Introduction

Recently, the strongly spin-orbit coupled 5d-electron iridates have aroused a great deal of interests1,2,3,4,5,6,7,8,9,10,11,12. Different from the well-studied 3d transition metal oxides, the much larger spin-orbit interaction (SOI) and relatively weak electron correlations are roughly of the same magnitude in iridates, and consequently their delicate interplay has been suggested to host some exotic quantum ground states, e.g., spin-orbit coupled Mott insulators1,13,14,15, topological semimetals4,5,6,7, axion insulators8, correlated topological insulators4,9,10,11,12,16,17, unconventional superconductors18,19 and spin liquids20,21,22,23.

Among all iridates, the Ruddlesden-Popper (RP) series Srn+1IrnO3n+1 have received the special attention. These compounds display distinct properties depending on the different n value. Sr2IrO4 (n = 1) has been regarded as a prototype of the so-called spin-orbit coupled Mott insulator, in which the strong SOI lifts the orbital degeneracy of the t2g bands and results in such a narrow half-filled Jeff = 1/2 band that even moderate electron correlations could induce a Mott metal-insulator transition (MIT) in this 5d-electron system1,2,13. As for the n = 2 case, Sr3Ir2O7 has been proven to form a similar effective Jeff = 1/2 band but just on the verge of the Mott insulator regime with a smaller band gap24,25. Naturally, the n = ∞ end-member SrIrO3 was supposed to be on the itinerant side of this family2,26. In this regard, this family of compounds could provide a unique opportunity to investigate the MIT in the strong SOI limit. Since Sr2IrO4 and Sr3Ir2O7 have been comprehensively studied, it is crucial to understand the low energy electronic structure of SrIrO3, so that a complete picture of this MIT could be obtained. Besides, theories based on tight bonding model have suggested that SrIrO3 should be an exotic semimetal induced by the delicate interplay between the SOI and electron correlations27,28,29, in which a Dirac nodal ring near the U point would render a non-trivial topological semimetallic state27,28. Such an exotic semimetallic state was suggested to be crucial in designing SrIrO3 based artificial superlattices with novel topological properties12,28. However, although some optical spectroscopy and transport measurements have shown signs of semimetallic properties2,30,31,32, the straightforward information on the possible semimetallic state of SrIrO3, particularly its low-lying electronic structure, is still lacking to date.

Before achieving such crucial information, researchers have to overcome two major obstacles. On the one hand, the bulk SrIrO3 prefers to crystallize the 6H-hexagonal structure rather than the perovskite phase, and only the polycrystalline perovskite SrIrO3 can be obtained under high pressure33,34. To date, there have been no bulk single crystals of perovskite SrIrO3 available yet. On the other hand, while its quasi-two-dimensional analogues Sr2IrO4 and Sr3Ir2O7 have been comprehensively studied using powerful electronic structure probing techniques, e.g., scanning tunneling spectroscopy (STS) and angle-resolved photoemission spectroscopy (ARPES)1,25,35, the inability to cleave the pseudocubic structured SrIrO3 prevents even a basic understanding of its low-lying electronic structure.

Aiming at the above difficulties, we applied reactive oxide molecular beam epitaxy (OMBE) to synthesize high-quality orthorhombic perovskite SrIrO3 (001) films on (001) orientated SrTiO3 single-crystal substrates, and then performed in-situ ARPES to study the low-lying electronic structure of films. Our data reveal that the hole-like and electron-like bands around R and U(T) of the orthorhombic perovskite Brillouin zone (BZ) simultaneously intersect the Fermi level (EF), providing an unambiguous evidence of the semimetallic ground state in this material. These bands crossing EFare extremely narrow and there exists a pronounced mixing between the Jeff = 1/2 and Jeff = 3/2 characters therein, which is in sharp contrast to the predictions in the strong SOI limit. In addition, our photoemission results reveal that there is an evident gap between the electron- and hole-like bands near the zone boundary, indicating that the predicted Dirac degeneracy protected by the crystal-symmetry is actually lifted in the perovskite SrIrO3 thin film.

Results

Valence band structure and Fermi-surface topology of perovskite SrIrO3

Figure 1(a) Illustrates the three-dimensional BZ of the orthorhombic perovskite structured SrIrO3, compared to that of the simple cubic lattice. Since IrO2 octahedra are rotated around the c axis and tilted around the [110] axis, epitaxial SrIrO3 has an orthorhombic perovskite structure and one orthorhombic unit cell contains four formula units with the space group of Pbnm. Thus, the two-dimensional projection (highlighted by the black thick lines) is reduced by half in the momentum space. More information of these epitaxial films can be found in the Supplementary Information. The left panel of Fig. 1(b) shows the second derivative of the valence band of epitaxial SrIrO3 with respect to binding energy, which is in a qualitative agreement with our density functional theory (DFT) calculations (black lines appended). The right panel illustrates the angle-integrated spectrum of the valence band. By comparing with DFT calculations, we can attribute features between −7.0 eV and −2.0 eV mostly to O 2p states, while the Ir t2g orbitals mainly distribute spectral weight from −2.0 eV to 0 eV. Distinct from the fully gapped Sr2IrO4 and Sr3Ir2O71,25, there still exists significant spectral weight in the vicinity of EF for SrIrO3, consistent with the more metallic behavior of this material2,36. For states near EF, it is worth noting that the Jeff = 1/2 and 3/2 manifolds of SrIrO3 are not well separated as in its two-dimensional counterpart Sr2IrO41, and there is a substantial mixing of Jeff = 1/2 and Jeff = 3/2 states.

Figure 1: Valence band and Fermi-surface topology of SrIrO3 films.
figure 1

(a) The three-dimensional Brillouin zone of orthorhombic perovskite SrIrO3 and its projection in the kx and ky plane. (b) The comparison between the second derivative plot of the valence band and DFT calculation of SrIrO3 (left panel), and the corresponding angle-integrated spectrum (right panel). (c) The photoemission intensity map integrated over [EF - 10 meV, EF + 10 meV] of the epitaxial SrIrO3 along with the underlying binding energy versus momenta spectra. The data were taken with He I (21.2 eV) photons.

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Figure 1(c) Shows the photoemission intensity map of the epitaxial SrIrO3 along with the underlying binding energy versus momenta spectra. The Fermi surface (FS) consists of a four-pointed-star shaped pocket surrounding the corner and the circular pockets around the reduced BZ boundary. This fermiology is reminiscent of the isoenergy spectral map (around 0.4 eV binding energy) of Sr2IrO41,35. Particularly, the four-pointed-star pocket around the zone corner and the underlying hole-like band dispersion look rather like those of Sr2IrO4, implying the similar low-lying band characters for this series of materials despite of their different chemical potentials. While, the MIT introduces some unexpected changes of the band structure as well. For example, the electron pocket around the X(U) point has never been reported before even in the isoenergy spectral maps of Sr2IrO4 and Sr3Ir2O71,25,35. Although our photoemission data taken with He I photons (21.2 eV) can only probe one kz plane but not the complete three-dimensional BZ, the simultaneous intersection of EF by hole- and electron-like bands is one straightforward evidence that the perovskite SrIrO3 has a semimetallic ground state, which has long been predicted to be caused by the delicate interplay between the strong SOI and electron correlations on the itinerant side of the RP series. This semimetallicity is also consistent with previous report on the transport measurements of epitaxial SrIrO3 films30,31,32. Here, we notice the “patch-like” Fermi pocket for SrIrO3, which is in contrast to the sharp FSs of Sr2IrO4 and Sr3Ir2O7. This is probably induced by the intrinsic kz broadening effects arising from the short photoelectron mean free path and the sizable band dispersion along the kz direction in this pseudocubic compound.

kz determination in the photoemission spectroscopy measurements

Since epitaxial SrIrO3 thin films have the orthorhombic perovskite structure, the kz dispersion of these films is expected to be substantial. Therefore, it is crucial in our work to verify that the kz plane we probed is rather close to Z-U-R-T plane, so that we can compare our data directly with theoretical predictions.

Using the free-electron final-state model37, in which the inner potential was set to 11 eV [the typical inner potential value for perovskite transition metal oxides38,39,40, and this value have been used in a recently published photoemission work on epitaxial SrIrO3 films]41, we can estimate the kz values probed with He I (21.2 eV) and He II (40.8 eV) photons and then append both of them on the kz–kx plane [the light blue one highlighted in Fig. 2(a)]. As illustrated in Fig. 2(b), photons with these two energies accidently probe the equivalent kz planes (the Z-U-R-T high-symmetry plane) in the Brillouin zone.

Figure 2: Schematics illustrating the sites of scan projected to kz-kx plane in three-dimensional Brillouin zone.
figure 2

(a) The Brillouin zone of orthorhombic perovskite structured epitaxial SrIrO3 films with compressive misfit strain. The symbols for high-symmetry momentum points (Γ, M, Z and R) follow the Brillouin zone of an orthorhombic perovskite structure. (b) Sites of two photon energies (He I & He II) scan projected to Γ-M-R-Z plane. (c,d) The photoemission intensity plots taken with He I (21.2 eV) photons and He II (40.8 eV) along Z-R, respectively.

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Actually, the predicted Dirac node discussed below is expected to be located in a rather narrow kz window, which requires that our ARPES cut position should be accurately close to the Z-U-R-T plane to probe this feature. The ARPES measurement would not even probe such Dirac cone like bands once the cut positon of kz is out of this range. However, later it will be shown that we have successfully detected such Dirac line nodes, which are in a good agreement with our and other theoretical predictions. This finding strongly supports our judgement that we have indeed probed the electronic structure around U. In addition, all the measured band dispersions with He II rather resemble those obtained with He I photons except for some photoemission intensity changes [Fig. 2(c,d)]. This finding indicates that both He II and He I photons should probe the equivalent kz planes in the BZ. Even if slightly deviating from this inner potential of 11 eV, the ARPES cuts taken with He I & II photons would not be possible to be located in the equivalent planes according to the free-electron final-state model. In that case, we should have observed the evident band dispersing through the comparison of ARPES data taken with He I & II photons, respectively, considering the pronounced three-dimensional nature of the band structure of SrIrO3. Clearly, this is inconsistent with our experimental results. This finding again confirms that both ARPES measurements with He I & II photons indeed probe the Z-U-R-T high-symmetry plane and our choice of 11 eV inner potential are reliable.

Details of band dispersions along the high-symmetry directions

To investigate more details of the semimetallic ground state of epitaxial SrIrO3 films, we further examined the band dispersions along several high-symmetry directions of the unfolded BZ, as indicated in the right panel of Fig. 3(j).

Figure 3: Low energy electronic structure along high-symmetry directions.
figure 3

(a–c) The photoemission intensity plots taken along Z-R, T-U, and R-A high-symmetry directions, respectively. (d–f) The corresponding second derivative images with respect to the energy for these cuts. (g–i) The MDCs for the data in (a–c). All these data were taken with 21.2 eV photons, corresponding to the Z-U-R-T kz plane. (j) The indication of the cut direction in the projected two-dimensional Brillouin zone.

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Figure 3(a) Show the photoemission data taken along R-Z direction (Cut #1). Around the Z point, two hole-like bands can be resolved through the second derivative with respect to energy [Fig. 3(d)], and we can assign them as bands α and β, respectively. As further shown by the corresponding momentum distribution curves (MDCs) [Fig. 3(g)], α just barely intersects EF, forming the small hole pocket around the Z point as aforementioned in Fig. 1(c). While, the β band sinks slightly below EF, with the top centering at the binding energy of ~20 meV. Here, both bands are degenerate at the Z point, which is protected by the lattice symmetry. Along this direction, both bands α and β further disperse backwards to EFaround the zone corner and then cross EF [Fig. 3(d,g)]. We note that this is in a qualitative agreement with the previous reports on Sr2IrO4 and Sr3Ir2O7, in which the tops of both valence bands appear at the zone corner rather than the center. Surrounding the R point, one more hole-like band with larger Fermi crossing (γ, marked by the orange dashed line) can be distinguished, which develops the outer four-pointed-star like Fermi pocket around the zone corner. Besides, the second derivative plot [Fig. 3(d)] clearly shows that there exist two weak hole-like features (ω and τ) with band tops at the binding energy of ~200 meV, which surprisingly replicate all features of bands β and γ, respectively. They will be discussed more in another work (Z. T. L., D. W. S. et al., manuscript in preparation).

For the U-T direction (Cut #2), a parabolic electron-like feature (assigned as δ) crosses EF, forming the circular electron pocket surrounding U(T), as illustrated by both the photoemission intensity [Fig. 3(b)] and second derivative plots [Fig. 3(e)]. The corresponding MDCs [Fig. 3(h)] further demonstrate that its band bottom is located at around 40 meV below EF. Here, the band top of γ is tight against the band bottom of δ, which rather resembles the predicted Dirac-like dispersion around U(T)27,28. However, we note this Dirac cone is obviously gapped from the node point. And here, the spectra look rather symmetrical along U-T direction though the U and T points are not equivalent for a single crystalline SrIrO3. As for epitaxial SrIrO3 films, the square SrTiO3 (100) (a = b ~ 3.905 Å) substrates underneath could well account for this symmetry. For simplicity, we will unify the U(T) points as U thereafter.

Figure 3(c,f,i) Illustrate the data along another high symmetry direction R-A (Cut #3), which are reminiscent of those along Z-R except for some differences in the relative spectral intensity caused by matrix elements. We note that the epitaxial SrIrO3 films are of the orthorhombic perovskite structure, in which the band structure would be folded along the diagonal lines of the tetragonal BZ [Fig. 1(a)]. Consequently, the R-A direction should be equivalent to R-Z in the two-dimensional projection of the orthorhombic BZ. Such band folding phenomena have been reported in Sr2IrO4 and Ba2IrO4 single crystals or films as well1,42.

Comparison between the DFT band structure and experimental results

In order to better understand the electronic structure of SrIrO3, we have performed the LDA + SO + U calculation with different U values to compare with our ARPES result, as shown in Fig. 4(a–c). We find that the only effect of applying different U for SrIrO3 is to induce some band energy shifts, in sharp contrast to the case of the insulating Sr2IrO4, in which an evident gap between the Jeff = 1/2 and 3/2 would be open with larger U value. The calculation with U = 0 eV [Fig. 4(a)] rather than those with U = 1 eV and 2 eV [Fig. 4(b,c)] is more in line with the experimental band structure, particularly around the Dirac cone at the U point. This result indicates that electron correlations in perovskite SrIrO3 is relatively weak, consistent with the factor that the screening would be larger in three-dimensional systems than that in two-dimensional Sr2IrO4. We find that our calculation is rather similar to previous theoretical works2,5,27,28,29. Particularly, all these calculations predict the Dirac cone like bands around the U point. However, as shown in Fig. 4(a), our calculation explicitly predicts that the degeneracy of this Dirac node is lifted, in better agreement with our experiments [Fig. 4(d)].

Figure 4: Bands of DFT calculations and experimental results.
figure 4

(a–c) Representative DFT band structures of orthorhombic perovskite SrIrO3 films for (a) U = 0 eV, (b) U = 1.0 eV, and (c) U = 2.0 eV. (d) Comparison of the ARPES results and the DFT calculations (U = 0 eV) along the high-symmetry directions in epitaxial SrIrO3 films. Experimental band dispersions are determined either by fitting both EDCs and MDCs of the raw data and or from peak positions in second derivative data. DFT calculations are marked by the solid lines.

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To analytically deduce the renormalization factor, we focus on β band since its large portion can be observed in the experiment. By applying parabolic fitting to the band dispersion of β around the zone corner, its band top is estimated to be around 20 meV above EF, and the total bandwidth is approximately 290 meV. Compared with calculations (360 meV), the renormalization factor is determined to be 1.24. The small value is consistent with the relatively weak electron correlations in these 5d-electron systems.

Qualitatively, most characteristic dispersions of bands α, β and δ near EF can be verified by the DFT calculation. Particularly, the predicted Dirac cone like feature around U can be well resolved. However, there still exist some inconsistencies between them. For example, along the Z-U direction, α and β bands from ARPES results do not intersect, while the DFT only predicts two degenerate bands. Besides, we find several bands which have been probed by experiments but cannot be well captured in the calculation, including part of γ and the replica bands ω and τ. We note that γ crosses with α and β but does not show any hybridization effects, implying it might be a shadow band that is a replica of some band transferred by specific momentum vector.

Gapped bands around the U point

One of the hottest topics on iridates is that the perovskite SrIrO3 based artificial superlattices might be the long-sought-after oxide topological insulators with relatively large band gap5,6,7,12,28. This non-trivial topological property was thought to be inseparably linked with the predicted nodal ring around the U point of SrIrO3. As shown in the Fig. 3(b), the band dispersion around U rather resembles the predicted linear Dirac cone crossing. However, the corresponding second derivative plot in Fig. 3(e) demonstrates that the electron- and hole-like features do not touch each other but are isolated by a gap of around 30 meV, and their dispersions deviate from the characteristic linearity of a typical Dirac cone. This means that the Dirac degeneracy protected by the mirror-symmetry in the theory might have been lifted in epitaxial perovskite SrIrO3 thin films.

To further validate this finding, we carried out a comprehensive study of the low-lying band structure near U. Typical second derivative plots and the corresponding EDCs spectra taken along some other high-symmetry directions are summarized in Fig. 5. Similar to the data taken along U-T direction as shown in [Fig. 3(b,e,h)], there is a more accurate estimated gap of about 28 meV determined by the corresponding EDCs separated between the upper and lower Dirac cones around U along both cut #1 (U-Z) and cut #2 (U-R) [Fig. 5(a,d)]. This is as well confirmed by our zoom-in DFT calculations, as illustrated in Fig. 5(e–f). Overall, we could conclude that the low energy band structure of epitaxial perovskite SrIrO3 films is not so consistent with the prediction based on the tight bonding model28, and the Dirac line nodes are gaped though the mirror-symmetry of the lattice is still conserved.

Figure 5: Dirac line node degeneracy lifting around the U point.
figure 5

(a,b) The second derivative images with respect to the energy for the photoemission data along Z-U and U-R high-symmetry directions, respectively. (c,d) The corresponding EDCs for the photoemission data in (a,b), respectively. (e,f) The calculated band dispersions along Z-U (cut #1) and U-R (cut #2) high-symmetry directions, respectively. All these data were taken with 21.2 eV photons. (g) The indication of the cut direction around U point in the projected two-dimensional Brillouin zone.

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Discussion

One intriguing finding of our work is that the bands crossing EFin epitaxial SrIrO3 disperse only 290 meV across nearly the whole BZ, indicating a rather narrow bandwidth of the Jeff = 1/2 bands. This bandwidth is close to that of the lower Hubbard band of Sr3Ir2O7 (150~200 meV)25, but even narrower than that of Sr2IrO4 (~500 meV)1. Our findings show that the bandwidth of the Jeff = 1/2 band does not increase evidently for SrIrO3 as expected1,2. Besides, for the bands in the vicinity of EF, neither our photoemission data nor DFT calculations show the clear energy gap between the Jeff = 1/2 and Jeff = 3/2 states, and there exists a significant mixing of these two states. This result is qualitatively consistent with the cases of Sr3Ir2O725 and Sr3CuIrO643, but in contrast to the expectations of the strong SOI limit.

Such narrow bandwidth of the Jeff = 1/2 band and the significant mixing of Jeff = 1/2 and 3/2 states (Fig. 3) pose a strong challenge to the current prevalent explanation for the MIT occurring in the RP series Srn + 1IrnO3n + 1. In this model, the cooperative interplay between the moderate electron correlations and strong SOI would result in the Mott MIT in the narrow half-filled Jeff = 1/2 band of Sr2IrO4. With increasing neighboring Ir atoms in the Srn+1IrnO3n+1 series, the bandwidth W of the Jeff = 1/2 band would keep rising, and the metallicity would restore until the W is comparable to or even larger than the electron correlation U, which is the case of SrIrO32. This departure from the idealized Jeff = 1/2 and 3/2 picture and the MIT in the RP series Srn+1IrnO3n+1 might be induced by the extremely large crystal field splitting comparable to the SOI in this system41.

Moreover, according to the previous tight binding calculations, Jean-Michel Carter et al. [ref. 28] conjectured that the line node near U point should not be gapped unless the mirror symmetry of the lattice is broken. They suggested that the breaking of this symmetry by introducing a staggered potential or spin-orbit coupling strength between alternating layers would turn this line node into a pair of three-dimensional nodal points, and consequently induce a transition to a strong topological insulator28. In our experiments, the SrTiO3 (100) substrate itself and the induced compressive strain would not expected to break such a Pbnm mirror-symmetry of the SrIrO3 lattice. However, neither the photoemission data nor calculations are consistent with that proposal. Recently, some works proposed that the Dirac line node in epitaxial SrIrO3 film is actually protected by the n-glide symmetry operation, which could be selectively broken by different hetero-epitaxial structures. The Dirac line node degeneracy could be lifted without breaking the Pbnm mirror-symmetry5,6. In this work, the authors applied (110)-oriented GdScO3 substrates to fabricate epitaxial SrIrO3 films, and they calculated that the 0.6% tensile strain would lead to a small gap of 5 meV. Instead, our films were grown on (100)-oriented SrTiO3, which leads to a 1.54% compressive strain to the pseudo-cubic SrIrO3. Based on the parameters of our own heterostructure, the gap size is calculated to be around 20 meV, remarkably close to our experimental result 28 meV. In this regard, our SrIrO3 (100)/SrTiO3 (100) heterostructure would have inevitably broken the n-glide symmetry, which would consequently result in the lifting of Dirac nodes in the perovskite SrIrO3 thin films.

Though our DFT calculation well reproduces the gapped Dirac nodes around the U point in epitaxial SrIrO3 film. However, our experimental findings are still not in complete agreement with the theory, and there still exist some inconsistencies between our band structure calculation and experiments. On the one hand, the delicate interplay between the comparable SOI and electron correlations would perplex the precise prediction of the band structure calculation. On the other hand, in the real calculation, it is difficult to fully consider all the subtle lattice distortions in epitaxial films, which would affect significantly the final band structure calculations5,40. Thus, further more sophisticated theoretical considerations are desired.

In summary, we have applied the combo of OMBE and in-situ ARPES to systematically study the low-lying electronic structure of the orthorhombic perovskite SrIrO3 films. Our data show that the hole-like bands around R and the electron-like bands around U intersect EF simultaneously, providing the direct evidence of the semimetallic ground state in the perovskite structured SrIrO3. In addition, we find that the bandwidth of the states in the vicinity of EF is extremely small, and there exists a pronounced mixing between the Jeff = 1/2 and Jeff = 3/2 bands, which is in sharp contrast to the predictions in the strong SOI limit. Both our photoemission results and DFT calculations reveal that there is an evident gap between the electron-and hole-like cones near the zone boundary, which lifts the predicted Dirac line node degeneracy of perovskite SrIrO3. Our findings pose strong constraints on the current theoretical models for the 5d iridates, and thus call for a further refinement.

Note Added

At this work was made public through posting as an e-print (arXiv: 1501.00654), we note that, a photoemission work, which reports some similar results as part of our findings and was carried out independently by another group, was published: see ref. [41].

Methods

Sample synthesis

Perovskite structured SrIrO3 films of 25 unit cells (~10 nm, referenced to the pseudocubic cell) were deposited on (001) SrTiO3 substrates using a DCA R450 OMBE system at a substrate temperature of 560 °C in a background pressure of 2 × 10−6 torr of distilled ozone. The growth temperature was verified by optical pyrometry. The lattice constant of SrTiO3 substrate is 3.90 Å, which leads to a 1.54% compressive strain to the pseudocubic SrIrO3 (3.96 Å). Strontium and iridium were evaporated from an effusion cell and an electron beam evaporator, respectively, and the co-deposition method with both elements’ shutters being open for the duration of the growth was applied. The strontium and iridium fluxes were approximately 1.2 × 1013 atoms/(cm2s), which were both checked before and after the deposition by a quartz crystal microbalance. During the growth, the in-situ reflection high-energy electron diffraction (RHEED) intensity oscillations and patterns were collected to monitor the overall growth rate and surface structure, respectively. The films’ structure was finally ex-situ examined by X-ray diffraction (XRD) using a high-resolution Bruke D8 discover diffractometer.

ARPES measurement

Thin films were transferred to the combined ARPES chamber for measurements immediately after the growth through an ultrahigh vacuum buffer chamber (~1.0 × 10−10 torr). This ARPES system is equipped with a VG-Scienta R8000 electron analyzer and a SPECS UVLS helium discharging lamp. The data were collected at 15 K under ultrahigh vacuum of 8.0 × 10−11 torr. The angular resolution was 0.3°, and the overall energy resolution was set to 15 meV. During the measurements, the films were stable and did not show any sign of degradation.

Additional Information

How to cite this article: Liu, Z. T. et al. Direct observation of the Dirac nodes lifting in semimetallic perovskite SrIrO3 thin films. Sci. Rep. 6, 30309; doi: 10.1038/srep30309 (2016).