Abstract
The zero field 53Cr nuclear magnetic resonance was measured at low temperatures to investigate the interactions in the bond-frustrated Sā=ā3/2 Heisenberg helimagnet ZnCr2Se4. A quadratic decrease of the sublattice magnetization was determined from the temperature dependence of the isotropic hyperfine field. We calculated the magnetization using linear spin wave theory for the incommensurate spiral spin order and compared this outcome with experimental results to estimate the coupling constants. The hyperfine fields at Cr and Se ions provide evidences that the spin polarization of Cr ions is transferred to neighboring Se ions due to the covalent bonding between them, resulting in reduced magnetic moment in the Cr ion. This observation indicates that the Jahn-Teller effect, which leads to distortion inducing spin-lattice coupling, is not completely missing in ZnCr2Se4.
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Introduction
In spinels consisting of a chromium and nonmagnetic ions, ACr2X4 (Aā=āZn, Cd, Hg and Xā=āO, S, Se), the combination of A and X ions allows control over the distance between neighboring Cr ions resulting in a broad range of interaction strength. The antiferromagnetic direct exchange interaction is dominant in ZnCr2O4 given the narrow distances between Cr ions. The tetrahedral structure of Cr ions subsequently predicts the three dimensional geometrical frustration1,2. At greater distances between the Cr ions, as in HgCr2Se4, the ferromagnetic superexchange interaction is dominant over the direct exchange interaction3,4,5. In ZnCr2Se4, the CrāCr distance is between these two. The resulting interaction is ferromagnetic as manifested by a positive Curie-Weiss temperature of Īøcwā=ā90āK6,7, but the actual spin order occurring at TNā=ā21āK8 is incommensurate helical. This discrepancy implies that nearest-neighbor interaction is comparable and opposite to farther neighbor interactions, that is, bond frustration plays an important role.
ZnCr2Se4 undergoes a structural transition from cubic to tetragonal (c/aā=ā0.9992)9 concurrent with the magnetic phase transition. It also exhibits negative thermal expansion8 and high magnetostriction10. All of these observations provide evidence of strong spin-lattice coupling11. This is an interesting feature because three d3 electrons of a Cr3+ ion half-fill the t2g triplet and the orbital angular momentum is quenched to zero. Therefore, the simultaneous transition of the structure and magnetic orders does not originate from the conventional Jahn-Teller (JT) distortion and magnetostriction effect is not due to spin-orbit coupling. The observed g-factor is in fact quite close to the spin-only value8,12. On the other hand, spin-lattice coupling in frustrated magnets can be generated by the spin driven JT effect13 that the frustration is released by structural distortion. That is, the strong spin-lattice coupling is the result of the competition between the ferromagnetic nearest neighbor interaction and the antiferromagnetic farther neighbor interactions.
Despite the necessity for information about these interactions to understand the spin-lattice coupling in ZnCr2Se4, reported values of the strength of the interactions have been inconsistent. The results of a neutron powder diffraction experiment provided suitable explanation with the combination of J1ā~āā1, J2ā~ā0.3āmeV14, where Ji is the coupling constant between the i-th nearest Cr neighbors as shown in Fig.Ā 1. However, a neutron scattering experiment with a single crystal reported J1ā~āā3, J2ā~ā0.03, J3ā~ā0.5, J4ā~āā0.04āmeV15. A calculation of the local spin density approximation plus U also predicted that the magnitudes of ferromagnetic J1 and antiferromagnetic J3 are larger than those of J2 and J4 by one order, though estimated values5 were quantitatively different from those in the neutron scattering data.
The magnetic moment of Cr3+ ions has also been the subject of some debate. The fit of susceptibility data to the Curie-Weiss law produced 3āĪ¼B per Cr ion12,16. Contrary to macroscopic measurements, neutron diffraction studies have reported that the magnetic moment of a Cr3+ ion is not greater than 2āĪ¼B17,18 and have suggested that spin fluctuation reduces the average magnetic moment. In contrast, a recent neutron diffraction study claimed that 3āĪ¼B was obtained in agreement with a spin-only Cr3+ ion and that smaller values may originate from the non-stoichiometry of samples14. In addition to spin fluctuation and non-stoichiometry, metal-ligand covalence can reduce the magnetic moment of a Cr ion in ZnCr2Se4. It is known that covalent hybridization spreads the spin polarization of a metal ion onto the ligand orbital19. Considering that covalence is relatively strong in selenides, this could in fact be the major cause of the reduced moment. The covalence is related to the spin-lattice coupling either because the changed electron density in Cr ions would induce distortion.
In this paper, we report the coupling constants and the magnetic moment of Cr ions in ZnCr2Se4 as obtained by zero-field nuclear magnetic resonance (NMR). Temperature dependence of the magnetic moment M(T) was obtained from the isotropic part of the hyperfine field. The sublattice magnetization was calculated by applying linear spin wave theory to the incommensurate helical spin distribution, which was in good agreement with experimental outcomes. The exchange constants were estimated by fitting the theory to the experimental results. The evidences of strong Cr-Se covalence were provided by the isotropic and anisotropic hyperfine fields obtained by Cr and Se NMR.
Results
The zero-field 53Cr NMR spectrum obtained from polycrystalline ZnCr2Se4 at 6āK is shown in Fig.Ā 2. As temperature increases to 15āK, the center frequency decreases and the peak positions shift a little while the spectral shape consisting of six peaks remains the same. This spectral shape is due to the anisotropic hyperfine and nuclear quadrupole interactions both of which produce U-shaped spectra when diverse spin directions generate diverse internal magnetic fields. In materials with an incommensurate helical spin structure such as BiFeO3, the spins pointing in all directions produce such a spectrum20,21. A similar spectrum is observed when an external magnetic field generates diverse spin directions in powder samples22. Because spectrum was obtained in a zero external field, the observed U-shape is not the characteristics of powder samples but instead represents the incommensurate spin helical structure of ZnCr2Se4.
The NMR resonance frequency for magnetic materials is determined by the interaction
where Hiso, Hani, and HNQR represent the isotropic and anisotropic hyperfine interactions, and the nuclear quadrupole interaction, respectively. The ordered electron spins in the d orbital polarize the spins in the inner s-shell, generating a strong isotropic hyperfine field at the nuclei through Fermi contact interaction. The spins in the same and neighboring atoms generate dipolar hyperfine fields which are anisotropic. The spectral shape expected from these interactions for an incommensurate helical spin distribution is derived in the Method.
We fit the data in Fig.Ā 2 using Eq. (9) in Method. The fitting parameters are Ī½0, Ī½1, and Ī½NQR, which are the resonance frequencies of the isotropic and anisotropic hyperfine fields, and the nuclear quadrupole resonance (NQR) frequency, respectively. The result of the fit drawn together in the Fig. appears to be quite satisfactory. The temperature dependence of Ī½0, Ī½1, and Ī½NQR obtained from the fit to the NMR spectra measured at various temperatures are shown in Fig.Ā 3 and the insets therein. Ī½0 shows a monotonic decrease of approximately 15% as the temperature increases from 4āK to 15āK. Ī½1 drawn in the lower left inset, also decreases by a similar amount. Because hyperfine fields are proportional to the magnetic moment of the electron spins, Ī½0 and Ī½1 are proportional to the electron magnetic moment either. Therefore, they should change with the temperature in the same way. The NQR frequency depends on the ion position in a crystal structure and is therefore independent of the temperature. Ī½NQR drawn in the upper right inset remains constant with the temperature, as expected. The same temperature dependence of Ī½0 and Ī½1 and the temperature-independent Ī½NQR strongly supports the legitimacy of the analysis.
Discussion
Since Ī½0 is proportional to the electron magnetic moment as mentioned above, the main graph in Fig.Ā 3 represents the temperature dependence of sublattice magnetization. To determine the experimental coupling constant from our data, we calculated the temperature dependence of the magnetic moment in a helical order using linear spin wave theory. The spin Hamiltonian
can be diagonalized by the lowest order of the Holstein-Primakoff transformation followed by the Bogoliubov transformation in the form of \(H={\sum }_{k}\,\hslash {\omega }_{k}{\alpha }_{k}^{\dagger }{\alpha }_{k}\) with the dispersion relation15 of
for a helical spin order with wave vector Q, where Jk is the Fourier transform of Jij.
The temperature dependence of the magnetic moment <Sz> is obtained from the Bose-Einstein distribution of magnons as
where Xkāā”āJkāāāJQ and \({Y}_{k}\equiv \frac{1}{2}{J}_{k+Q}+\frac{1}{2}{J}_{k-Q}-{J}_{Q}\). The second term is the magnetic moment reduction due to quantum fluctuation which is temperature-independent. The temperature dependence of magnetization comes from the third term. At low temperatures, only the low-energy spin wave excitations are considered. The dispersion relation in Eq. (3) shows that the main contribution to the summation over k comes mostly near |k|ā=ā|Q| and kā=ā0. However, it has been reported that magnon-magnon scattering opens gaps at (0, Ā±Q, 0) and (Ā±Q, 0, 0)15. Therefore, we need to sum only around (0, 0, 0) and the Goldstone modes centered at (0, 0, Ā±Q). Then it can be shown that the magnetic moment reduction depends on temperature as
where Ī±(Jij) is a constant depending on the coupling constants Jij. For example,
if the Hamiltonian in Eq. (1) contains only two coupling constants, J1 and J3. Here Ī³ is the angle between the spins in the neighboring ab planes. The magnetic moment decreases in proportion to T2, as in antiferromagnets.
The fit of the data in Fig.Ā 3 to Ī±T2 gives Ī±ā=ā33(Ā±1)āĆā10ā3 MHz/K2. The result is depicted as the black solid curve in the figure. It appears that the theoretical model describes the data well. Considering the uncertainty in the estimation of Ī± by the fit, we searched for J1 and J3 pairs which gives |Ī±(Jij)āāāĪ±|/Ī±ā<ā0.03. All the pairs of J1 and J3 satisfying this condition are depicted as red open circles in Fig.Ā 4. There are two different couplings between the third-nearest neighbors (\({J}_{3}^{^{\prime} }\) and \({J}_{3}^{^{\prime\prime} }\), see Fig.Ā 1) but we simply used the same J3 value because the difference is negligible5.
As |J1| increases, the points approach asymptotically a linear curve that passes through the origin, \({J}_{3}\, \sim \,-\,0.2\,{J}_{1}\). This means that the same helical order can be generated for different pairs of ferromagnetic J1 and antiferromagnetic J3 as long as their ratio is fixed. When only J1 and J3 are considered, the ground-state energy of a helical order of classical spins is given by E(Ī³)ā=ā4J1(cosĪ³āāā1)ā+ā8J3(cos2Ī³āāā1)5. The ground-state configuration is obtained by requiring (dE/dĪ³)Ī³0ā=ā0. The experimentally observed angle between the spins on the neighboring ab planes Ī³0ā=ā42Ā° gives J3/J1ā~āā0.17, which roughly matches with the value estimated from the fit. The black squares in Fig.Ā 4 represent J1 and J3 values reported in the experimental and theoretical works claiming that J1 and J3 are one order of magnitude stronger than J2 or J45,14,15. Although these values are different from each other, they follow the relationship trend we introduce here.
We repeated the same fit procedure with J1 and J2 instead of J1 and J3. The result shows that the pairs of J1ā>ā|ā2.4| meV and J2ā>ā0.8āmeV fit the data similarly. However, the result is incompatible with that of a neutron powder diffraction experiment which was explained with J1ā~āā1 and J2ā~ā0.3āmeV14. The NMR result supports the bonding scheme with the ferromagnetic J1 competing with antiferromagnetic J3, rather than that with J1 and J2. We also attempted to fit the data to the form Tā3/2exp(āEG/kBT) which is the temperature dependence of magnetization expected when energy gap EG exists in the spin wave dispersion relation. The result was EGā=ā1āĀ±ā13āmeV, indicative of practically no energy gap and, consistent with the neutron scattering experiment.
The NMR center frequency of the Cr3+ ions extrapolated to 0āK in Fig.Ā 3 is about 46āMHz. Zero-field Cr NMR for other ACr2Se4 compounds was also observed at a similar frequency23. Cr NMR for ACr2O4 compounds is, however, observed in the frequency range of 68āĀ±ā7āMHz24,25,26,27,28. The resonance frequency of Mn2+ NMR for manganese compounds is also reduced by about a third when O or F ion ligands are replaced by Se ions27. The difference in the resonance frequencies of the selenides and oxides is attributed to the difference in the magnetic moments and the hyperfine coupling constants. Given that the magnetic moment of Cr3+ ions in chromium oxide spinels is 3āĪ¼B, the magnetic moment of the chromium selenide should be less than 3āĪ¼B.
Supporting evidences for the reduced magnetic moment of Cr3+ ions are also provided by the Se NMR and the anisotropic hyperfine field at a Cr ion. When macroscopic measurements of the magnetic moment gives 3āĪ¼B per Cr ion12,16, and one Cr ion has less than 3āĪ¼B, the remaining moment should be found in the other ions of ZnCr2Se4. In general, the covalence increases in metal-ligand bonding as the oxygen ligand is replaced by sulfur, and sulfur by selenium. Covalent hybridization due to the strong overlap between the Cr 3d and Se 4p orbitals is expected to transfer the spin polarization of Cr ions to Se ions27. We measured the transferred hyperfine field at the Se nuclei of ZnCr2Se4 by zero-field Se NMR. The resulting hyperfine field strength is 8ā~ā10T, which is about half of that in Cr nuclei, 18.3āT. Cr and Se NMR for CdCr2Se4 and HgCr2Se4 show the similar results23. This large hyperfine field in nonmagnetic Se ions provides one clear evidence of a large spin polarization transfer from Cr ions. It is known that the intensity of spin fluctuations measured in neutron scattering experiment decreases due to reduced magnetic moment associated with such strong covalence19,29.
The anisotropic hyperfine field is generated by L or S at the same or neighboring atoms. In the simple ionic picture in which three d electrons occupy t2g orbitals, the orbital angular momentum L is quenched and the hyperfine field due to S at the same atom is isotropic because the shape of the half-filled t2g orbitals is spherical. Therefore, only the dipolar field due to S in the neighboring Cr ions can contribute to the anisotropic hyperfine field. We calculated the dipolar field generated by the helically ordered spins in ZnCr2Se4. Considering up to the third nearest neighbors, the sum of the dipolar field is estimated to be approximately 340 mT. Extrapolation of the anisotropic hyperfine field data in the inset of Fig.Ā 3 to 0āK gives a value of 2.5āMHz, which approximately corresponds to 1T.
Because the dipolar field is only a third of the observed value, the major anisotropic hyperfine field should be generated in the same atom. This means that either there should be an unquenched L or that the orbital is not exactly spherical. The g-factor measured along the [111] direction of a single crystal8 is identical to that obtained from poly-crystals12, 1.996. Therefore, the unquenched orbital angular momentum is negligible and the most plausible cause of the anisotropic hyperfine field is the spin in the non-spherical d orbital. The orbital in Cr3+ ions might become non-spherical when the effective number of electrons changes from three by covalence. A small fraction of a pair of up and down electrons is shifted from Se to Cr ions in the covalent bonding, and a similar fraction of one electron is shifted in the opposite direction in the antibonding30. In this way, a net electron is transferred from a Se ion to a Cr ion, while a spin polarization is transferred in the opposite direction. The changed electron density in Cr ions should then induce distortion together with the spin-driven JT effect, generating spin-lattice coupling in ZnCr2Se4 where the JT effect is missing from the pure ionic point of view.
In summary, the strong spin-lattice coupling in ZnCr2Se4, where the conventional JT effect is missing, can be explained by the spin driven JT effect. That is, the spin-lattice coupling in the frustrated magnet ZnCr2Se4 is the result of competing ferromagnetic and antiferromagnetic couplings. To determine the coupling constants, we obtained M(T) from the temperature dependence of the zero-field Cr NMR spectrum and compared with theory. We derived \(M(T) \sim {T}^{2}\) using linear spin wave theory. The comparison supports the claim that J1 and J3 are dominant couplings rather than J1 and J2. The result yielded the asymptotic relationship J3ā~āā0.2J1 for large couplings.
We have shown evidences for the spin polarization transfer from Cr ions to Se ions due to strong covalence. First, the strength of the isotropic hyperfine field implies that the effective number of d electron spins in a Cr ion is less than three. Second, the anisotropic hyperfine field indicates that the total d electron orbital is not spherical. Third, Se NMR supports a large spin polarization transfer from Cr ions to Se ions. The changed number of electrons can then induce distortion of the lattice in addition to the spin-induced JT distortion. Covalence plays a role in the spin-lattice coupling in ZnCr2Se4.
Methods
NMR experiment
For NMR experiments, polycrystalline ZnCr2Se4 samples were used because single crystals produced much lower signal intensity levels, most likely due to conductivity. The samples were prepared in a closed quartz ampule using a stoichiometric quantities of Zn (99.99%), Cr (99.999%), and Se (99.999%). The elements were thoroughly mixed, pressed into pellets, and heated to 650āĀ°C for 24 hrs. The product was reground and the same heating procedure was repeated once more. The phase purity of the polycrystalline sample was checked at room temperature via powder X-ray diffraction. All experiments were performed without external magnetic fields. A conventional 90-Ļ-180 pulse sequence was used to obtain the spin echo signal at temperatures lower than TN. The echo signal was measured in a wide frequency range between 35 and 50āMHz at an interval of 0.1āMHz with rf pulses of 0.25āMHz bandwidth. The full NMR spectrum was obtained by summing the Fourier-transformed signals31.
NMR spectrum analysis
Considering all three interactions in Eq. (1), the NMR resonance frequency is given as follows:
Here, Ī± and Ī² represent the angles between the spin direction and the anisotropy axis of the hyperfine field and the principal axis of the NQR, respectively. Ī½0 and Ī½1 are the resonance frequencies of the isotropic and anisotropic hyperfine fields, respectively, and the first order NQR frequency for māāāmāāā1 transition, Ī½NQRā=āā(3e2qQ/2hI(2Iāāā1))(māāā1/2)/2. Because the spins of ZnCr2Se4 lie on the ab plane, the spin direction is describable with only the azimuthal angle Ļ. The crystal symmetry implies that the NQR principal axis is along the [111] axis, along which Cr ions are located symmetrically. It is known CdCr2Se4 has the principal axis of NQR in this direction32. The angle dependence of the NQR term, 3cos2Ī²āāā1, can then be replaced by sin(2Ļ). Expressing the angle dependence of the anisotropic hyperfine field in terms of Ļ, Eq. (7) can be rewritten as20,21
where Ī“ is the azimuthal angle of the axis of the anisotropic hyperfine field. Ī½0 is the sum of all angle-independent terms and Ī½1 is the value of Ī½ani projected on the ab plane.
A simple trigonometric calculation of Eq. (8) gives
Here, Ļ0 is a constant. The equation shows that the frequency change with the azimuthal angle is minimal at every 90 degrees. In an incommensurate spiral spin distribution, all spins are uniformly distributed in the angle domain. Such a spatially uniform distribution appears as a U-shaped distribution in the frequency domain. NQR gives three different spectral shifts mā=ā3/2, 1/2, ā1/2, to split the spectrum into three. As a result, the superposition of three U-shaped spectra with six peaks is generated.
We fit the data in Fig.Ā 2 using Eq. (9). The center frequency Ī½0ā+āĪ½1/2 was determined according to the symmetry point of the spectrum, and the fitting parameters were Ī½1, Ī½NQR, and Ī“. The result of the fit drawn together in Fig.Ā 2 appears to be quite satisfactory. The best fit resulted in Ī“ā=āĻ/4, meaning that the axis of the anisotropic hyperfine field is on the (1\(\bar{1}\)0) plane. The principle axis of NQR is along the symmetry axis of Cr ions, i.e., the [111] direction. Because this axis is on the (1\(\bar{1}\)0) plane, the fitting result strongly implies that the axis of the anisotropic hyperfine field coincides with the principle axis of the NQR. The NMR signal of CdCr2Se4, having a crystal structure identical to that of ZnCr2Se4, was also suitably described using the same axis of the anisotropic hyperfine field32.
Data availability
The datasets generated during and/or analysed during the current study are available from the corresponding author on reasonable request.
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Acknowledgements
This work was supported by the National Research Foundation under grants 2019R1F1A1051982 and 2016R1A5A1008184. Work at SNU was financially supported byĀ HYU-HPSTAR-CIS High Pressure Research Center (NRF-2016K1A4A3914691) and Korea Institute of Energy Technology Evaluation and Planning (20173010012940).
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S. Kwon conceived the project. S.P. conducted the experiments. S.P. and S.L. analysed and discussed the results. S. Khim, D.B., C.P. and K.K. prepared the sample. All authors reviewed the manuscript.
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Park, S., Kwon, S., Lee, S. et al. Interactions in the bond-frustrated helimagnet ZnCr2Se4 investigated by NMR. Sci Rep 9, 16627 (2019). https://doi.org/10.1038/s41598-019-52962-4
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DOI: https://doi.org/10.1038/s41598-019-52962-4
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