P bond, along with the moderate thermal disorder in theSb−P shell (σ2 = 0.0083 Å2), suggests a flexible, solution-phasecomplex, consistent with the dynamic coordination behaviorinferred from the 31P NMR study. Importantly, the formationof a well-dispersed and labile Sb−TOP complex ensuresefficient delivery of reactive Sb(+III) species into the reactionmedium. Its thermal instability is a critical factor enablinginteraction with the In−P system under the synthesisconditions, thereby providing a favorable pathway for theformation of InP1−xSbx alloyed QDs. As discussed above, theSb−TOP complex promotes the reduction of Sb(+III) tometallic antimony, while P(NMe2)3 primarily functions toFigure 3. 31P NMR spectra of TOP/SbCl3 mixtures with molar ratiosof 20, 3, and 1, respectively.Chemistry of Materials pubs.acs.org/cm Articlehttps://doi.org/10.1021/acs.chemmater.5c03273Chem. Mater. 2026, 38, 3486−34953490https://pubs.acs.org/doi/suppl/10.1021/acs.chemmater.5c03273/suppl_file/cm5c03273_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acs.chemmater.5c03273/suppl_file/cm5c03273_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acs.chemmater.5c03273/suppl_file/cm5c03273_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acs.chemmater.5c03273/suppl_file/cm5c03273_si_001.pdfhttps://pubs.acs.org/doi/10.1021/acs.chemmater.5c03273?fig=fig3&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.chemmater.5c03273?fig=fig3&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.chemmater.5c03273?fig=fig3&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.chemmater.5c03273?fig=fig3&ref=pdfpubs.acs.org/cm?ref=pdfhttps://doi.org/10.1021/acs.chemmater.5c03273?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asreduce In(Palm)3. Concurrently, the reaction environmentfacilitates the disproportionation of tris(oleylamino)-phosphine�generated from the interaction between OlNH2and P(NMe2)3�thereby increasing the availability of reducedphosphide species. Supporting this interpretation, InP QDswere observed as minor byproducts exclusively when TOPserved as the coordinating ligand. To evaluate whether TOPcould also reduce the indium precursor, a control reaction wasconducted under identical conditions in the absence ofP(NMe2)3. XRD analysis of the resulting products revealedmetallic antimony, confirming that TOP alone is incapable ofreducing the indium precursor, and thus, cannot independentlygenerate InSb or InP1−xSbx. These observations underscore theessential role of P(NMe2)3 in reducing indium precursors.Based on these findings, a mechanistic pathway is proposedin Scheme 3, in which multiple key reactions proceedconcurrently during QD formation. The first step involvesthe reduction of Sb(+III) in the Sb−TOP complex to metallicSb (Scheme 3a). In this process, P(NMe2)3 plays a minimalrole due to the steric shielding imposed by the [SbCl(TOP)3]complex. Consequently, the reduction of Sb(+III) ispredominantly mediated by TOP, which undergoes mildoxidation to P(+V), consistent with the 31P NMR observations(Figure S17). The second step (Scheme 3b) represents thereduction of the indium precursor by P(NMe2)3, yieldingmetallic indium and promoting the formation of InP units.Formation of metallic indium is directly observed in theinsoluble byproducts obtained at a Sb/In feed ratio of 0.2(Figure S21, Supporting Information). The resulting In(0)subsequently reacts with Sb(0) to generate InSb units, asdepicted in Scheme 3a. In parallel, the reaction betweenIn(Palm)3 and P(NMe2)3 produces InP units, with the processstrongly influenced by the relative concentration of P(NMe2)3.Since TOP reduces Sb(+III), the consumption of P(NMe2)3 ispartially suppressed, ensuring sufficient phosphine availabilityfor InP formation. Additionally, steric hindrance from thetetrahedral [SbCl(TOP)3] complex further impedes thereduction of antimony by P(NMe2)3, leaving excess phosphinein solution and promoting InP generation. In contrast, in theSb−OlNH system, reduction of both antimony and indiumprecursors proceeds rapidly, resulting in swift P(NMe2)3consumption and suppression of InP formation. Finally, asthe reaction progresses, interparticle alloying between InSb andInP units occurs, giving rise to InP1−xSbx QDs (Scheme 3c).According to this mechanism, extended reaction times shouldfacilitate further alloying, eventually eliminating the InP phaseand yielding phase-pure InP1−xSbx QDs. To test thisprediction, the reaction time was prolonged, and the PLspectra of the resulting products were measured (Figure S22,Supporting Information). As anticipated, the InP emissionpeak disappeared entirely, replaced by a single broad emissionband, confirming the proposed alloying mechanism.■ CONCLUSIONSIn this work, we report the colloidal synthesis of InP1−xSbxQDs (0.6 ≤ x ≤ 1) using P(NMe2)3 as both the phosphorussource and a reductant, circumventing the need for hazardousmetal-hydride reagents. While P(NMe2)3 primarily reduces theFigure 4. XAFS spectra: (a) XANES and (b) k2χ(k) spectra of the SbCl3 and the TOP/SbCl3 mixture with molar ratio of 3. (c) FT-EXAFS spectraof SbCl3 mixed with TOP at various molar ratios (1:3, 1:6, 1:12, and 1:20), showing changes in the local coordination environment around Sbupon complexation with TOP.Scheme 3. Formation of InP1−xSbx Proceeds Through the Following Steps: (a) Sb(0) is Generated Through the Reduction ofSb(+III) by TOP; (b) P(NMe2)3 Reduces the In Precursor to Produce In(0), Which Subsequently Reacts with Sb(0) to FormInSb Units; Because P(NMe2)3 Remains in Excess under the Reaction Conditions, InP Units Were Formed Simultaneously;and (c) Formation of InP1−xSbx QDs Can Be Attributed to Thermally Induced Interdiffusion between InP and InSb UnitsChemistry of Materials pubs.acs.org/cm Articlehttps://doi.org/10.1021/acs.chemmater.5c03273Chem. Mater. 2026, 38, 3486−34953491https://pubs.acs.org/doi/suppl/10.1021/acs.chemmater.5c03273/suppl_file/cm5c03273_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acs.chemmater.5c03273/suppl_file/cm5c03273_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acs.chemmater.5c03273/suppl_file/cm5c03273_si_001.pdfhttps://pubs.acs.org/doi/10.1021/acs.chemmater.5c03273?fig=fig4&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.chemmater.5c03273?fig=fig4&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.chemmater.5c03273?fig=fig4&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.chemmater.5c03273?fig=fig4&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.chemmater.5c03273?fig=sch3&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.chemmater.5c03273?fig=sch3&ref=pdfpubs.acs.org/cm?ref=pdfhttps://doi.org/10.1021/acs.chemmater.5c03273?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asindium and antimony precursors, its role as a P(−III) sourcedepends critically on the coordination environment of theSbCl3 precursor. In particular, the Sb−TOP complex enablesformation of InP1−xSbx QDs (0.6 ≤ x < 1), as its low thermalstability facilitates partial reduction of Sb(+III) to Sb(0),generating a reaction medium conductive to P(−III) speciesformation. NMR and EXAFS analyses demonstrate that theSb−TOP complex exists in a dynamic equilibrium betweenTOP- and Cl-bound states with EXAFS fitting indicating anaverage coordination of three TOP ligands and 0−1 chlorideper Sb center, rationalizing its lability. In contrast, in the Sb−OlNH system, P(NMe2)3 is primarily consumed in reducingindium and antimony precursors, yielding phase-pure InSbQDs. These results establish a safe and versatile syntheticplatform for InP1−xSbx QDs and highlight the importance ofprecursor design in controlling reaction pathways.The strategy of controlling the coordination environment ofpnictogen precursors demonstrated in this study may provide auseful design guideline for other III−V systems, including Ga-based precursors that are difficult to handle. Furthermore,although the PLQY of InP1−xSbx QDs reached up to 1.3%,further improvement is expected through core−shell engineer-ing. Selecting shell materials with relatively close latticeconstants, such as ZnTe, or tuning the composition ofInP1−xSbx to improve lattice matching are viable strategies.Enhancing the PLQY would expand the potential of these QDsin photodetectors, LED devices, and other SWIR applications.■ EXPERIMENTAL SECTIONReagents and MaterialsIndium(III) acetate [In(Ac)3, 99.99%, Aldrich], zinc acetate [Zn-(Ac)2, 99.99%, Aldrich], antimony(III) chloride [SbCl3, 99.95%,Aldrich], zinc oxide [ZnO, 99.999%, Aldrich], tris(dimethylamido)-antimony(III) [Sb[NMe2]3, 99.99%, Aldrich], palmitic acid [PA, 98%,Tokyo Chemical Industry], tris(dimethylamino)phosphine [P-[NMe2]3, 97%, Aldrich], 1-octadecene [ODE, 90%, Aldrich],trioctylphosphine [TOP, 97%, Aldrich], oleylamine [OlNH2, 80−90%, Thermo Scientific Chemicals], tris(trimethylsilyl)-phosphine[(TMS)3P, 98% Strem Chemicals] and oleic acid [OA, 90%, Aldrich]were used without further purification. The purity of argon gas usedfor the synthesis was 99.999%.Preparation of Sb-TOP PrecursorSbCl3 (0.045−0.075 mmol) was dissolved in TOP (1 mL) by stirringthe mixture at 50 °C for 10 min in an Ar-filled glovebox that wascontinuously monitored to maintain both oxygen and water levels ofO2 ≤ 1 ppm and H2O ≤ 5 ppm.Preparation of Sb-OlNH PrecursorSbCl3 (0.045−0.075 mmol) was dissolved in OlNH2 (1 mL) bystirring the mixture at 70 °C for 12 h in an Ar-filled glovebox that wascontinuously monitored to maintain both oxygen and water levels ofO2 ≤ 1 ppm and H2O ≤ 5 ppm.Preparation of P(NMe2)3-OlNHP(NMe2)3 (1.8∼3.0 mmol) was dissolved in 1 mL of OLA at roomtemperature in a same glovebox.Preparation of P(TMS)3-TOPAccording to our protocol reported before,26 P(TMS)3 (0.12 mmol)was dissolved in 1 mL of TOP at room temperature in a glovebox toprepare a P(TMS)3-TOP solution. This stock solution was storedovernight in an Ar-filled vial before use.Preparation of ZnOA-ODEZnO (2.0 mmol) and OA (8.0 mmol) were mixed with 10 mL ofODE in a 50 mL three-necked flask. The mixture was degassed at 120°C for 2 h under vacuum conditions, filled with Ar gas, and then themixture was quickly heated to 290 °C and held for 1 h, after which themixed solution became a transparent, signifying the formation of Zn-oleate (ZnOA). After that, the solution was cooled down to roomtemperature and stored in Ar-filled vial until the use.Synthesis of InP1−xSbx QDs0.15 mmol of In(Ac)3, 0.075 mmol of Zn(Ac)2 and PA (0.575 mmol)were mixed with 6.3 mL of ODE in a 50 mL three-necked flask, withthe reflux condenser attached to the central neck and connected tothe Schlenk line. Using an oil rotary vacuum pump, the flask wasdegassed and purged with Ar gas five times under vacuum conditionsbelow 60 Pa. Degassing of the mixture was performed under vacuumconditions at 120 °C for 12 h. After filled with Ar gas, the solution washeated to 190 °C in 4 min. The preprepared Sb−TOP or Sb−OlNHprecursor solution was rapidly injected in its entirety into the flaskunder flowing Ar. In the case of the Sb−TOP precursor, the initiallycolorless solution turned light brown upon injection, whereas thesolution remained transparent when the Sb−OlNH precursor wasused. After 2 min, the preprepared P[NMe2]3/OlNH2 mixture wasrapidly injected into the flask in its entirety, resulting in a color changeof the solution from light brown to black. The flask was further heatedto 280 °C within 5 min and maintained at 280 °C for 2 min. Theheating mantle heater was removed, and the flask was allowed to coolunder air flow to approximately 200 °C. The flask was then furthercooled with water until the temperature fell below 100 °C. The totalcooling time from 280 °C to below 100 °C was approximately 2 min.Synthesis of InP/ZnS QDs Emitting at 490 nmThe precursor and degassing process were the same as those used forInP1−xSbx QDs. The degassed mixture was cooled to roomtemperature and purged with Ar gas. The P(TMS)3-TOP solutionwas injected into the flask, and the resulting mixture was degassedunder vacuum at 40 °C for 10 min. After refilling with Ar gas, thesolution was heated at 300 °C for 5 min. For shell growth, the InPsolution was cooled to 230 °C, followed by the injection of 2 mL ofZnOA and 250 μL of DDT, and maintained at this temperature for 20min. To further increase the shell thickness, the previous procedurewas repeated twice at an elevated temperature of 240 °C. Afterachieving the desired shell thickness, the solution was cooled to roomtemperature.Synthesis of InP/ZnS QDs Emitting at 600 nmSynthesis of InP/ZnS QDs emitting at 600 nm: In a 50 mL three-neckround-bottom flask, 0.5 mmol of InCl3, 0.5 mmol of ZnCl2, and 7.2mL of oleylamine were added. The flask was evacuated under vacuumat 50 °C for 25 min. Subsequently, the solution was rapidly heated to220 °C under an Ar atmosphere, followed by the swift injection of 5mmol of P(NMe2)3. After 30 min, the temperature was raised to 230°C, and the shell was grown using the same method as for the InP/ZnS QDs emitting at 500 nm. Once shell formation was complete, thesolution was cooled to room temperature.Synthesis of InP/ZnS QDs Emitting at 760 nmFollowed by the hot-injection method reported by Ranjana et al.,52 weprepared the InP/ZnS QDs emitting to In a 50 mL three-neck round-bottom flask, 0.5 mmol of In(I) Cl, 0.7 mmol of TOP, and 7.2 mL ofoleylamine were added. The flask was evacuated under vacuum at 50°C for 25 min. Subsequently, the solution was rapidly heated to 220°C under an Ar atmosphere, followed by the swift injection of 0.5mmol of P(NMe2)3 dissolved in 0.5 mL of ODE. After 30 min, thetemperature was raised to 230 °C, and the shell was grown using thesame method as for the InP/ZnS QDs emitting at 500 nm. Once shellformation was complete, the solution was cooled to room temper-ature.Purification of QDsThe as-synthesized solution (named “product” in the Figure S1) wastransferred to a centrifuge tube and centrifuged at 9000 rpm for 10min. The precipitate and supernatant liquid were separated intorespective centrifuge tubes. Acetone 20 mL was added to the entiresupernatant solution, and the mixture was centrifuged at 9000 rpm for5 min. The supernatant was then discarded. The precipitate wasChemistry of Materials pubs.acs.org/cm Articlehttps://doi.org/10.1021/acs.chemmater.5c03273Chem. Mater. 2026, 38, 3486−34953492https://pubs.acs.org/doi/suppl/10.1021/acs.chemmater.5c03273/suppl_file/cm5c03273_si_001.pdfpubs.acs.org/cm?ref=pdfhttps://doi.org/10.1021/acs.chemmater.5c03273?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asredispersed in 5 mL of hexane and 15 mL of methanol was addeduntil the solution became turbid, followed by centrifugation at 9000rpm for 5 min. This washing process was repeated two times toprepare a mother sample as defined in Figure S1.Separation of InP1−xSbx QDsSeparation of InP1−xSbx QDs was performed by modifying thecentrifugation process reported in elsewhere.53 The mother samplewas subjected to the centrifugation process for separation ofInP1−xSbx QDs from other kinds of QDs. The mother sample wasdispersed in a 5 mL of hexane. The mother solution was centrifugatedat 9000 rpm with incremental addition of ethanol by 0.5 m as shownin Figure S1. For example, the fraction obtained with hexane 5 mLand ethanol 2.5∼3.5 mL was designated as “Sample A” in Figure S1.The centrifugations were all performed at 9000 rpm for 5 min.Despite this separation process, in rare cases weak emissionattributable to InP QDs was still observed in Sample A after PLmeasurements. In such cases, the contribution could be effectivelyremoved by repeating the centrifugation under the same conditions(hexane 5 mL and ethanol 3.5 mL for Sample A).CharacterizationX-ray powder diffraction (XRD) patterns were measured on MiniFlex600 (Rigaku, Japan). High-resolution transmission electron micro-scopic (HR-TEM) images were obtained from JEOL-JEM 2100microscope, operating at 200 kV, equipped with energy dispersive X-ray (EDX) elemental analysis system. Additional high-resolutionSTEM imaging and elemental mapping were conducted using aSpectra Ultra S/TEM (Thermo Fisher Scientific) instrument operatedat 200 kV to achieve improved spatial resolution in compositionalanalysis. Some of the samples were studied by X-ray photoelectronspectroscopy (XPS; Ulvac, PHI Quantera) using AlKα (E = 1486.6eV) radiation. The binding energy (BE) scale was calibrated toprovide Au 4f7/2 = 83.9 eV and Cu 2p3/2 = 932.8 eV. The X-ray sourcewas operated at 10 mA and 12 kV. The core-level signals wereobtained at a photoelectron takeoff angle of 90° (with respect to thesample surface). The BE scales were referenced to 284.6 eV asdetermined by the locations of the maximum peaks on the C 1sspectra of hydrocarbon, associated with an adventitious contami-nation. Optical absorption and emission properties were measuredwith colloidal solution of the QDs. Optical absorption spectra weremeasured by a UV−vis spectrophotometer (JASCO V-650, Japan)with an integrated sphere. Photoluminescence (PL) measurement wascarried out using a modular double grating Czerny−Turnermonochromator and an iHR 320 emission monochromator (1200lines/mm of gratings) coupled to a photomultiplier tube (PMT) on aNanoLog Horiba Jovin Yvon spectrofluorometer with a 450 W xenonarc lamp. The spectral resolution of the system is around 0.3 nm. Toavoid scattered excitation lights, a cut filter for 395 nm-light wasplaced in front of the monochromator-PMT setup. The absolute PLquantum yields (QYs) were measured at room temperature using theQY measurement extended system C13534−01 from HamamatsuPhotonics Co., Ltd. with a 150 W xenon lamp coupled to amonochromator for wavelength discrimination, an integrating sphereas a sample chamber, and a multichannel analyzer for signal detection.Nuclear magnetic resonance (NMR) spectroscopy was employed toinvestigate the coordination environment of phosphorus in SbCl3−TOP mixtures. All spectra were recorded on a 600 MHz NMRspectrometer (JNM-ECZL600R, JEOL) using toluene-d8 as thesolvent. The SbCl3 and TOP solutions were prepared in an argon-filled glovebox to prevent hydrolysis and oxidation, and were sealed inairtight NMR tubes prior to measurement. The molar ratio of TOP toSb was systematically varied between 3 and 20. The 31P NMR spectrawere collected at room temperature without further purification oraddition of reference standards. EXAFS measurements wereconducted at the AR-NW10A beamline of the Photon FactoryAdvanced Ring (PF-AR, 6.5 GeV, 50 mA) at the High EnergyAccelerator Research Organization (KEK), Tsukuba, Japan. A Si(311) double-crystal monochromator was used to monochromatizethe incident X-ray beam. The samples were prepared by mixing SbCl3with TOP, adjusting the TOP/Sb molar ratio in the range of 3 to 20.The mixtures were measured in liquid phase, and antimony K-edgeEXAFS spectra were recorded in transmission mode. The energy scalewas calibrated using a standard pellet of Sb2O3 mixed with boronnitride, by defining the first inflection point of the antimony K-edge as30,492.0 eV. The XAFS spectra were processed using the ATHENAsoftware in the Demeter package.54 The spectra were first subjected tobackground subtraction and normalization, followed by Fouriertransform of the k3-weighted χ(k) functions to obtain the radialstructure function in R-space. EXAFS oscillations were fitted using thefollowing equation implemented in the Artemis software:= +k SNF k kkRkR k( )( )exp( 2 )sin(2 ( ))jj j jjj j022 22(S1)In this equation, Nj is the coordination number, Rj is the bondlength, S02 is the amplitude reduction factor, and σj2 is the Debye−Waller factor. The terms Fj(k) and Φj(k) represent the backscatteringamplitude and phase shift, respectively, both of which weretheoretically calculated using the FEFF code based on the structuralmodel of SbCl3.■ ASSOCIATED CONTENT*sı Supporting InformationThe Supporting Information is available free of charge athttps://pubs.acs.org/doi/10.1021/acs.chemmater.5c03273.Detailed information on synthetic conditions and opticalproperties of indium pnictides QDs; microscopicobservation and elemental mapping results of theprecipitate and InP1−xSbx QDs; size distributions andPLQY spectra of the InP1−xSbx QDs; photographs ofSbCl3 mixed with various solvents and XRD profiles ofthe samples prepared by reaction of these antimonyspecies with indium palmitate; and 31P NMR spectra ofpure TOP and TOP mixed with InCl3 (PDF)■ AUTHOR INFORMATIONCorresponding AuthorsKazuhiro Nemoto − Research Center for MaterialsNanoarchitectonics (MANA), National Institute forMaterials Science (NIMS), Tsukuba 305-0047, Japan;Email: nemoto.kazuhiro@nims.go.jpNaoto Shirahata − Research Center for MaterialsNanoarchitectonics (MANA), National Institute forMaterials Science (NIMS), Tsukuba 305-0047, Japan;Graduate School of Chemical Sciences and Engineering,Hokkaido University, Sapporo 060-0814, Japan;orcid.org/0000-0002-1217-7589;Email: shirahata.naoto@nims.go.jpAuthorsCong Zhang − Research Center for MaterialsNanoarchitectonics (MANA), National Institute forMaterials Science (NIMS), Tsukuba 305-0047, Japan;Graduate School of Chemical Sciences and Engineering,Hokkaido University, Sapporo 060-0814, JapanDaiki Kido − Institute of Materials Structure Science (IMSS),High Energy Accelerator Research Organization (KEK),Tsukuba 305-0801, Japan; Materials Structure ScienceProgram, Graduate Institute for Advanced Studies,SOKENDAI, Tsukuba, Ibaraki 305-0801, JapanDaniel Limouchi − Research Center for MaterialsNanoarchitectonics (MANA), National Institute forMaterials Science (NIMS), Tsukuba 305-0047, Japan;Graduate School of Chemical Sciences and Engineering,Chemistry of Materials pubs.acs.org/cm Articlehttps://doi.org/10.1021/acs.chemmater.5c03273Chem. Mater. 2026, 38, 3486−34953493https://pubs.acs.org/doi/suppl/10.1021/acs.chemmater.5c03273/suppl_file/cm5c03273_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acs.chemmater.5c03273/suppl_file/cm5c03273_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acs.chemmater.5c03273/suppl_file/cm5c03273_si_001.pdfhttps://pubs.acs.org/doi/10.1021/acs.chemmater.5c03273?goto=supporting-infohttps://pubs.acs.org/doi/suppl/10.1021/acs.chemmater.5c03273/suppl_file/cm5c03273_si_001.pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Kazuhiro+Nemoto"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfmailto:nemoto.kazuhiro@nims.go.jphttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Naoto+Shirahata"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://orcid.org/0000-0002-1217-7589https://orcid.org/0000-0002-1217-7589mailto:shirahata.naoto@nims.go.jphttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Cong+Zhang"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Daiki+Kido"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Daniel+Limouchi"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfpubs.acs.org/cm?ref=pdfhttps://doi.org/10.1021/acs.chemmater.5c03273?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asHokkaido University, Sapporo 060-0814, Japan;orcid.org/0009-0005-0205-447XMasaki Takeguchi − Research Center for Energy andEnvironmental Materials, NIMS, Tsukuba 305-0047, Japan;orcid.org/0000-0002-0282-6020Hong-Tao Sun − Research Center for MaterialsNanoarchitectonics (MANA), National Institute forMaterials Science (NIMS), Tsukuba 305-0047, Japan;orcid.org/0000-0002-0003-7941Complete contact information is available at:https://pubs.acs.org/10.1021/acs.chemmater.5c03273Author ContributionsK.N. and C.Z. contributed equally to this work; K.N., C.Z., andN.S. designed research; K.N., C.Z., and H.-T.S. performedresearch; K.N., C.Z. H.-T.S., and N.S. discussed the result; andK.N. and N.S. wrote the paper. All authors commented on thepaper.FundingJSPS KAKENHI (grant no. 24K01462, 24K21720, and24K01278) and Hosokawa Powder Technology Foundation(grant number HPTF24111).NotesThe authors declare no competing financial interest.■ ACKNOWLEDGMENTSA part of this work was supported by “Advanced ResearchInfrastructure for Materials and Nanotechnology in Japan(ARIM)” of the Ministry of Education, Culture, Sports,Science and Technology (MEXT): Proposal NumberJPMXP1224NM5178. The authors thank to the financialsupport by WPI program, JSPS KAKENHI (grant no.24K01462, 24K21720, 24K01278, and 25K22207) andHosokawa Powder Technology Foundation (grant numberHPTF24111).■ ABBREVIATIONSHR-TEM, high-resolution transmission electron microscopy;HAASF-STEM, high-angle annular dark field scanning trans-mission electron microscopy; EDX, energy dispersive X-rayspectroscopy; XRD, X-ray powder diffraction; NMR, nuclearmagnetic resonance; PL, photoluminescence; fwhm, full widthat half-maximum; XPS, X-ray photoelectron spectroscopy■ REFERENCES(1) del Alamo, J. A. Nanometre-Scale Electronics with III−VCompound Semiconductors. Nature 2011, 479 (7373), 317−323.(2) Carey, G. H.; Abdelhady, A. L.; Ning, Z.; Thon, S. M.; Bakr, O.M.; Sargent, E. H. Colloidal Quantum Dot Solar Cells. Chem. Rev.2015, 115 (23), 12732−12763.(3) Kim, T.; Lim, S.; Yun, S.; Jeong, S.; Park, T.; Choi, J. DesignStrategy of Quantum Dot Thin-Film Solar Cells. 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