# Fileset
[pressure-induced superconductivity in La4NiO10+δ(δ0.04 and -0.01).docx](https://mdr.nims.go.jp/filesets/87ac51db-0bfe-4b2b-9ada-bfd518fee0cd/download)
## Creator
[Hibiki Nagata](https://orcid.org/0009-0003-2656-4920), [Hiroya Sakurai](https://orcid.org/0000-0003-1964-6023), [Yuta Ueki](https://orcid.org/0009-0006-5893-1096), [Kazuki Yamane](https://orcid.org/0000-0002-0162-5411), [Ryo Matsumoto](https://orcid.org/0000-0001-6294-5403), [Kensei Terashima](https://orcid.org/0000-0003-0375-3043), Keisuke Hirose, Hiroto Ohta, Masaki Kato, [Yoshihiko Takano](https://orcid.org/0000-0002-1541-6928)
## Rights
[In Copyright](http://rightsstatements.org/vocab/InC/1.0/)
## Other metadata
[Pressure-Induced Superconductivity in La4Ni3O10+ δ (δ = 0.04 and −0.01)](https://mdr.nims.go.jp/datasets/f1276c75-b542-4289-9f76-9b30843422b3)
## Fulltext
Title of Paper Goes Here:Pressure-induced superconductivity in La4Ni3O10+δ (δ = 0.04 and −0.01)Hibiki Nagata1,2*, Hiroya Sakurai1, Yuta Ueki1,2, Kazuki Yamane1,2, Ryo Matsumoto1, Kensei Terashima1, Keisuke Hirose3‡, Hiroto Ohta3, Masaki Kato3, and Yoshihiko Takano1,2†1MANA, National Institute for Materials Science, 1-2-1 Sengen, Tsukuba, Ibaraki 305-0047, Japan2Graduate school of pure and applied sciences, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8577, Japan3Faculty of Science and Engineering, Doshisha University, 1-3 Tataramiyakotani, Kyo-Tanabe 610-0321, JapanThe superconducting transition temperatures, Tc, of La4Ni3O10+δ (δ = 0.04 and −0.01) were determined under various pressures up to 124.9 GPa by electrical resistance measurements with a diamond anvil cell. Tc exhibits a strong dependence on oxygen content within the pressure range of approximately 20 GPa and 80 GPa. At 48.0 GPa, Tc of La4Ni3O10.04 peaks at 36 K, marking the highest Tc reported thus far. The recent discovery of superconductivity in La3Ni2O7 has made a significant impact, not only because of its high transition temperature (Tc ~ 80 K under 14 GPa)1) but also due to its structural resemblance to high-Tc cuprates. These characteristics have sparked intense research into superconductivity on NiO2 layers from both theoretical and experimental perspectives. A major experimental endeavor has been made to discover new superconductors related to the compound, akin to the approach taken with the high-Tc cuprates, as such discoveries are expected to contribute to the characterization and understanding of superconductivity. In this context, we made the initial discovery that La4Ni3O9.99, featuring triple NiO2 layers, also undergoes a superconducting transition at 23 K under a high pressure of 79.2 GPa.2) Although the superconductivity was promptly confirmed by other research groups,3-6) the reported transition temperatures have shown inconsistency. This has motivated us to investigate a variety of samples with different chemical compositions. As a first trial, we synthesized La4Ni3O10.04 and measured its electrical resistance under various pressures to compare it with that of La4Ni3O9.99 additionally measured at higher pressures than in the previous study. 2)A powder sample of La4Ni3O10.04 was synthesized using a similar method to that employed for La4Ni3O9.99.2) The only difference lies in the heat treatment during hot isostatic pressing: for the former, the sample was annealed for 1hour at 1200℃ under a 400 atm oxygen partial pressure, whereas for the latter, it was annealed for 2hours at 600℃ under a 300 atm oxygen partial pressure. The determination of oxygen content was carried out as described in the previous paper.2)The samples were characterized by powder X-ray diffraction measurements using a commercial diffractometer, MiniFlex600 (Rigaku). All observed peaks were indexed assuming an orthorhombic crystal structure of space group Cmca,7) as depicted in Fig. 1, indicating that each sample was of a single phase. The lattice parameters were estimated from the peak positions to be a = 5.413 Å, b = 5.465 Å, and c = 27.97 Å for La4Ni3O10.04, and a = 5.412 Å, b = 5.464 Å, c = 27.98 Å for La4Ni3O9.99. The electrical resistance of the sample was measured under various pressures up to 124.9 GPa using conventional four-probe method employing a diamond anvil cell with boron-doped diamond electrodes.2, 8-9)The temperature dependence of the resistance of the samples is shown in Fig. 2. The resistance decreases with increasing pressure for both samples. One may notice that the resistance increases with decreasing temperature under certain conditions. However, we maintain that the samples are metallic at any temperature under the pressures, as evidenced by the absence of divergent behavior toward 0 K. The observed upturns are likely attributed to extrinsic factors, such as grain-boundary scattering, as sometimes seen in the resistance obtained using polycrystalline samples.3, 10-14) In the case of La4Ni3O10.04, the resistance exhibits a slight suppression below 5 K at 20.2 GPa, with this suppression becoming more pronounced under higher pressures, as depicted in Fig. 2a. The suppression is most likely attributable to the onset of superconductivity, as it displayed a similar field dependence to that observed with La4Ni3O9.99.2) For La4Ni3O9.99, it is evident that the drop in resistance, which has been attributed to superconductivity below 79.2 GPa,2) persists even at pressures of 112.6 GPa and 124.9 GPa. Notably, this marks the first observation of superconductivity in La4Ni3O10 at pressures exceeding 100 GPa.The superconducting transition temperature was estimated as the temperature at which the resistance began to deviate from an almost linear temperature dependence just above it, as indicated by the arrows in Fig. 2. These temperatures are summarized in Fig. 3. For La4Ni3O10.04, Tc rapidly increases with increasing pressure from 20.2 GPa, reaches at 36 K at 48.0 GPa, and then gradually decreases with further pressure increase. This Tc of 36 K represents the highest value reported thus far. In contrast, for La4Ni3O9.99, superconductivity begins to appear at a higher pressure of 32.8 GPa and gradually increases with increasing pressure. Thus, Tc of La4Ni3O10 exhibits a strong dependence on oxygen-content within the pressure range of approximately 20 GPa and 80 GPa. Clearly, oxygen content plays a crucial role in the emergence of superconductivity. Interestingly, most reported Tc values thus far fall between those of La4Ni3O10.04 and La4Ni3O9.99 within the pressure range of 20 GPa and 80 GPa. 3-6) Although some of the samples used in the previous reports3-6) were synthesized under lower oxygen partial pressures than La4Ni3O9.99, the variation in Tc may be attributed to difference in oxygen content.AcknowledgmentWe would like to express our gratitude to Professors K. Kuroki (Osaka Univ.), H. Sakakibara (Tottori Univ.), and M. Ochi (Osaka Univ.) for fruitful discussion. This work is supported by JSPS KAKENHI Grants No. JP20H05644 and JP24K01333.*E-mail: NAGATA.Hibiki@nims.go.jp†E-mail: TAKANO.Yoshihiko@nims.go.jp‡On leave from1) H. Sun, M. Huo, X. Hu, J. Li, Z. Liu, Y. Han, L. Tang, Z. Mao, P. Yang, B. Wang, J. Cheng, D.-X. Yao, G.-M. Zhang, and M. Wang, Nature 621, 493 (2023).2) H. Sakakibara, M. Ochi, H. Nagata, Y. Ueki, H. Sakurai, R. Matsumoto, K. Terashima, K. Hirose, H. Ohta, M. Kato, Y. Takano, and K. Kuroki, Phys. Rev. B 109, 144511 (2024).3) Q. Li, Y.-J. Zhang, Z.-N. Xiang, Y. Zhang, X. Zhu, and H.-H. Wen, Chinese Phys. Lett. 41, 017401 (2024).4) J. Li, C.-Q. Chen, C. Huang, Y. Han, M. Huo, X. Huang, P. Ma, Z. Qiu, J. Chen, X. Hu, L. Chen, and T. Xie, Science China: Physics, Mechanics and Astronomy 67, 117403 (2024).5) Y. Zhu, E. Zhang, B. Pan, X. Chen, D. Peng, L. Chen, H. Ren, F. Liu, N. Li, Z. Xing, J. Han, J. Wang, D. Jia, H. Wo, Y. Gu, Y. Gu, L. Ji, W. Wang, H. Gou, Y. Shen, T. Ying, X. Chen, W. Yang, C. Zheng, Q. Zheng, J.-g. Cuo, J. Zhao, arXiv:2311.07353.6) M. Zhang, C. Pei, X. Du, W. Hu, Y. Cao, Q. Wang, J. Wu, Y. Li, H. Liu, C. Wen, Y. Zhao, C. Li, W. Cao, S. Zhu, Q. Zhang, N. Yu, P. Chen, L. Zhang, Z. Li, J. Zhao, Y. Chen, H. Guo, C. Wu, F. Yang, S. Yan, L. Yang, and Y. Qi, arXiv:2311.07423.7) E. A. Kiselev, N. V. Proskurnina, V. I. Voronin, and V. A. Cherepanov, Inorg. Mater. 43, 167 (2007).8) R. Matsumoto, Y. Sasama, M. Fujioka, T. Irifune, M. Tanaka, T. Yamaguchi, H. Takeya, and Y. Takano, Rev. Sci. Instrum. 87, 076103 (2016)9) R. Matsumoto, A. Yamashita, H. Hara, T. Irifune, S. Adachi, H. Takeya, and Y. Takano, Appl. Phys. Express 11, 053101 (2018).10) T. Hosoya, K. Igawa, Y. Takeuchi, K. Yoshida, T. Uryu, H. Hirabayashi, and H. Takahashi, J. Phys.: Conf. Ser. 121, 052013 (2008).11) K. Oka, T. Yamauchi, S. Kanungo, T. Shimizu, K. Oh-ishi, Y. Uwatoko, M. Azuma, and T. Saha-Dasgupta, J. Phys. Soc. Jpn. 87, 024801 (2018).12) A. A. Belik, T. Yamauchi, H. Ueda, Y. Ueda, H. Yusa, N. Hirao, and M. Azuma, J. Phys. Soc. Jpn. 83, 074711 (2014).13) H. Sakurai, Phys. Rev. B 78, 094410 (2008).14) Y. Mizuguchi, S. Demura, K. Deguchi, Y. Takano, H. Fujihisa, Y. Gotoh, H. Izawa, and O. Miura, J. Phys. Soc. Jpn. 81, 114725 (2012).Fig. 1 (Color online) Powder X-ray diffraction patterns of La4Ni3O10.04 and La4Ni3O9.99, alongside a simulated pattern from the structural data.7) Miller indices are shown for some characteristic peaks.Fig. 2 (Color online) Temperature dependence of the resistance of La4Ni3O10.04 (a) and La4Ni3O9.99 (b) under various pressures. The dashed lines represent the linear temperature dependence just above Tc, and the arrows indicate Tc estimated (see the text).Fig. 3 (Color online) Tc of La4Ni3O10.04 (red filled circles), La4Ni3O9.99 (blue filled squares). The lines are guides to eye.image2.tifimage3.tifimage1.tif