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of the peaked conductivity and its decaying tendency un- der the application of the potential gradient will strongly support the superconducting multiphase. IV. LINEAR AND NONLINEAR PARACONDUCTIVITY IN THE IN-PLANE MAGNETIC FIELD In this section, we study the linear and nonlinear para- conductivity of the system in the in-plane magnetic field with and without the potential gradient. 8 (a) 0 0.5 1 1.5 2 2.5 0 0.2 0.4 0.6 0.8 1 H/Tc0 T/Tc0 (b) 0 0.01 0.02 0.03 0.04 0.05 0.06 0 0.5 1
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2 2.5 0 0.2 0.4 0.6 0.8 1 H/Tc0 T/Tc0 (b) 0 0.01 0.02 0.03 0.04 0.05 0.06 0 0.5 1 1.5 2 2.5 q H/Tc0 (c) 0.0 0.5 1.0 1.5 2.0 0 0.5 1 1.5 2 2.5 σxx/σ0 H/Tc0 (d) 0.00 0.02 0.04 0.06 0.08 0.10 0.12 -0.1 -0.05 0 0.05 0.1 αµ(q) qx (e) 0.00 0.02 0.04 0.06 0.08 0.10 0.12 -0.1 -0.05 0 0.05 0.1 αµ(q) qx (f) 0.00 0.02 0.04 0.06 0.08 0.10 -0.1 -0.05 0 0.05 0.1 αµ(q) qx FIG. 6. (a) The superconducting transition line of the sys-
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0.10 -0.1 -0.05 0 0.05 0.1 αµ(q) qx FIG. 6. (a) The superconducting transition line of the sys- tem in the in-plane magnetic field. (b) The magnetic field dependence of Cooper pair’s momentum along the transition line. Superconducting state changes from the BCS state to the FFLO state near H/Tc0 ∼ 1.4. (c) The linear paracon- ductivity. (d-f) Momentum dependence of αµ for qy = 0. (d), (e), and (f) correspond to H = 0.00, 0.35, and 0.70, respec- tively. A. The system with inversion symmetry
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tively. A. The system with inversion symmetry In the beginning, we consider the system without the potential gradient. In this case, the system has inversion symmetry, and therefore the nonlinear paraconductivity vanishes. We calculate the superconducting transition line and the linear paraconductivity in the same way as Sec. III. As understood from Figs. 6(a) and 6(b), the super- conducting phase diagram has the BCS phase in the low magnetic field and the FFLO phase in the high magnetic
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magnetic field and the FFLO phase in the high magnetic field [76]: The Cooper-pair momentum becomes finite for the magnetic field H ≳ 1.4Tc0. Furthermore, the lin- ear paraconductivity σxx 1s has a peak near the tricritical point as shown in Fig. 6(c). The origin of this peak is at- tributed to the shape of αµ(q). We show the momentum dependence of αµ(q) for the system in the BCS phase (H = 0.00) and FFLO phase (H = 0.70) and near the tricritical point (H = 0.35), in Figs. 6(d), 6(f) and 6(e),
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tricritical point (H = 0.35), in Figs. 6(d), 6(f) and 6(e), respectively. It should be noted that the contribution to the paraconductivity formula Eq. (21) mainly comes from the region where αµ(q) is vanishingly small. Near the tricritical point, we can see from Fig. 6(e) that the area of small αµ(q) is much larger than that in Figs. 6(d) and 6(f). This naturally leads to the peak of paraconduc- tivity. In other words, the peaked paraconductivity near the tricritical point may be interpreted as coming from
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the tricritical point may be interpreted as coming from the degeneracy of the BCS and FFLO states, in analogy with the case in the perpendicular magnetic field. The result obtained here is consistent with the previous study which pointed out the enhanced linear paraconductivity with the anomalous temperature scaling near the tricriti- cal point [70, 71]. This result implies that the observation of the linear paraconductivity can be used as a probe of FFLO superconductors. B.
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of the linear paraconductivity can be used as a probe of FFLO superconductors. B. The system without inversion symmetry In this section, we apply the potential gradients v = 0.01 and v = 0.10, which are smaller and larger than the transition temperature Tc0 ∼ 0.0255, and correspond to weakly and strongly noncentrosymmetric supercon- ductors, respectively. We consider not only the linear paraconductivity but also the nonlinear paraconductiv- ity, which is allowed due to the broken inversion sym-
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ity, which is allowed due to the broken inversion sym- metry and C2z rotation symmetry. As an indicator of the nonreciprocity, in addition to σxxx 2s , we focus on the quantity ηxxx = σxxx 2s (σxx 1s )2 , (33) to study the nonreciprocal charge transport. This quan- tity is convergent as approaching the transition temper- ature, in contrast to σ1s and σ2s. It has the dimension of the inverse of the current density and, therefore, repre- sents the typical value of the current density where non-
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sents the typical value of the current density where non- reciprocity becomes visible [74]. We show the calculation results in Fig. 7. First, we discuss the difference of the superconducting phase dia- grams in the presence and absence of the inversion sym- metry, by comparing Figs. 6 and 7. By switching on the potential gradient v, due to the inversion symmetry breaking, the BCS-FFLO transition in Fig. 6 begins to change to the crossover of the so-called helical supercon-
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change to the crossover of the so-called helical supercon- ductivity [74, 80–90]. Indeed, the Cooper-pair momen- tum takes finite values in the low-field regime before it takes large values in the high magnetic field, as shown in Figs. 7(b) and 7(g). For clarity, we call the crossover in weakly and strongly noncentrosymmetric cases as BCS- FFLO-like crossover and helical crossover, respectively. When the inversion symmetry breaking is weak (v = 0.01), the behavior of the linear paraconductivity in the
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0.01), the behavior of the linear paraconductivity in the moderate magnetic field is similar to that near the BCS- PDW transition. Indeed, we can see that the linear para- conductivity has a peak in the BCS-FFLO-like crossover region [Fig. 7(c)] as well as near the BCS-FFLO transi- tion point [Fig. 6(c)]. By contrast, Fig. 7(h) shows that 9 0 0.01 0.02 0.03 0.04 0.05 0.06 0 0.5 1 1.5 2 2.5 q H/Tc0 0 0.5 1 1.5 2 2.5 0 0.2 0.4 0.6 0.8 1 H/Tc0 T/Tc0 0 0.01 0.02 0.03 0.04 0.05
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0 0.5 1 1.5 2 2.5 0 0.2 0.4 0.6 0.8 1 H/Tc0 T/Tc0 0 0.01 0.02 0.03 0.04 0.05 0.06 0 0.5 1 1.5 2 2.5 q H/Tc0 0 0.5 1 1.5 2 2.5 0 0.2 0.4 0.6 0.8 1 H/Tc0 T/Tc0 0.0 0.2 0.4 0.6 0.8 1.0 0 0.5 1 1.5 2 2.5 σxx/σ0 H/Tc0 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0 0.5 1 1.5 2 2.5 ηxxx H/Tc0 0.0 10.0 20.0 30.0 40.0 50.0 60.0 70.0 0 0.5 1 1.5 2 2.5 σxxx H/Tc0 ×10! ×10" 0.0 0.2 0.4 0.6 0.8 1.0 0 0.5 1 1.5 2 2.5 σxx/σ0 H/Tc0 0.0 10.0 20.0 30.0 40.0 50.0 0 0.5 1 1.5 2
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0.6 0.8 1.0 0 0.5 1 1.5 2 2.5 σxx/σ0 H/Tc0 0.0 10.0 20.0 30.0 40.0 50.0 0 0.5 1 1.5 2 2.5 σxxx H/Tc0 0.0 0.2 0.4 0.6 0.8 1.0 1.2 0 0.5 1 1.5 2 2.5 ηxxx H/Tc0 ×10! ×10" (a) (b) (d) (c) (f) (e) (g) (i) (h) (j) FIG. 7. The superconducting transition line [(a),(f)], Cooper-pair momentum [(b),(g)], linear [(c),(h)] and nonlinear [(d),(i)] paraconductivities, and nonreciprocity [(e),(j)] of the system in the in-plane magnetic field and potential gradient. (a-e) show
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the results of v = 0.01 and (f-j) are the results of v = 0.10. the peak vanishes in the strongly noncentrosymmetric system, i.e., in the helical crossover regime. These are natural results because the peaked linear paraconductiv- ity signals the degenerate superconducting states and the degeneracy is sufficiently lifted in the strongly noncen- trosymmetric case in Fig. 7(h). Interestingly, the behavior of the nonlinear paracon- ductivity is significantly different from the linear para- conductivity.
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ductivity is significantly different from the linear para- conductivity. We can see in Figs. 7(d) and 7(i) that there is a peak in the nonlinear paraconductivity in both weakly and strongly noncentrosymmetric systems with comparable strengths of σxxx 2s and ηxxx. The obtained peak in strongly noncentrosymmetric superconductors is consistent with the results of Ref. [74], which studies the enhancement of nonlinear paraconductivity associated with the helical crossover in a strongly noncentrosym-
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with the helical crossover in a strongly noncentrosym- metric mono-layer Rashba model. Our results indicate that the enhanced nonlinear paraconductivity associated with the evolution of finite-momentum superconductivity also exists in the weakly noncentrosymmetric regime. To understand the behavior of the nonlinear paracon- ductivity, we show in Figs. 8 and 9 the momentum dependence of αµ(q) with q = (qx, 0) in the moderate and strong magnetic fields. Here, µ specifies the min- imum eigenvalue of ˆα(q).
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and strong magnetic fields. Here, µ specifies the min- imum eigenvalue of ˆα(q). These figures clearly show the realization of finite-momentum superconductivity in the in-plane magnetic field. The results of αµ(q) for v = 0.01 is similar to those of the FFLO state shown in Figs. 6(e) and 6(f), reflecting the weak inversion breaking (v ≪ Tc0), while the strongly noncentrosymmetric case (v ≫ Tc0) in Figs. 8(c) and 8(d) shows a large devia- tion. We also show in Figs. 9(a) and 9(b) the enlarged
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tion. We also show in Figs. 9(a) and 9(b) the enlarged figures of Figs. 8(a) and 8(c), respectively, to consider the main contribution to the paraconductivity coming from the region αµ(q) ∼ 0. When seen in this energy scale, (a) 0.00 0.02 0.04 0.06 0.08 0.10 -0.1 -0.05 0 0.05 0.1 αµ(q) qx (b) 0.00 0.02 0.04 0.06 0.08 0.10 -0.1 -0.05 0 0.05 0.1 αµ(q) qx (c) 0.00 0.02 0.04 0.06 0.08 0.10 -0.1 -0.05 0 0.05 0.1 αµ(q) qx (d) 0.00 0.02 0.04 0.06 0.08 0.10 -0.1 -0.05 0 0.05 0.1 αµ(q) qx
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-0.05 0 0.05 0.1 αµ(q) qx (d) 0.00 0.02 0.04 0.06 0.08 0.10 -0.1 -0.05 0 0.05 0.1 αµ(q) qx FIG. 8. The momentum dependence of αµ(q). (a) and (b) are the case of v = 0.01, while (c) and (d) are the case of v = 0.10. (a) and (c) are for the moderate magnetic field H = 0.036 and H = 0.039, respectively, where the nonlinear paraconductivity shows the peak. (b) and (d) are obtained in the high magnetic field, H = 0.070. the structure of αµ(q) for v = 0.01 is essentially the same
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the high magnetic field, H = 0.070. the structure of αµ(q) for v = 0.01 is essentially the same as that for v = 0.1. Actually, the values of αµ(q) at the local minima q ∼ ±0.02, dubbed α±, are not degenerate due to the inversion symmetry breaking v = 0.01 ̸= 0, and satisfy α− − α+ ≫ α+ ≳ 0. This means that the α+ valley mainly contributes to the nonlinear paraconductiv- ity in the same way as the strongly noncentrosymmetric case. Thus, at the temperatures considered here, the sys- 10 (a) 0.000 0.001 0.002
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case. Thus, at the temperatures considered here, the sys- 10 (a) 0.000 0.001 0.002 0.003 0.004 0.005 -0.02 0 0.02 αµ(q) qx (b) 0.000 0.001 0.002 0.003 0.004 0.005 -0.02 0 0.02 αµ(q) qx FIG. 9. Enlarged figures of Figs. 8(a) and 8(c) for small αµ(q). The panels (a) and (b) correspond to Figs. 8(a) and 8(c), respectively. tem is sufficiently noncentrosymmetric for the nonlinear paraconductivity even though v ≪ Tc0. This explains the appearance of the peaked nonlinear paraconductiv- ity in Fig. 7(d).
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This explains the appearance of the peaked nonlinear paraconductiv- ity in Fig. 7(d). We expect that the peak width will decrease when v is decreased from v = 0.01 with fix- ing the reduced temperature, and eventually will vanish when α− − α+ ∼ α+ is always satisfied along the tran- sition line. This is consistent with σxxx 2s = 0 at v = 0 as enforced by the inversion symmetry. The important point is that a small potential gradi- ent v ≪ Tc0 is sufficient to obtain the sizable nonlin-
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ent v ≪ Tc0 is sufficient to obtain the sizable nonlin- ear paraconductivity. Such a small v does not usually modify superconducting properties. In this case, on the other hand, each valley of the FFLO state shown e.g., in Fig. 6(f), has the intrinsic nonreciprocity even without v: The αµ(q) dispersion has a (cubic) asymmetry with re- spect to each local minimum, which has been identified as the origin of the nonreciprocal charge transport in non- centrosymmetric superconductors [62, 72–74]. The appli-
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centrosymmetric superconductors [62, 72–74]. The appli- cation of the potential gradient lifts the degeneracy of the two valleys, and one of the valleys selectively contributes to the nonlinear paraconductivity, picking up the intrin- sic nonreciprocity of finite-momentum Cooper pairs. A small potential gradient inevitably exists in most thin film superconductors owing to substrate effects. Since the other contributions to the nonlinear paraconductiv- ity unrelated to the FFLO state, if any, would be small
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ity unrelated to the FFLO state, if any, would be small when v ≪ Tc0, the observation of the peaked nonlinear paraconductivity in intrinsically centrosymmetric super- conductors under a small potential gradient serves as the strong evidence for the FFLO state. V. SUMMARY AND CONCLUSION In this study, we have investigated the linear and non- linear paraconductivity in the bilayer system under the perpendicular and in-plane magnetic fields. We have re- vealed that the linear paraconductivity has a peak ac-
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vealed that the linear paraconductivity has a peak ac- companied by the BCS-PDW transition in the system with a perpendicular magnetic field. The peak of linear paraconductivity tends to vanish by applying the poten- tial gradient, signaling the lifted degeneracy of the BCS and PDW states. Similar results of the linear paracon- ductivity are obtained for the in-plane magnetic field. In this case, the degeneracy of the BCS and FFLO states gives rise to the peak structure of the linear paraconduc-
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gives rise to the peak structure of the linear paraconduc- tivity, which is also smeared out by applying the strong potential gradient. We have also studied the nonlinear paraconductivity of the system in the in-plane magnetic field. In contrast to the linear paraconductivity, a peak appears robustly in both the weakly and strongly noncen- trosymmetric cases, i.e., both near the BCS-FFLO-like crossover and the helical crossover regions. Since we neglected the orbital magnetic field in this
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crossover and the helical crossover regions. Since we neglected the orbital magnetic field in this paper, our results, particularly those in the perpendic- ular magnetic field, apply to the superconductors with large Maki parameters. Even when the orbital magnetic field can not be neglected, the qualitative results such as the peaked linear paraconductivity are expected to be unaffected. The peaked nonlinear paraconductivity in finite-momentum superconductors is also expected to
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The peaked nonlinear paraconductivity in finite-momentum superconductors is also expected to survive to some extent in the orbital magnetic field [74], leaving a quantitative study as a future issue. Based on the results obtained in this paper, we propose to use linear and nonlinear paraconductivity to probe multiphase and/or finite-momentum superconductors. In particular, this proposal is expected to be useful in thin film superconductors because the thermodynamic mea- surements are challenging there.
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film superconductors because the thermodynamic mea- surements are challenging there. The linear and non- linear paraconductivity have different advantages and disadvantages. The linear paraconductivity can gener- ally be used to probe degenerate superconducting states, through the detection of the peak structure, while it seems not sensitive to the detailed nature of the supercon- ducting states. The nonlinear paraconductivity can only be used by breaking the inversion symmetry. However,
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be used by breaking the inversion symmetry. However, once the symmetry allows a finite response, it can pro- vide strong evidence for the finite-momentum supercon- ductivity, including (nearly-)FFLO and helical supercon- ducting states. A sizable response is obtained by lifting the degeneracy of the finite-momentum Cooper pairs. It is known that there are a variety of finite-momentum su- perconducting states such as the layer-decoupled state or the orbital FFLO state [59, 91–93], and pair-density-wave
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the orbital FFLO state [59, 91–93], and pair-density-wave state in strongly correlated superconductors [94] (refer- ring to a different state from the that studied in this pa- per, accompanying the in-plane modulation of the order parameter). It is an interesting future issue to quantita- tively study the nonreciprocal charge transport of such finite momentum superconductors. ACKNOWLEDGMENTS T.M. thank fruitful discussion with Sho Ishikawa. This work was supported by JSPS KAKENHI
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T.M. thank fruitful discussion with Sho Ishikawa. This work was supported by JSPS KAKENHI No. JP21K13880, No. JP22H01181, No. JP22H04933, No. JP22H04476, No. JP23K17353, No. JP23K22452, No. JP24H00007, and No. JP24H01662. 11 [1] M. Sigrist and K. Ueda, Phenomenological theory of un- conventional superconductivity, Rev. Mod. Phys. 63, 239 (1991). [2] X.-L. Qi and S.-C. Zhang, Topological insulators and su- perconductors, Rev. Mod. Phys. 83, 1057 (2011). [3] Y. Tanaka, M. Sato, and N. Nagaosa, Symmetry and
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tivity of the Two-Phase superconductor CeRh2As2, Frontiers in Electronic Materials 2, 10.3389/fe- mat.2022.880579 (2022). [8] J. F. Landaeta, P. Khanenko, D. C. Cavanagh, C. Geibel, S. Khim, S. Mishra, I. Sheikin, P. M. R. Brydon, D. F. Agterberg, M. Brando, and E. Hassinger, Field- Angle dependence reveals Odd-Parity superconductivity in CeRh2As2, Phys. Rev. X 12, 031001 (2022). [9] S. Ogata, S. Kitagawa, K. Kinjo, K. Ishida, M. Brando, E. Hassinger, C. Geibel, and S. Khim, Parity transition of
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131, 016001 (2023). [93] K. Nakamura, A. Daido, and Y. Yanase, Orbital effect on the intrinsic superconducting diode effect, Phys. Rev. B Condens. Matter 109, 094501 (2024). [94] D. F. Agterberg, J. C. S. Davis, S. D. Edkins, E. Fradkin, D. J. Van Harlingen, S. A. Kivelson, P. A. Lee, L. Radz- ihovsky, J. M. Tranquada, and Y. Wang, The physics of Pair-Density waves: Cuprate superconductors and be- yond, Annu. Rev. Condens. Matter Phys. 11, 231 (2020). 14 Appendix A: Derivation of GL factor ˆα
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yond, Annu. Rev. Condens. Matter Phys. 11, 231 (2020). 14 Appendix A: Derivation of GL factor ˆα In this section, we demonstrate the derivation of GL factor ˆα from GL free energy, F = − 1 β tr log e−β ˆ H. (A1) Here, we can rewrite the Hamiltonian as ˆH = 1 2 � k Ψ(k)† ˆHBdG(k)Ψ(k) + 2 � k ξ(k) + � m,k |∆|2 U (A2) with the BdG Hamiltoninan ˆHBdG, ˆHN(k) = �HN(k) 0 0 −HN(−k)T � , (A3) ∆ = ∆1φ1 + ∆2φ2 (A4) ˆ∆ = � 0 ∆ ∆† 0 � , (A5) ˆHBdG(k) = ˆHN(k) + ˆ∆, (A6) and the Nambu spinor, Ψ(k)† = (c† k↑1, c†
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ˆ∆ = � 0 ∆ ∆† 0 � , (A5) ˆHBdG(k) = ˆHN(k) + ˆ∆, (A6) and the Nambu spinor, Ψ(k)† = (c† k↑1, c† k↓1, c† k↑2, c† k↓2, c−k,↑1, c−k↓1, c−k,↑2, c−k↓2). (A7) Then, the GL free energy is F = − 1 2β � k tr log � 1 + e−βEn(k)� + 2 � k ξ(k) + � m,k |∆|2 U (A8) = F|∆=0 + δF, (A9) where En(k) represents eigenvalues of ˆHBdG(k). By ex- panding δF by ∆, we can obtain the GL factor ˆα, δF/V = � m |∆|2 U + 1 2βV � k,ωn trN � 1 iωn − HN(k)∆(k) 1 iωn + HN(−k)T ∆(k)† � + O � ∆4� = � m |∆m|2 U + 1 2V � k,n,m Fnm(k) � ∆∗
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trN � 1 iωn − HN(k)∆(k) 1 iωn + HN(−k)T ∆(k)† � + O � ∆4� = � m |∆m|2 U + 1 2V � k,n,m Fnm(k) � ∆∗ 1∆1|⟨un(k)| φ1 |u∗ m(−k)⟩|2 + ∆∗ 2∆2|⟨un(k)| φ2 |u∗ m(−k)⟩|2 + ∆∗ 1∆2 ⟨u∗ m(−k)| φ† 1 |un(k)⟩ ⟨un(k)| φ2 |u∗ m(−k)⟩ +∆∗ 2∆1 ⟨u∗ m(−k)| φ† 2 |un(k)⟩ ⟨un(k)| φ1 |u∗ m(−k)⟩ � + O � ∆4� = �∆∗ 1 ∆∗ 2 � ˆα � ∆1 ∆2 � + O � ∆4� (A10) with Fmn(k) in Eq. (12). Then we obtain the expression of ˆα given in Eq. (11). We prove that σBCS−PDW vanishes in the system in the
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of ˆα given in Eq. (11). We prove that σBCS−PDW vanishes in the system in the perpendicular magnetic field. In this case, the system has both C2z symmetry and Mz symmetry, ˆα(q) = ˆα(−q), (A11) σx ˆα(q)σ† x = ˆα(q). (A12) Thus, we can express ˆα(q) by, ˆα(q) = � a(q) b(q) b(q) a(q) � , (A13) with real numbers a(q) and b(q). Accordingly, eigenvec- tors of ˆα are given by |BCS⟩ = 1 √ 2 � 1 1 � , (A14) |PDW⟩ = 1 √ 2 � 1 −1 � , (A15) regardless of q. This forces σBCS−PDW to vanish, since ⟨BCS| ji |PDW⟩ = 1 2
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1 √ 2 � 1 −1 � , (A15) regardless of q. This forces σBCS−PDW to vanish, since ⟨BCS| ji |PDW⟩ = 1 2 �1 1� ∂i � a(q) b(q) b(q) a(q) �� 1 −1 � = 1 2∂i(a(q) + b(q) − a(q) − b(q)) = 0. (A16) Thus, the linear paraconductivity is given by summing up the BCS and PDW contributions, σBCS and σPDW, in the system in the perpendicular magnetic field.
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Progress in Developing Highly Efficient p-Type TCOs for Transparent Electronics: A Comprehensive Review Jarnail Singh1 and Pankaj Bhardwaj2,* 1Department of Mechanical Engineering, University Centre for Research and Development, Chandigarh University, Mohali 140413, Punjab, India 2Department of Material Science and Engineering, National Institute of Technology Hamirpur- 177005 *E-mail address: [email protected] ORCID ID: 0000-0001-8341-525X Abstract
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177005 *E-mail address: [email protected] ORCID ID: 0000-0001-8341-525X Abstract Transparent conducting oxides (TCOs) represent a remarkable class of materials that possess both excellent electrical conductivity and high optical transparency, which are typically considered mutually exclusive in traditional materials. This unique combination of properties makes TCOs highly desirable for various applications, particularly in optoelectronic devices such
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makes TCOs highly desirable for various applications, particularly in optoelectronic devices such as transparent electrodes for displays, solar cells, and touchscreens. However, developing high- performance TCOs, especially p-type materials, has been a significant challenge. In conventional materials, achieving both high electrical conductivity and optical transparency is difficult. Because materials with wide optical band gap (≥ 3.1 eV) are transparent in the visible region but
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Because materials with wide optical band gap (≥ 3.1 eV) are transparent in the visible region but lack electrical conductivity, while conductive metals are opaque. Hence, the only way to induce both properties in a single material is to create non-stoichiometry and/or defects. By introducing shallow defects near the conduction band for n-type materials and the valence band for p-type materials, it is possible to enhance the conductivity of the material at room temperature.
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materials, it is possible to enhance the conductivity of the material at room temperature. However, developing efficient p-type TCOs has been particularly difficult due to the localized nature of the valence band derived from O 2p orbitals and the challenges associated with shallow acceptors, resulting in large effective mass of holes. While commercially available TCOs are predominantly n-type, such as Sn:In2O3, Al:ZnO, and F:SnO2, the development of efficient p-
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predominantly n-type, such as Sn:In2O3, Al:ZnO, and F:SnO2, the development of efficient p- type TCOs lags. In this review, we have discussed the origin of p-type conductivity in TCOs, and the difficulties encountered in developing efficient p-type materials. We have also demonstrated the fundamental materials physics of p-type TCOs, including electronic structures, doping, defect properties, and optical properties. A range of deposition techniques has been adopted to prepare
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properties, and optical properties. A range of deposition techniques has been adopted to prepare TCO films, and this review provides a detailed discussion of these techniques and their relative deposition parameters. Overall, we have presented an up-to-date and comprehensive review of different p-type transparent conducting oxide thin films, providing insights into ongoing research and potential future directions in this field. 1. Introduction
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and potential future directions in this field. 1. Introduction Transparent conducting oxide (TCO) materials hold excellent potential in a wide variety of applications, including thin-film solar cells, flat panel display, liquid crystal display (LCDs), light-emitting diodes (LEDs), thin-film transistors (TFTs), smart windows, invisible circuits, flexible and transparent devices [1]. For instance, transparent display devices with great refresh
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flexible and transparent devices [1]. For instance, transparent display devices with great refresh frequency and excellent resolution or pixel density can be realized by employing highly effective TCO materials. Furthermore, energy-efficient displays that operate in typical lighting atmospheres can be fabricated using TCO materials. TCOs may allow the removal of panel backlight (that accounts for power consumption around 90% in current displays) [2,3]. However,
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backlight (that accounts for power consumption around 90% in current displays) [2,3]. However, TCOs acquire a wide range of optoelectronic applications, but very modest work has been done on the development of p-type TCOs. The p-type TCOs with comparable performance to their n- type counterparts are necessary for the fabrication of active electronic devices based on transparent p-n junction. But the p-type TCOs were missing in literature for a long time until
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transparent p-n junction. But the p-type TCOs were missing in literature for a long time until Kawazoe and co-workers (from Tokyo Institute of Technology, Japan) in 1997 came up with an article in which p-type conductivity is reported in the thin film form of CuAlO2 [4]. This discovery helped other researchers to realize that the development of p-type TCOs is not an unfeasible task and unlocked a new field of “invisible electronics” or “transparent electronics”.
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electronics”. However, it is worth discussing that the first p-type semi-transparent conducting material in the form of nickel oxide (NiO) was reported by Sato et al. in 1993 [5]. They have deposited a thin film of NiO at various O2 content by using RF magnetron sputtering technique. A very low value of resistivity of 0.14 Ω-cm with a carrier concentration of 1.3×1019 cm-3 was observed in pristine NiO thin film at substrate temperature and oxygen partial pressure of 200 ⁰C
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observed in pristine NiO thin film at substrate temperature and oxygen partial pressure of 200 ⁰C and 1.33 Pa, respectively. Hall measurement results demonstrated the p-type conductivity in NiO thin film. But transparency was not upto the mark with an average value of 40% in the visible region for 110 nm thin film of NiO. They have also fabricated the p-i-n diode on a glass substrate, consisting of p-NiO/i-NiO/i-ZnO/n-ZnO and observed that optical transparency further
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substrate, consisting of p-NiO/i-NiO/i-ZnO/n-ZnO and observed that optical transparency further narrows down to 20%, which cannot be considered for superior optoelectronics devices-based applications. Still, this report has turned out to be a landmark in the field of “invisible electronics” and optoelectronic technology development. The research for developing p-type TCOs has been accelerated when Kawazoe et al.
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The research for developing p-type TCOs has been accelerated when Kawazoe et al. demonstrated the significant hole conductivity at room temperature [4]. Copper aluminium oxide (CuAlO2) thin film having a thickness of 500 nm was deposited on (0001) sapphire substrate using pulsed laser deposition (PLD) technique. As-deposited CuAlO2 thin film illustrated a wide optical band of 3.5 eV. The presence of Al3+ ions in between Cu+ ions reduced the cross-linking
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optical band of 3.5 eV. The presence of Al3+ ions in between Cu+ ions reduced the cross-linking of d10 electrons of Cu+ network along the c-axis. This may be responsible for the larger optical band gap of CuAlO2. The electrical conductivity of 1 S/cm was achieved in CuAlO2 thin film. The positive value of Hall coefficient and Seebeck coefficient confirmed the p-type nature of CuAlO2 thin film. Excellent Hall mobility of 10.4 cm2/Vs (like that of ITO) is responsible for the
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CuAlO2 thin film. Excellent Hall mobility of 10.4 cm2/Vs (like that of ITO) is responsible for the significant conductivity value of p-type CuAlO2. However, its conductivity value is still lower than the highly effective n-type TCOs. Nevertheless, these results demonstrated that both properties' simultaneous existence in p-type TCOs is not an invincible goal. After this report, intensive research has been conducted to explore other materials as p-type TCOs. Here, we have
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