•The helical structure of [email protected] nanorods was formed with achiral reagents•The stability of chiral crystal dislocation of [email protected] nanorods was calculated•Spontaneous chiral symmetry breaking occurred in the self-assembly of [email protected] nanorod Spontaneous chiral symmetry breaking (SCSB) of inorganic compounds is a fundamental issue in the origin of biochirality in the prebiotic environment. Although the spontaneous formation of chiral inorganic compounds with chiral space groups, stacking faults, and dislocations has been extensively investigated, enantiomeric excess has rarely been considered for inorganics, which have long been regarded as a racemate. Here, we found helical lattice distortion of [email protected] nanorods formed with achiral reagents, and the enantiomeric excess assemblies were spontaneously organized during evaporation of nanorod colloidal solution. These findings are likely to be phenomena that exist in many substances and drop a hint for studying the origin of chirality. The SCSB of inorganics might provide extending information for studying chirality in other disciplines. The enantiomeric excess phenomenon in spontaneous chiral symmetry breaking (SCSB) is a crucial issue in the origin of homochirality in nature, whereas chiral inorganic compounds have long been reckoned as racemates. Here, we report the SCSB in the self-assembly of cadmium chalcogenide nanorods, leading to chiral biases away from the racemate. In the presence of achiral organics, helical [email protected] nanorods (HCCNs) with unidirectionally rotated crystal lattices along the rod axis were stochastically formed on the epitaxial interface of the {111}cub/{0001}hex planes. The stability of helical dislocation structures, as supported by a theoretical analysis of their binding energies, suggested the possibility of the emergence of helical structures in an achiral environment. Hierarchical chiral films induced by simple solvent evaporation self-assembly of HCCNs exhibited spontaneous enantiomeric excess between batches, which was speculated to be originated from the enantiomeric excess seed assembly that induce one-handedness dominated system based on the majority rules. The enantiomeric excess phenomenon in spontaneous chiral symmetry breaking (SCSB) is a crucial issue in the origin of homochirality in nature, whereas chiral inorganic compounds have long been reckoned as racemates. Here, we report the SCSB in the self-assembly of cadmium chalcogenide nanorods, leading to chiral biases away from the racemate. In the presence of achiral organics, helical [email protected] nanorods (HCCNs) with unidirectionally rotated crystal lattices along the rod axis were stochastically formed on the epitaxial interface of the {111}cub/{0001}hex planes. The stability of helical dislocation structures, as supported by a theoretical analysis of their binding energies, suggested the possibility of the emergence of helical structures in an achiral environment. Hierarchical chiral films induced by simple solvent evaporation self-assembly of HCCNs exhibited spontaneous enantiomeric excess between batches, which was speculated to be originated from the enantiomeric excess seed assembly that induce one-handedness dominated system based on the majority rules. Chirality is manifest in nature from microscopic to macroscopic world, which has fascinated scientists for being the linchpins of many natural phenomena. 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As a typical semiconductor, chalcogenide with a band gap of 2.4 eV tends to form a one-dimensional nanorod along the [0001]hex direction under a high concentration of monomers due to the high reaction activity of organics on the (0001)hex facet.38Hughes S.M. Alivisatos A.P. Anisotropic formation and distribution of stacking faults in II-VI semiconductor nanorods.Nano Lett. 2013; 13: 106-110Crossref PubMed Scopus (34) Google Scholar The small diameter of the nanorod would lead to easy distortion along the axial [0001]hex direction. The encapsulation of a CdSe core with a small band gap of 1.7 eV in a CdS shell with a large band gap increases the photoluminescence quantum yield through its heterojunction.39Borys N.J. Walter M.J. Huang J. Talapin D.V. Lupton J.M. The role of particle morphology in interfacial energy transfer in CdSe/CdS heterostructure nanocrystals.Science. 2010; 330: 1371-1374Crossref PubMed Scopus (161) Google Scholar Here, a small CdSe core quantity was introduced into CdS rods for effective characterization. The chiral [email protected] nanorods with a diameter of ∼3.8 nm were synthesized via a hot-injection technique with achiral precursors, including wurtzite CdSe cores, trioctylphosphine (TOP), trioctylphosphine oxide (TOPO), trioctylphosphine sulfide (TOPS), octadecylphosphoric acid (ODPA), n-hexylphosphonic acid (HPA), and CdO (see the experimental procedures section for details). All organics were proved to be pure and achiral (Figures S1 and S2). The wide-angle X-ray diffraction (XRD) pattern of [email protected] nanorods (Figure 1A) shows five major reflections at 2θ = 24.8°, 26.5°, 28.1°, 43.7°, and 51.8°, which can be assigned to the 101¯0, 0002, 101¯1, 112¯0, and 112¯2 reflections, respectively, of cadmium chalcogenide with a hexagonal close-packing structure. Compared with the intensities of the reflection peaks of bulk materials, the intensities of the 101¯0 and 112¯0 reflections are much stronger, while the 0002 reflection is weaker, suggesting that the preferred orientation of the nanorods is to stack parallel on the substrate, which can be further confirmed by electron microscopy observations. The [email protected] colloidal solutions are composed of monodispersed single-crystalline nanorods with an average length of ∼65 nm and a diameter of ∼3.8 nm, as shown in transition electron microscopy (TEM) images (Figures 1B and S3). The detailed lattice dislocation structure of the [email protected] nanorods was further investigated by high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) investigations. As shown in Figure 2A, the energy-dispersive spectroscopy (EDS) linear scan along the axial direction showed that the [email protected] (length of 67 nm and diameter of 3.7 nm) was composed of a uniform CdS structure with two sections of CdSe. As the seed of epitaxial growth, CdSe cores with a size of ∼2.3 nm (determined by Peng’s method,40Yu W.W. Qu L. Guo W. Peng X. Experimental determination of the extinction coefficient of CdTe, CdSe, and CdS nanocrystals.Chem. Mater. 2003; 15: 2854-2860Crossref Scopus (4614) Google Scholar Figure S4) were distributed in the 22 ∼ 25 and 40 ∼ 48 nm regions of the nanorod. The fine structure can be observed in the high-magnification HAADF-STEM image (Figure 2B), in which the bright dot corresponds to the high electrostatic potential area, namely, the atoms. The grain shown in Figure 2B mainly consists of hexagonal close-packing structures with ABAB stacking domains (blue dots in Figure 2B) bounded by thin layers of cubic close-packing structures with an ABCABC stacking sequence (red dots in Figure 2B), which corresponds to the wurtzite phases and zinc blende, respectively. At the boundary of the CdS/CdSe interface, as determined by the EDS analysis (Figure 2A), a distorted lattice arrangement is observed, which could have been induced by the lattice mismatch or lattice/basis fluctuation between CdS and CdSe (red shaded areas in Figure 2B). It is worth noting that a continuous twisting of the crystal lattice along the axial direction can also be observed in this grain. A possible 3D model was proposed to explain the experimental observation, and the model consisted of the epitaxial intergrowth of the CdSe core and CdS along the [0001]hex axis with the wurtzite phase mixed with zinc-blende stacking faults (Figure 2D). The detailed dislocation connectivity is shown in Figure S5. According to this model, the contrast in the simulated HAADF-STEM image41Oleynikov P. eMap and eSlice: a software package for crystallographic computing.Cryst. Res. Technol. 2011; 46: 569-579Crossref Scopus (25) Google Scholar from the [112¯0]hex direction closely resembles the experimental results (Figure 2C). The similarity is confirmed by comparing their corresponding FDs (insets of Figures 2B and 2C). This result suggests that an intergrowth model is a plausible structural model for the [email protected] nanorods (Figure 2D). The helical nature of the [email protected] nanorods was characterized by high-resolution TEM (HRTEM) observations. The nanorod showed the typical contrast of the close-packing structure along the [110]cub/[112¯0]hex direction, and the axial direction was determined to be [111]cub/[0001]hex. Notably, only the left part of the nanorod could align with the zone axis, while the right region gradually tilted away from the electron beam (Figure 3A1). Upon sequential left-handed tilting of the sample along the axial direction, the well-aligned region (indicated by the red box) was gradually moved from the left to the right side (Figures 3A2–3A5). Fourier diffractograms (FDs) were taken at local positions of the nanorod to judge the alignment of the corresponding regions. A right-handed twisting lattice structure of helical [email protected] nanorods (HCCNs) was determined with an approximate 6° of rotation along the c axis over a distance of 72 nm, suggesting a tilting angle of ∼0.08°/nm. Moreover, upon sequential right-handed tilting of other HCCNs in the same sample (Figure S6), the left-handedness feature was also found. To reveal the dislocation of the nanorods, we tried dark-field imaging via a single beam condition using 101¯0 diffraction of HCCN from which the corresponding lattice plane aligned to the electron beam is highlighted. Initially, only the left part of the nanorod could be observed, which could be determined from the comparison of the dark-field image and the conventional TEM image (Figures S7B1 and S7A1). Upon sequential tilting of the sample along the axial direction as the direction mark shown in the top-left corner of Figure S7A1, the well-aligned region was gradually moved from the left to the right side (Figure S7B2–S7B9), which directly proved the chiral dislocation structure of a single HCCN. In addition, the almost unchanged selected area electron diffraction patterns of a single HCCN over 9° tilting also indicate the one-handedness continuously helical structure of a single [email protected] To understand the generation of crystal dislocations in HCCNs, we investigated the change in binding energy with chiral defect formation. Due to the heterogeneous composition of [email protected], a mismatch of 3.8% is expected on the {0001}hex crystal planes of the wurtzite phase, which is derived from the difference between the distance between adjacent atoms in the close-packing layer of CdSe and CdS (4.1365 Å for CdS and 4.3000 Å for CdSe). This structural mismatch may lead to stacking faults on the epitaxial interface. The large permanent dipole moment along the long axis of the nanorod structure results in an attraction force that could cause the two nanoparticles to merge, which results in “oriented attachment” due to lowering the total free energy of the crystal suspension. If the attachment process is likely to be imperfect, it results in certain defects in the final products.42Tang Z.Y. Kotov N.A. Giersig M. Spontaneous organization of single CdTe nanoparticles into luminescent nanowires.Science. 2002; 297: 237-240Crossref PubMed Scopus (1756) Google Scholar,43Nie Z.H. Petukhova A. Kumacheva E. Properties and emerging applications of self-assembled structures made from inorganic nanoparticles.Nat. Nanotechnol. 2010; 5: 15-25Crossref PubMed Scopus (1309) Google Scholar44Talapin D.V. Shevchenko E.V. Murray C.B. Titov A.V. Kral P. Dipole−dipole interactions in nanoparticle superlattices.Nano Lett. 2007; 7: 1213-1219Crossref PubMed Scopus (292) Google Scholar As noted above, defects in nanocrystals could be the original cause of the symmetry breaking in HCCNs. As shown in the TEM images, the helical axis of HCCNs is along the axial [0001]hex direction. As displayed in Figure 3B, and as viewed along [1¯1¯1¯]cub/[0001¯]hex, three models of the wurtzite phase CdS with stacking faults and a right-handed dislocation show a chiral structure after relaxation (viewed along [110]cub/[112¯0]hex, [211]cub/[101¯0]hex, and the perspective models are shown in Figure S8), which were obtained by using the DMol3Soai K. Sato I. Shibata T. Komiya S. Hayashi M. Matsueda Y. Imamura H. Hayase T. Morioka H. Tabira H. et al.Asymmetric synthesis of pyrimidyl alkanol without adding chiral substances by the addition of diisopropylzinc to pyrimidine-5-carbaldehyde in conjunction with asymmetric autocatalysis.Tetrahedron Asymmetry. 2003; 14: 185-188Crossref Scopus (209) Google Scholar program in Materials Studio. The defects in the wurtzite CdS lattice occurred through translation along the [101¯0]hex direction and through the rotation operation along the [0001]hex direction (detailed modeling for the calculation is shown in Figures S9–S13). The rotation and translational operations were subject to restrictions within 5° and 1.2 Å, respectively, considering the requirements of the bond length of Cd-S in the lattice (Tables S1 and S2). In the defect model shown in Figure 3Bi, the atomic position and bonding of the wurtzite structure were distorted counterclockwise by 3.2° compared with the perfect wurtzite structure (gray colored structure below, viewed along the [1¯1¯1¯]cub/[0001¯]hex direction). On the other hand, two structures with dislocations were obtained with a counterclockwise crystal lattice distortion at 5.6° and 1.9° (Figures 3Bii and 3Biii) compared with the original structures (gray colored structures below, viewed along the [1¯1¯1¯]cub/[0001¯]hex direction). As a criterion to judge the stability of the CdS dislocation structure, it was found that the binding energies of perfect wurtzite and zinc-blende structures are −83.48 and −83.19 eV, respectively. The binding energies for all defect structures are −83.47, −83.24, and −83.19 eV, indicating that these structures are thermodynamically stable in the CdS structure (Table S3). Thus, the calculation results indicate that the binding energies of the chiral dislocation structure and achiral structure are almost the same. Similar results were also found for the clockwise rotation operation for left-handed CdS. The TEM images of HCCN synthesized at 300°C indicate that the helical structure with chiral dislocation is a stable structure as evidenced by the samples synthesized at different temperatures (Figures S14 and S15). Both transmitted circular dichroism (CD) and circularly polarized luminescence (CPL) spectra of HCCNs dispersed in toluene solution show silent signals, probably because of their racemate state of HCCNs colloidal solution or too weak interaction selectivity between HCCNs and circularly polarized light (Figure S16). A significant SCSB phenomenon was found in the self-assembly of HCCNs. The purity and smoothness of the quartz substrate were examined by XRD, scanning electron microscopy (SEM), and CD spectra (Figures S17–S19). Smooth transparent thin films were simply obtained by facilely dropping the HCCNs in toluene on a quartz substrate and subsequent evaporation. Figure 4A shows the CD spectra and the absorbance of [email protected] nanorod films (CCNFs) with enantiomeric excess with opposite handedness. The mirror-symmetrical CD spectra of CCNFs show a sharp negative peak centered at ∼466 nm with two shoulder peaks at ∼430 and ∼380 nm and a relatively weak peak centered at ∼550 nm, coinciding with the UV-vis bands. According to the characteristic mechanism (Figure S20), the CD spectra of CCNFs include both absorption- and scattering-based OAs. Compared with the CD spectra of CCNFs, the diffuse reflection CD with a white background (Figure S21A) shows that the disappearance of the peaks centered in the range of 300–475 nm and the emergence of new peaks in the range of 475–600 nm indicate that the strong signals in the CD spectra in the range of 300–475 nm are due to the combination of the coupling of strong negative scattering-based OA (SOA) and weak electron transition-based OA (ETOA). It can be considered that the strong circular Bragg resonance was induced by the optical interface between the chiral assembly structure and air and that the new peaks were due to the generation of new electronic states by the coupling between adjacent nanorods. The diffuse reflection CD with a black background displays peaks in the range of 300–475 nm that are opposite to those of the CD spectra, confirming the existence of scattering-based OA (SOA) (Figure S21B), as shown in the simulated CD spectra (Figures S22 and S23). The CPL spectra of CCNFs (Figure 4B) have opposite signals at ∼567 nm, confirming the presence of antipodal chiral assembly structures, in which the redshift emission compared with that of the HCCN colloidal solution might be attributed to the hybridization of the band edge orbitals in the assembly structure. The artifacts, such as the linear dichroism (LD) of all CD and CPL spectra, have been eliminated by the accumulation of data generated at 8 rotation degrees in the range of 360° (Figures S24 and S25). The strong OA might be attributed to the amplification of the chirality level by level in the hierarchical structure. The SCSB of the hierarchical chiral CCNFs was stochastic and uncontrollable based on the CPL signal results of 18 experiments (Figure 4C). The detailed elimination procedure of LD in the CD, LD, and CPL spectra is shown in Figures S26–S42 and Table S4. The OAs of the chiral CCNFs indicate that the chirality of the nanorods is amplified through the assembly, but there is no relationship between the handedness of the HCCNs and that of the chiral CCNFs. The low-angle XRD patterns of antipodal chiral CCNFs (Figure 4D) have two well-resolved reflections centered at q values of 0.20 and 0.37 nm−1, which can be indexed as the first- and second-order reflections of the lamella structure with an interlayer distance of ∼5.2 nm. The space between neighboring HCCNs is ∼1.4 nm considering the HCCN diameter of 3.8 nm. The distribution of the chiral handedness in the chiral CCNFs was investigated with Muller matrix microscopy45Goldstein D.H. Mueller matrix dual-rotating retarder polarimeter.Appl. Opt. 1992; 31: 6676-6683Crossref PubMed Scopus (316) Google Scholar,46Pezzaniti J.L. Chipman R.A. Mueller matrix imaging polarimetry.Opt. 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