Abstract
One of key challenges in current material research is to search for new topological materials with inverted bulkband structure. In topological insulators, the band inversion caused by strong spin–orbit coupling leads to opening of a band gap in the entire Brillouin zone, whereas an additional crystal symmetry such as pointgroup and nonsymmorphic symmetries sometimes prohibits the gap opening at/on specific points or line in momentum space, giving rise to topological semimetals. Despite many theoretical predictions of topological insulators/semimetals associated with such crystal symmetries, the experimental realization is still relatively scarce. Here, using angleresolved photoemission spectroscopy with bulksensitive softxray photons, we experimentally demonstrate that hexagonal pnictide CaAgAs belongs to a new family of topological insulators characterized by the inverted band structure and the mirror reflection symmetry of crystal. We have established the bulk valenceband structure in threedimensional Brillouin zone, and observed the Diraclike energy band and ringtorus Fermi surface associated with the line node, where bulk valence and conducting bands cross on a line in the momentum space under negligible spin–orbit coupling. Intriguingly, we found that no other bands cross the Fermi level and therefore the lowenergy excitations are solely characterized by the Diraclike band. CaAgAs provides an excellent platform to study the interplay among lowenergy electron dynamics, crystal symmetry, and exotic topological properties.
Introduction
Topological insulators (TIs) exhibit a novel quantum state with metallic edge or surface state (SS) within the bulk band gap generated by the strong spin–orbit coupling (SOC). The topological SS in threedimensional (3D) TIs is characterized by a linearly dispersing Diraccone energy band,^{1,2,3} which hosts massless Dirac fermions protected by the timereversal symmetry (TRS). The discovery of TIs triggered the search for new types of topological materials containing surface or bulk Diraccone bands protected by crystal symmetries, as represented by topological crystalline insulators with the Diraccone SSs protected by mirror symmetry,^{4,5,6} as well as 3D Dirac semimetals (DSMs) with bulk Diraccone bands protected by rotational symmetry (such as Cd_{3}As_{2} and Na_{3}Bi).^{7,8,9,10,11} While the Dirac cone in DSMs is spin degenerate, breaking the TRS or spaceinversion symmetry leads to the Weylsemimetal (WSM) phase with pairs of spinsplit Dirac (Weyl) cones, as recently verified in transitionmetal monopnictides.^{12,13,14} Such Diraccone states are known to provide a platform to realize outstanding physical properties such as extremely high mobility, gigantic linear magnetoresistance, and chiral anomaly.^{15,16,17,18,19,20,21,22}
While the DSMs and WSMs are characterized by the crossing of bulk bands at the discrete points in k space (point nodes), there exists another type of topological semimetal characterized by the band crossing along a onedimensional curve in k space (line node), called linenode semimetal (LNSM). The LNSMs are expected to show unique physical properties different from the DSMs and WSMs, such as a flat Landau level, the Kondo effect, longrange Coulomb interaction, and peculiar charge polarization and orbital magnetism.^{23,24,25,26} Despite many theoretical predictions of LNSMs in various material platforms,^{27,28,29,30,31,32,33,34,35,36,37,38,39,40,41,42,43,44,45,46,47,48,49,50,51,52,53,54} experimental studies on the LNSMs are relatively scarce.^{55,56,57,58,59,60,61,62}
Recently, it was theoretically proposed by Yamakage et al. that noncentrosymmetric ternary pnictides CaAgX (X = P, As) are the candidate of LNSM and TI.^{41} These materials crystalize in the ZrNiAltype structure with space group P\({\it{\bar 6}}\)2m (No. 189)^{63} (for crystal structure, see Fig. 1a). Firstprinciples bandstructure calculations have shown that, under negligible SOC, CaAgX displays a fairly simple band structure near the Fermi level (E_{F}) with a ringlike line node (nodal ring) surrounding the Γ point of bulk hexagonal Brillouin zone (BZ) (bulk BZ is shown in Fig. 1b). The line node is associated with the crossing of bulk conduction band (CB) and valence band (VB) with Ag s and P/As p character, respectively, and is protected by the mirror reflection symmetry of crystal. When the SOC is included in the calculation, CaAgP still keeps the line node due to the very small spin–orbit gap (~1 meV) while a relatively large spin–orbit gap (~75 meV) opens along the line node in CaAgAs to make this material a narrowgap TI.^{41} The SOC thus plays a crucial role in switching the LNSM and TI phases in CaAgX. Transport measurements on the CaAgP and CaAgAs polycrystalline samples by Okamoto et al. have demonstrated the lowcarrierdensity nature of these samples, consistent with the existence of line node^{64} (note that this is further corroborated by the recent transport measurements on CaAgX single crystals.^{62}) They have further suggested that E_{F} in holedoped CaAgAs sample lies in the middle of linearly dispersive Diraclike band, and concluded that CaAgAs is well suited to study the lowenergy excitations related to the Dirac electrons. While the electronic states of CaAgX and its relationship to physical properties should be experimentally examined, there exist no experimental outputs on the band structure of CaAgX. It is thus urgently required to establish the fundamental electronic states.
In this work, we report the ARPES study of CaAgAs. By utilizing bulksensitive softxray photons from synchrotron radiation, we established the bulk VB structure in the 3D bulk BZ. We suggest that CaAgAs is a narrowgap TI with an ideal band structure suitable to study the lowenergy excitations linked to the bulk Diraclike band arising from the line node. This is demonstrated by observing the bulk Fermi surface which is solely derived from the VB and CB associated with the singleline node, consistent with our firstprinciples band structure calculations. We discuss the consequence of our observation in relation to the exotic physical properties.
Results and Discussion
Samples and experimental
Highquality single crystals of CaAgAs were grown on the sintered pellets of CaAgAs (for details, see Method). A typical photograph of our single crystal is shown in Fig. 1c. ARPES measurements were performed with synchrotron light at BL2 in Photon Factory, KEK. Samples were cleaved in situ along the (\(11\bar{2}0\)) crystal plane (a shiny mirror plane in Fig. 1c) as confirmed by the Laue xray diffraction measurement on the cleaved surface (typical Laue pattern is shown in Fig. 1d) and the photonenergy (hν) dependence of the band dispersion. This indicates that the cleaved plane is the k_{ y }–k_{ z } plane in the hexagonal BZ (Fig. 1b). Figure 1e displays the energy distribution curve (EDC) in the wide energy region measured at hν = 580 eV. One can recognize several corelevel peaks originating from the Ca (3 s, 3p), Ag (4 s, 4p, 4d), and As (3 s, 3p, 3d) orbitals. No other corelevel peaks were found in this energy range, confirming the clean sample surface.
Valenceband structure
First, we present the overall VB structure of CaAgAs. We found that softxray photons are useful for revealing the bulk electronic states of CaAgAs as in the case of noncentrosymmetric Weyl semimetals such as TaAs,^{12,13,14} although we need to sacrifice the energy/momentum resolution compared to the vacuum ultraviolet (VUV) photons. In fact, the obtained VUV data were found to suffer large broadening along wave vector perpendicular to the surface probably because of the finalstate effect and rather rough nature of the cleaved surfaces, and therefore we concluded that the VUV photons are not best suited for resolving 3D electronic states of CaAgAs. Figure 2a displays the EDCs at the normal emission measured with various photon energies in the softxray region of 530–700 eV. One can identify several dispersive bands. For example, a band located at binding energy (E_{B}) of ~1 eV at hν ~ 700 eV, which is attributed to the topmost bulk VB, disperses toward E_{F} on decreasing hν to 650 eV, and it disperses back again toward ~1 eV at hν = 600 eV. On further decreasing hν down to ~550 eV, this band again approaches E_{F}, similarly to the case of hν = 650–700 eV. Such periodic band dispersion was also observed for the bands located at E_{B} ~1.5 and ~3 eV. To visualize the experimental band dispersion more clearly, we plot in Fig. 2b the band structure obtained from the second derivative of the ARPES intensity plotted as a function of wave vector perpendicular to the sample surface (k_{ x }), which corresponds to the ΓM cut in the bulk BZ (cut A in Fig. 2c). One can immediately recognize that the overall experimental band dispersion shows a reasonable agreement with the calculated bulk bands (red curves) regarding the periodicity and location of bands; this confirms that the cleaving plane is (\(11\bar{2}0\)). The holelike dispersion approaching E_{F} around the Γ point is well reproduced by the calculations, and therefore it is assigned as the topmost VB with the As 4p orbital character. Moreover, a good agreement of the band width between experiment and calculation signifies no apparent bandrenormalization effect, suggesting the weak electron correlation. It is noted that we observe a single holelike band within 1.5 eV of E_{F} in the experiment, while the calculation predicts two holelike bands. Such difference may be due to the finite k/energybroadening effect as well as the matrix–element effect of photoelectron intensity, which turned out to be rather strong in this material.
We comment here that our Hall conductivity measurement of CaAgAs single crystal suggests the existence of hole carriers with carrier concentration of ~1.6 × 10^{20} cm^{−3}, which corresponds to the E_{F} location of 0.27 eV below the VB top. On the other hand, the VB structure determined by ARPES shows a reasonable agreement with the calculated band structure without sizable E_{F} shift. While we do not know the exact origin of such a difference, some possibilities like downward surface bandbending may be considered.
To see the band dispersion along the inplane wave vector, we used the photon energy of hν = 550 eV which traces the k cut crossing the Γ point of 13th BZ, and measured the EDC along the ΓKM (k_{ y }) cut (cut B in Fig. 2c), as shown in Fig. 2d. One can recognize highly dispersive holelike band centered at the Γ point, similarly to the case of ΓM cut in Fig. 2a, b. This band is better visualized in the ARPESintensity plot in Fig. 2e in which a holelike band with linear dispersion shows up in the E_{B} range of 0 ~ 1.5 eV (note that the intensity distribution around the M and Γ points is different between Fig. 2b, e and also among different BZs due to aforementioned matrix–element effect). We have confirmed by the bandstructure mapping in 3D BZ that the Fermi surface exists only around the Γ point. This conclusion is supported by the experimental band dispersion along the AHL cut in Fig. 2f (cut C in Fig. 2c) where the topmost VB always stays below E_{B} ~ 1 eV without crossing E_{F}.
Ringtorus Fermi surface
Having established the overall VB structure, a next important issue is the electronic structure in the vicinity of E_{F} responsible for the physical properties. Figure 3a displays the ARPES intensity at E_{F} as a function of k_{ x } and k_{ y } (the ΓKM plane). One immediately finds a bright intensity pattern surrounding the Γ point, in particular in 13th BZ, confirming the absence of additional Fermi surface away from the Γ point. It is also obvious from Fig. 3b that no Fermi surface exists away from Γ in the k_{ y }–k_{ z } (ΓAKH) plane. As shown in Fig. 3a, b, when we overlaid the calculated Fermi surface (green curves) onto the ARPES intensity (note that we assumed the location of E_{F} to be 0.05 eV below the VB top in the calculation to account for a small but finite holedoping effect in experiment), the highintensity region coincides with the k region where the calculated Fermi surface exists.
To gain further insight into the Fermisurface topology, we show in the top panels of Fig. 3c, d the ARPES intensity near E_{F} and the intensity obtained by taking second derivative of the EDCs, respectively, along the k cut nearly crossing the Γ point (cut A in Fig. 3a). One finds a linearly dispersive holelike band originating from the As 4p states, which is better visualized in the secondderivative plot in Fig. 3d (by a linear extrapolation of the band dispersion around E_{F}, we have estimated the Fermi velocity to be v_{F} = 2.1 ± 0.1 eVÅ). This band is reproduced by our calculation as shown by red curves in Fig. 3c, and is responsible for the outer ring in Fig. 3a. As shown in cut A of Fig. 3c, there exists another electronlike band in the calculation which originates from the Ag 5 s orbital; this band forms the inner ring in Fig. 3a. While the intensity of the electronlike band seems weak in the original intensity (Fig. 3c), the secondderivative image in Fig. 3d shows a finite spectral weight likely arising from the electronlike band.
As shown in cut A of Fig. 3c, the calculated electronlike band intersects the holelike band at ~0.1 eV above E_{F}, and forms the nodes at k_{ y } ~ ± 0.15 Å^{−1} under negligible SOC, since cut A is on the (0001) mirror plane (the k_{ x }–k_{ y } plane) and the nodes are protected by mirror reflection symmetry.^{41} This indicates that the electronic states within two opposite nodes across the Γ point have an inverted band character. Thus, our observation of electronlike feature can be regarded as a hallmark of the band inversion, which is a prerequisite for realizing LNSM or TI. It is remarked that with a finite SOC, an energy gap of 75 meV opens in the caluclation, as can be seen from a difference in the band dispersion with (solid curves) and without (dashed curves) SOC in Fig. 3c.^{41} The opening of a spin–orbit gap at the node is also seen in some other LNSM candidates, such as Cu_{3}(Pd,Zn)N,^{34,35} Ca_{3}P_{2},^{37,49} ZrSiS,^{40} CaTe,^{50} and fcc alkalineearth metal.^{51}
To clarify whether the nodelike feature in CaAgAs is seen at a point or on a line in k space, it is necessary to measure the band dispersion along different k slices around the Fermi surface. For this sake, we show in the middle and bottom panels of Fig. 3c, d the intensity for cuts slightly away from the Γ point (cuts B and C in Fig. 3a) obtained with different hν’s. One can recognize that overall band structure along cut B is similar to that along cut A regarding the E_{F} crossing of holelike band and the presence of electronlike feature. This is reasonable since cut B is also on the mirror plane and still crosses the calculated nodal points. On the other hand, along cut C, the holelike band moves downward and shows no E_{F} crossing. These behaviors are consistent with the presence of a ringshaped nodal feature (nodal ring) on the mirror plane shown by a dashed curve in Fig. 3a.
It should be stressed again that there exists a spin–orbit gap along the nodal line in the calculation. Since the gap is almost isotropic (75 ± 1 meV) along the nodal ring (not shown), the lowenergy excitations in CaAgAs are characterized by the excitations across the band gap in the k region involving the entire line node. Unfortunately, such a band gap (as well as the topological SSs) was not resolved in the ARPES experiment, likely due to the slightly holedoped nature of crystal. Considering the fact that (i) the calculated spin–orbit gap is not so small compared to other TIs and (ii) the ARPESderived band dispersion shows a reasonable agreement with the calculation near E_{F}, it would be more reasonable to regard CaAgAs as a narrowgap TI, rather than a LNSM. It is also emphasized here that the TI nature of CaAgAs should be distinguished from that of prototypical TIs such as Bi_{2}Se_{3} since the node never shows up even without SOC in Bi_{2}Se_{3} unlike CaAgAs.
Figure 3e illustrates the calculated equienergy contour maps in k space for selected energy slices (energy with respect to the VB top, E_{VB} = 0.1, 0.27, and 0.6 eV). The energy contour around E_{F} (E_{VB} = 0.1 eV) shows a ringtorus shape. On increasing E_{VB,} it gradually expands and fattens. Eventually it transforms into the spheroid as soon as the E_{VB} passes the bottom of electronlike band. As shown in Fig. 3f, such evolution of the ringtorus contours can be seen from the ARPESintensity mapping for representative E_{B} slices compared with the calculated energy contours.
From all these experimental results, we concluded that CaAgAs is likely a narrowgap TI characterized by the bulk Diraclike band and ringtorus Fermi surface associated with the line node on the (0001) mirror plane, in line with the firstprinciples bandstructure calculations. Intriguingly, we revealed that the bulk Fermi surface is solely derived from the Diraclike bands associated with a single line node (which appears under negligible SOC), and no other bands cross E_{F}. In this regard, the CaAgX family can be distinguished from some other LNSM candidates which contain additional normal bands crossing E_{F} and multiple line nodes.^{55,56,57,58,59,60,61} Thus, CaAgX is a promising platform to study the interplay among mirror symmetry, lowenergy excitations, and transport properties in LNSMs. Also, it would provide an excellent platform to study the influence of SOC to the lowenergy excitations involving the line node, because the SOC strength can be controlled by replacement of P and As in the crystal. Since the bulk electronic states of CaAgAs have been established in this study, a next important challenge is to clarify the nature of predicted topological SSs in the band inverted region.^{33} Such an experiment would require an access to the band dispersion above the line node via the fabrication of electronrich CaAgAs.
Methods
Sample preparation
Highquality single crystals of CaAgAs were synthesized by the following procedure. An equimolar mixture of calcium chips, silver powder, and arsenic chunks were put in an alumina crucible and sealed in an evacuated quartz tube. The tubes were kept at 773 K for 12 h and then at 1273 K for 12 h, followed by furnace cooling to room temperature. The obtained samples were pulverized, pressed into pellets, and sealed in quartz tubes. The pellets were sintered at 1173 K for 2 h and cooled to room temperature at a rate of 30 K h^{−1}, resulting in that shiny hexagonalprismatic single crystals of CaAgAs were grown on the pellets. The quality of the crystal was checked by xray diffraction technique using a RIGAKU RAXIS IP diffractometer.
ARPES experiments
ARPES measurements were performed with a ScientaOmicron SES2002 electron analyzer with energytunable synchrotron light at BL2 (Multiple Undulator beamline for Spectroscopic Analysis on Surface and HeteroInterface; MUSASHI) in Photon Factory, KEK. We used linearly polarized light (horizontal polarization) of 500975 eV. The energy and angular resolutions were set at 150 meV and 0.2°, respectively. Samples were cleaved in situ in an ultrahigh vacuum better than 1 × 10^{−10} Torr along the (\(11\bar{2}0\)) crystal plane, as confirmed by the Laue xray diffraction measurement on the cleaved surface and the photonenergy dependence of the band dispersion shown in Fig. 2b. Sample temperature was kept at T = 40 K during the ARPES measurements. The Fermi level (E_{F}) of samples was referenced to that of a gold film evaporated onto the sample holder.
Calculations
Electronic bandstructure calculations were carried out by means of firstprinciples band structure calculations by using WIEN2k code^{65} with the fullpotential linearized augmented planewave method within the generalized gradient approximation. We used the experimental structural parameters for the calculations.^{63} 24 × 24 × 36 kpoints sampling was used for the selfconsistent calculations.^{41}
Data availability
The data that support the findings of this study are available from the corresponding author upon reasonable request.
References
 1.
Ando, Y. Topological insulator materials. J. Phys. Soc. Jpn. 82, 102001 (2013).
 2.
Qi, X.L. & Zhang, S.C. Topological insulators and superconductors. Rev. Mod. Phys. 83, 1057–1110 (2011).
 3.
Hasan, M. Z. & Kane, C. L. Colloquium: topological insulators. Rev. Mod. Phys. 82, 3045–3067 (2010).
 4.
Fu, L. Topological crystalline insulators. Phys. Rev. Lett. 106, 106802 (2011).
 5.
Hsieh, T. H. et al. Topological crystalline insulators in the SnTe material class. Nat. Commun. 3, 982 (2012).
 6.
Tanaka, Y. et al. Experimental realization of a topological crystalline insulator in SnTe. Nat. Phys. 8, 800–803 (2012).
 7.
Borisenko, S. et al. Experimental realization of a threedimensional Dirac semimetal. Phys. Rev. Lett. 113, 027603 (2014).
 8.
Neupane, M. et al. Observation of a threedimensional topological Dirac semimetal phase in highmobility Cd_{3}As_{2}. Nat. Commun. 5, 3786 (2014).
 9.
Liu, Z. K. et al. Discovery of a threedimensional topological Dirac semimetal, Na_{3}Bi. Science 343, 864–867 (2014).
 10.
Wang, Z. et al. Dirac semimetal and topological phase transitions in A_{3}Bi (A = Na, K, Rb). Phys. Rev. B 85, 195320 (2012).
 11.
Wang, Z., Weng, H., Wu, Q., Dai, X. & Fang, Z. Threedimensional Dirac semimetal and quantum transport in Cd_{3}As_{2}. Phys. Rev. B 88, 125427 (2013).
 12.
Xu, S.Y. et al. Discovery of a Weyl fermion semimetal and topological Fermi arcs. Science 349, 613–617 (2015).
 13.
Lv, B. Q. et al. Experimental discovery of Weyl semimetal TaAs. Phys. Rev. X 5, 031013 (2015).
 14.
Yang, L. X. et al. Weyl semimetal phase in the noncentrosymmetric compound TaAs. Nat. Phys. 11, 728–732 (2015).
 15.
Zyuzin, A. A. & Burkov, A. A. Topological response in Weyl semimetals and the chiral anomaly. Phys. Rev. B 86, 115133 (2012).
 16.
Liu, C.X., Ye, P. & Qi, X.L. Chiral gauge field and axial anomaly in a Weyl semimetal. Phys. Rev. B 87, 235306 (2013).
 17.
Wang, Z. & Zhang, S.C. Chiral anomaly, charge density waves, and axion strings from Weyl semimetals. Phys. Rev. B 87, 161107(R) (2013).
 18.
Landsteiner, K. Anomaly related transport of Weyl fermions for Weyl semimetals. Phys. Rev. B 89, 075124 (2014).
 19.
Chernodub, M. N., Cortijo, A., Grushin, A. G., Landsteiner, K. & Vozmediano, M. A. H. Condensed matter realization of the axial magnetic effect. Phys. Rev. B 89, 081407(R) (2014).
 20.
Liang, T. et al. Ultrahigh mobility and giant magnetoresistance in the Dirac semimetal Cd_{3}As_{2}. Nat. Mater. 14, 280–284 (2015).
 21.
Xiong, J. et al. Evidence for the chiral anomaly in the Dirac semimetal Na_{3}Bi. Science 350, 413–416 (2015).
 22.
Weng, H., Dai, X. & Fang, Z. Topological semimetals predicted from firstprinciples calculations. J. Phys. Condens. Matter 28, 303001 (2016).
 23.
Rhim, J.W. & Kim, Y. B. Landau level quantization and almost flat modes in threedimensional semimetals with nodal ring spectra. Phys. Rev. B 92, 045126 (2015).
 24.
Mitchell, A. K. & Fritz, L. Kondo effect in threedimensional Dirac and Weyl systems. Phys. Rev. B 92, 121109 (2015).
 25.
Huh, Y., Moon, E.G. & Kim, Y. B. Longrange Coulomb interaction in nodalring semimetals. Phys. Rev. B 93, 035138 (2016).
 26.
Ramamurthy, S. T. & Hughes, T. L. Quasitopological electromagnetic response of linenode semimetals. Phys. Rev. B 95, 075138 (2017).
 27.
Mikitik, G. P. & Sharlai, Y. V. Bandcontact lines in the electron energy spectrum of graphite. Phys. Rev. B 73, 235112 (2006).
 28.
Phillips, M. & Aji, V. Tunable line node semimetals. Phys. Rev. B 90, 115111 (2014).
 29.
Heikkilä, T. T. & Volovik, G. E. Nexus and Dirac lines in topological materials. New J. Phys. 17, 093019 (2015).
 30.
Mullen, K., Uchoa, B. & Glatzhofer, D. T. Line of Dirac nodes in hyperhoneycomb lattices. Phys. Rev. Lett. 115, 026403 (2015).
 31.
Weng, H. et al. Topological nodeline semimetal in threedimensional graphene networks. Phys. Rev. B 92, 045108 (2015).
 32.
Chen, Y. et al. Nanostructured carbon allotropes with Weyllike loops and points. Nano Lett. 15, 6974–6978 (2015).
 33.
Zeng, M. et al. Topological semimetals and topological insulators in rare earth monopnictides. Preprint at https://arxiv.org/abs/1504.03492 (2015).
 34.
Yu, R., Weng, H., Fang, Z., Dai, X. & Hu, X. Topological nodeline semimetal and Dirac semimetal state in antiperovskite Cu_{3}PdN. Phys. Rev. Lett. 115, 036807 (2015).
 35.
Kim, Y., Wieder, B. J., Kane, C. L. & Rappe, A. M. Dirac line nodes in inversionsymmetric crystals. Phys. Rev. Lett. 115, 036806 (2015).
 36.
Fang, C., Chen, Y., Kee, H.Y. & Fu, L. Topological nodal line semimetals with and without spinorbital coupling. Phys. Rev. B 92, 081201 (2015).
 37.
Xie, L. et al. A new form of Ca_{3}P_{2} with a ring of Dirac nodes. APL Mater. 3, 083602 (2015).
 38.
Chen, Y., Lu, Y.M. & Kee, H.Y. Topological crystalline metal in orthorhombic perovskite iridates. Nat. Commun. 6, 6593 (2015).
 39.
Kim, H.S., Chen, Y. & Kee, H.Y. Surface states of perovskite iridates AIrO_{3}: signatures of a topological crystalline metal with nontrivial Z_{2} index. Phys. Rev. B 91, 235103 (2015).
 40.
Xu, Q. et al. Twodimensional oxide topological insulator with ironpnictide superconductor LiFeAs structure. Phys. Rev. B 92, 205310 (2015).
 41.
Yamakage, A., Yamakawa, Y., Tanaka, Y. & Okamoto, Y. Linenode Dirac semimetal and topological insulating phase in noncentrosymmetric pnictides CaAgX (X = P, As). J. Phys. Soc. Jpn. 85, 013708 (2016).
 42.
Liu, J. et al. Straininduced nonsymmorphic symmetry breaking and removal of Dirac semimetallic nodal line in an orthoperovskite iridate. Phys. Rev. B 93, 085118 (2016).
 43.
Liang, Q.F., Zhou, J., Yu, R., Wang, Z. & Weng, H. Nodesurface and nodeline fermions from nonsymmorphic lattice symmetries. Phys. Rev. B 93, 085427 (2016).
 44.
Huang, H., Liu, J., Vanderbilt, D. & Duan, W. Topological nodalline semimetals in alkalineearth stannides, germanides, and silicides. Phys. Rev. B 93, 201114(R) (2016).
 45.
Zhu, Z., Li, M. & Li, J. Topological semimetal to insulator quantum phase transition in the Zintl compounds Ba_{2} X (X = Si, Ge). Phys. Rev. B 94, 155121 (2016).
 46.
Li, R. et al. Dirac node lines in pure alkali earth metals. Phys. Rev. Lett. 117, 096401 (2016).
 47.
Wang, J.T. et al. Bodycentered orthorhombic C_{16}: a novel topological nodeline semimetal. Phys. Rev. Lett. 116, 195501 (2016).
 48.
Zhao, J., Weng, H. & Fang, Z. Topological nodeline semimetal in compressed black phosphorus. Phys. Rev. B 94, 195104 (2016).
 49.
Chan, Y.H., Chiu, C.K., Chou, M. Y. & Schnyder, A. P. Ca_{3}P_{2} and other topological semimetals with line nodes and drumhead surface states. Phys. Rev. B 93, 205132 (2016).
 50.
Du, Y. et al. CaTe: a new topological nodeline and Dirac semimetal. Npj Quantum Matter 2, 3 (2017).
 51.
Hirayama, M., Okugawa, R., Miyake, T. & Murakami, S. Topological Dirac nodal lines and surface charges in fcc alkaline earth metals. Nat. Commun. 8, 14022 (2017).
 52.
Xu, Q., Yu, R., Fang, Z., Dai, X. & Weng, H. Topological nodal line semimetals in the CaP_{3} family of materials. Phys. Rev. B 95, 045136 (2017).
 53.
Takahashi, R., Hirayama, M. & Murakami, S. Topological nodalline semimetals arising from crystal symmetry. Phys. Rev. B 96, 155206 (2017).
 54.
Li, J. et al. Topological nodal line states and a potential catalyst of hydrogen evolution in the TiSi family. Preprint at https://arxiv.org/abs/1704.07043 (2017).
 55.
Bian, G. et al. Topological nodalline fermions in spinorbit metal PbTaSe_{2}. Nat. Commun. 7, 10556 (2016).
 56.
Schoop, L. M. et al. Dirac cone protected by nonsymmorphic symmetry and threedimensional Dirac line node in ZrSiS. Nat. Commun. 7, 11696 (2016).
 57.
Neupane, M. et al. Observation of topological nodal fermion semimetal phase in ZrSiS. Phys. Rev. B 93, 201104(R) (2016).
 58.
Wu, Y. et al. Dirac node arcs in PtSn_{4}. Nat. Phys. 12, 667–671 (2016).
 59.
Takane, D. et al. Diracnode arc in the topological linenode semimetal HfSiS. Phys. Rev. B 94, 121108(R) (2016).
 60.
Hosen, M. M. et al. Tunability of the topological nodalline semimetal phase in ZrSiXtype materials (X = S, Se, Te). Phys. Rev. B 95, 161101(R) (2017).
 61.
Chen, C. et al. Dirac line nodes and effect of spinorbit coupling in the nonsymmorphic critical semimetals MSiS (M = Hf, Zr). Phys. Rev. B 95, 125126 (2017).
 62.
Emmanouilidou, E. et al. Magnetotransport properties of the “hydrogen atom” nodalline semimetal candidates CaTX (T = Ag, Cd, X = As, Ge). Phys. Rev. B 95, 245113 (2017).
 63.
Mewis, A. & Naturforsch., Z. CaAgP und CaAgAs –Zwei Verbindungen mit Fe_{2}PStuktur. (CaAgP and CaAgAs –Two Compounds with Fe_{2}PStructure). Z. Nat. B 34, 14–17 (1979).
 64.
Okamoto, Y., Inohara, T., Yamakage, A., Yamakawa, Y. & Takenaka, K. Low carrier density metal realized in candidate linenode Dirac semimetals CaAgP and CaAgAs. J. Phys. Soc. Jpn. 85, 123701 (2016).
 65.
Blaha, P., Schwarz, K., Madsen, G., Kvasnicka, D. & Luiz, J. WIEN2k, An Augmented Plane Wave + Local Orbitals Program for Calculating Crystal Properties (Tech. Univ. Wien, Vienna, 2001).
Acknowledgements
We thank H. Oinuma and T. Nakamura for their assistance in the ARPES measurements and T. Yajima for his assistance in the singlecrystal xray diffraction experiments. This work was supported by GrantinAid for Scientific Research on Innovative Areas “Topological Materials Science” (JSPS KAKENHI No: JP15H05853), GrantinAid for Scientific Research (JSPS KAKENHI No: JP17H01139, JP15H02105, JP26287071, JP25287079, JP25220708, JP16K13664, and JP16K17725), KEKPF (Proposal No: 2015S2003 and 2016G555), and UVSOR (Proposal No: 28542 and 28828).
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The work was planned and proceeded by discussion among D.T., A.Y., Y.O., T.S., T.W., Y.O., and K.T. carried out the samples’ growth and their characterization. D.T., K.N., S.S., T.M., K.H., H.K, T.T., and T.S. performed ARPES measurements. Y.Y. and A.Y. performed the firstprinciples band structure calculations. D.T. and T.S. finalized the manuscript with inputs from all the authors.
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Takane, D., Nakayama, K., Souma, S. et al. Observation of Diraclike energy band and ringtorus Fermi surface associated with the nodal line in topological insulator CaAgAs. npj Quant Mater 3, 1 (2018). https://doi.org/10.1038/s415350170074z
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