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. 2025 May 7;15:15917. doi: 10.1038/s41598-025-01019-w

Valley crossed Andreev reflection in graphene periodic line defect superlattice junctions

Chongdan Ren 1,, Minglei Sun 2, Hongyu Tian 3, Sake Wang 4
PMCID: PMC12059181  PMID: 40335541

Abstract

We study the crossed Andreev reflection and the nonlocal transport in the staggered graphene/superconductor/periodic line defect superlattice (LDGSL) junctions. The staggered pseudospin potential in the left graphene electrode suppress the local Andreev reflection, while the elastic cotunneling of K′ valley electrons is inhibited due to the exclusive rightward motion of K valley electrons in the right LDGSL electrode, thereby enabling the realization of dominant intravalley crossed Andreev reflection for incident electrons from the K′ valley. Meanwhile, the intravalley elastic cotunneling occurs while both local Andreev reflection and crossed Andreev reflection are completely eliminated for incident electrons in the K valley. Furthermore, the probability of intervalley crossed Andreev reflection scattering is significantly lower than that of intravalley CAR scattering across a broad range of incident angles and electron energies. Our results are helpful for designing the flexible and high-efficiency Cooper pair splitter based on the valley degree of freedom.

Keywords: crossed Andreev reflection, periodic line defect superlattice, elastic cotunneling

Subject terms: Electronic properties and devices, Electronic properties and materials

Introduction

Quantum entanglement among microscopic particles has garnered significant attention due to its intrinsic importance and prospective applications in quantum information technologies1. Superconductors are considered natural sources of entangled electrons, as Cooper pairs consist of two electrons with interdependent spin and momentum characteristics29. Through the process of Cooper pair splitting, spatially separated spin-entangled electrons can be generated at the junction of a conductor and a superconductor. This mechanism’s time-reversed counterpart is known as crossed Andreev reflection (CAR) or non-local Andreev reflection. CAR represents a nonlocal process that converts an incoming electron from a voltage-biased lead into an outgoing hole in a spatially separated grounded lead via Cooper pair formation within the grounded superconductor10,11. The efficiency of CAR serves as a direct indicator of the effectiveness of Cooper pair splitting.

The realization of the CAR has garnered significant attention in both theoretical and experimental researchers1225. However, the emergence of CAR is generally accompanied by competing processes such as local Andreev reflection (LAR), normal reflection (NR), and elastic cotunneling (ECT). The LAR process converts an incoming electron from one electrode into a hole within the same electrode via Andreev reflection. In contrast, NR occurs when an electron is simply reflected at the interface without Andreev conversion, while ECT refers to the coherent transfer of an electron from one electrode to the other without forming a Cooper pair. These competing processes can obscure the detection of CAR, leading to a complete cancellation of the conductivities associated with ECT and CAR. This necessitates the use of noise measurements to identify the distinct signature of the CAR process in superconducting heterostructures.

Recent advancements have proposed methods to enhance CAR signals by mitigating both ECT and LAR processes through various types of leads, including normal metals, ferromagnetic metals, antiferromagnetic metals, and topological insulators2634. For instance, perfect CAR has been achieved in hybrid junctions formed by n-type and p-type semiconductors through band-structure-induced energy filtering6. Specialized circuits utilizing helical edge states of topological insulators have been designed to achieve perfect CAR27. Additionally, a mechanism for achieving perfect CAR has been theoretically proposed in superconductors situated between two antiferromagnetic layers, with one being electron-doped and the other hole-doped32.

Furthermore, CAR can be realized in graphene/superconductor/graphene junctions by exploiting the valley degree of freedom3540. Initial investigations into graphene-based devices aimed to achieve perfect CAR primarily focused on the zero density of states at the Dirac point35. In a zigzag graphene nanoribbon/superconductor/nanoribbon junction, exclusive CAR can be attained with complete suppression of both ECT and LAR, attributable to the valley selection rule in even zigzag nanoribbons37. The introduction of a staggered pseudo-spin potential and intrinsic spin-orbit coupling within graphene enables perfect CAR for electrons with a designated spin-valley index40.

In this study, we propose a distinct mechanism to achieve valley-dependent dominant CAR in proximitized graphene/ superconductor/ periodic line defect superlattice (LDGSL) junctions. The lattice structure of the LDGSL consists of extended line defects that are periodically embedded along the y-direction, forming a superlattice41. Due to this periodicity, Inline graphic remains a conserved quantum number. In Fig. 1a, we illustrate one such extended line defect, while in reality, they repeat periodically along y. The heterojunction extends along the x-direction, where electronic transport occurs. The dispersion of the LDGSL for Inline graphic is shown on the right side of Fig. 1b. Notably, the LDGSL functions as a valley filter by utilizing valley-dependent transmission properties near the bottom conduction band edge, where electrons near the K and K′ points exhibit distinct group velocities. This feature allows the LDGSL to selectively permit rightward propagation for electrons (holes) in the K (K′) valley and leftward propagation for electrons (holes) in the K′ (K+) valley. In our junction configuration, the left graphene electrode features a pseudospin staggered potential induced by the proximity effect of the substrate4247. We first demonstrate that if the left graphene electrode is gapless, LAR diminishes the occurrence of CAR. Upon introducing the staggered pseudospin potential, the left graphene electrode becomes insulating for the hole band, enabling exclusive CAR for K′ electrons while completely suppressing LAR and ECT. Conversely, ECT can manifest for K electrons while both LAR and CAR are suppressed. Moreover, both CAR and ECT processes are predominantly governed by intra-valley scattering. Additionally, we analyze the relationship between scattering probabilities and the incident angle Inline graphic, demonstrating that both inter-valley and intra-valley scattering probabilities rise with increasing Inline graphic, while intra-valley scattering probabilities considerably surpass those of inter-valley scattering. This indicates that dominant CAR with incident K′ valley electrons can be achieved across a wide range of incident angles and energy.

Fig. 1.

Fig. 1

(a) Schematic of the proposed proximitized staggered graphene/superconductor/LDGSL junction. The shaded green area in the right LDGSL region indicates the unit cell of the superlattice, with Inline graphic as primitive vectors. Inline graphic denotes the transverse dimension of the LDGSL unit cell, while its longitudinal dimension is Inline graphic. The junction is translationally symmetric along the Inline graphic-axis with periodicity Inline graphic. Hopping energies Inline graphic and Inline graphic represent the carbon-carbon bonds around the line defect. A external bias voltage Inline graphic is applied to the left graphene electrode, while the superconductor and the right LDGSL are grounded (i.e., their external bias voltage is set to zero), with the chemical potential Inline graphic tunable via gate voltage. (b) Band structure showing the dispersion of electrons (solid black lines) and holes (dashed red lines) in the left proximitized graphene and the right LDGSL for fixed Inline graphic. The expanded unit cell in the left proximitized graphene (shaded green region above) introduces additional subbands. The electron gap in the left proximitized graphene spans from Inline graphic to Inline graphic, and the hole gap ranges from Inline graphic to Inline graphic, where Inline graphic is the on-site staggered potential and Inline graphic is the chemical potential. Arrows indicate group velocity directions for each state. The solid red circle represents Inline graphic electrons, while solid and hollow blue circles denote Inline graphic electrons and holes, respectively. For incident Inline graphic electrons within the hole gap range, LAR is suppressed; these electrons can only tunnel to Inline graphic holes via intra-valley CAR. In contrast, incident Inline graphic electrons can tunnel to Inline graphic electrons through inter-valley ECT. (c) The original Dirac points Inline graphic and Inline graphic at Inline graphic in pristine graphene are shifted to Inline graphic and Inline graphic in the superlattice at Inline graphic.

The structure of the remainder of the paper is as follows. Section 2 presents the proposed structure and establishes the theoretical framework for calculating valley-related scattering probabilities as well as local and nonlocal conductances. In Section 3, we provide numerical results regarding intra-valley and inter-valley scattering for the NR, LAR, ECT, and CAR processes, along with the local and nonlocal conductance within the proposed structure. Finally, Section 4 offers a brief summary of the findings.

Theoretical model

In Fig. 1a, we present a schematic representation of the proximitized graphene /superconductor/LDGSL configuration within the Inline graphic plane, with junction interfaces located at Inline graphic and Inline graphic, where electronic transport is directed along the Inline graphic-axis. The staggered potential Inline graphic in the left graphene is attributed to the substrate, while the superconducting gap Inline graphic in the central region is induced by a bulk superconductor via the proximity effect. The right section features a one-dimensional LDGSL superlattice, created by periodically embedding extended line defects along the Inline graphic direction in pristine graphene. The unit cell size of the LDGSL in the Inline graphic direction measures Inline graphic with a being the graphene lattice constant, while the dimension in the Inline graphic direction is characterized by the integer Inline graphic41. The left pristine graphene sheet is infinitely wide along the Inline graphic direction. Due to the distinct lattice vectors of the LDGSL compared to graphene, the original Dirac points Inline graphic and Inline graphic at Inline graphic in pristine graphene shift to the new Dirac points Inline graphic and Inline graphic in the superlattice, now located at Inline graphic, as illustrated in Fig. 1c. The hopping energies Inline graphic and Inline graphic between nearest-neighbor lattice points on the line defect within the tight-binding model may differ from the uniform nearest-neighbor hopping energy Inline graphic of pristine graphene, indicating lattice distortion surrounding the line defect.

The following model Hamiltonian is employed here to describe the system:

graphic file with name d33e651.gif 1

where Inline graphic describes the left proximitized graphene with straggered potential, Inline graphic denoted a superconducting graphene caused by a bulk superconductor through proximity effect, and Inline graphic stands for the LDGSL electrode. In the tight-binding representation, the Hamiltonians Inline graphic, Inline graphic and Inline graphic are defined as follows:

graphic file with name d33e695.gif 2
graphic file with name d33e701.gif 3
graphic file with name d33e707.gif 4

where Inline graphic and Inline graphic represent the creation operators for an electron at lattice site Inline graphic and in sublattice Inline graphic of the line defect, respectively. Inline graphic refer to nearest-neighbor sites. The hopping integral is represented by Inline graphic, and Inline graphic denotes the on-site staggered potential, where Inline graphic corresponds to sublattice Inline graphic and Inline graphic to sublattice Inline graphic. Inline graphic refers to the induced superconducting pairing. Additionally, Inline graphic signifies the hopping energy associated with carbon-carbon bonds surrounding the line defect, and Inline graphic represents the Fermi level, which can be modulated through gate voltage technology. Note that the line defect atoms and the surrounding graphene atoms in the right electrode share the same chemical potential Inline graphic, as they are part of the same electronic system.

The valley-dependent transmission coefficients are determined utilizing the S-matrix method, a widely recognized approach in the field of mesoscopic physics48. In this investigation, we numerically implement the S-matrix method through KWANT49, a Python library specifically designed for calculating the S-matrix of scattering regions within tight-binding frameworks. The model previously defined is compatible with the KWANT methodology for S-matrix computations. The scattering matrix Inline graphic yields the scattering amplitude Inline graphic, which describes the transmission from the incoming Inline graphic state of particle type Inline graphic in lead Inline graphic to the outgoing Inline graphic state of particle type Inline graphic in lead Inline graphic50. Subsequently, the valley-dependent transmission coefficients can be derived using the following formula:

graphic file with name d33e870.gif 5

where Inline graphic and Inline graphic denote the valley-dependent NR and LAR processes, respectively, while Inline graphic and Inline graphic refer to the valley-related ECT and CAR processes. Furthermore, the condition Inline graphic=Inline graphic signifies intravalley scattering, whereas Inline graphic Inline graphic indicates intervalley scattering.

Based on the Blonder-Tinkham-Klapwijk framework51, the valley-dependent normalized conductance matrix at a bias voltage Inline graphic and at zero temperature can be expressed as follows:

graphic file with name d33e938.gif 6

where Inline graphic represents the number of transverse modes associated with the KInline graphic valley in the left graphene at the transverse wavevector Inline graphic. The terms Inline graphic correspond to the local conductance when Inline graphic and the nonlocal conductance when Inline graphic. Additionally, Inline graphic serves as a conserved quantum number due to the translational symmetry along the Inline graphic-axis. The Fourier transformation is performed using the wraparound function in Kwant.

Numerical results

In our calculations, we use the superconducting gap Inline graphic as the unit of energy. Inline graphic is taken as Inline graphic. Similarly, Inline graphic is also set to Inline graphic, ensuring that the energy range under consideration remains within the flat lowest conduction band and the corresponding hole band, thereby excluding minor dips near the K and KInline graphic points from transport. Inline graphic is designated as Inline graphic. Suppose a variation of less than 5Inline graphic in the hopping terms Inline graphic and Inline graphic, and here we adopt Inline graphic52. The length of the superconducting region is set to Inline graphic, while the width of a unit cell of the LDGSL is set to Inline graphic.

Firstly, we consider the left graphene without the pseudospin staggered potential, i.e., Inline graphic, resulting in gapless and linear dispersion for both electrons and holes in graphene. Fig. 2 illustrates the intra- and intervalley scattering spectra for NR, LAR, CAR, and ECT processes as a function of incident energy Inline graphic at Inline graphic (i.e., normal incidence with Inline graphic). For the ECT process, only the intra-valley transmission Inline graphic is significant, while other processes can be disregarded (see Fig. 2c). This phenomenon can be attributed to the valley filtering effect, which originates from the presence of a single rightward-propagating mode in the K valley within the right LDGSL electrode. In the case of LAR, intervalley scattering associated with both the K and KInline graphic valleys (Inline graphic and Inline graphic) occurs within the energy range Inline graphic, as illustrated in Fig. 2b. Notably, Inline graphic is less than Inline graphic due to the ability of K valley electrons to tunnel into the right LDGSL electrode, whereas KInline graphic valley electrons can only be normally reflected (see Fig. 2a). In contrast to LAR and ECT, all intra- and intervalley CAR processes can be neglected, as demonstrated in Fig. 2d. Thus, this configuration employs the right LDGSL electrode to block tunneling of KInline graphic valley electrons. Additionally, for CAR to take place, it is essential to suppress LAR process occurring in the left electrode.

Fig. 2.

Fig. 2

Plots of the transmission probabilities for intra- and intervalley NR (a), LAR (b), ECT (c), and CAR (d) as functions of the incident electronic energy Inline graphic at an incident angle of Inline graphic, specifically for the condition where Inline graphic. Inline graphic denotes the transmission probability of Inline graphic valley particles to Inline graphic valley particles.

The LAR process can be effectively suppressed by employing either Inline graphic-type or Inline graphic-type graphene. This suppression relies on the principle that an electron cannot be reflected as a hole within the same electrode if the hole band is artificially rendered insulating. When a pseudospin staggered potential Inline graphic is introduced, an energy gap of Inline graphic emerges. This gap for electrons extends from Inline graphic to Inline graphic, while the corresponding gap for holes spans from Inline graphic to Inline graphic, as shown in Fig. 1b. Within the energy range defined by the hole band gap, LAR is absent for incident electrons. In Fig. 3, we consider the scattering spectra under a finite pseudospin staggered potential of Inline graphic, with other parameters consistent with those in Fig. 2. As anticipated, LAR is zero within the energy range Inline graphic and nonzero outside this interval, as demonstrated in Fig. 3b. Furthermore, nonlocal ECT processes associated with intravalley scattering Inline graphic are prohibited, while those related to intervalley scattering Inline graphic are minimal (refer to Fig. 3c). Consequently, CAR can occur in the injection of KInline graphic electrons Inline graphic without LAR and ECT (shown in Fig. 3d), even outside the superconducting gap, as depicted in the inset of Fig. 3d. In contrast, for incident K electrons within the energy gap of hole gap, both LAR processes (Inline graphic and Inline graphic) as well as intra-valley CAR Inline graphic are zero, while inter-valley CAR Inline graphic is negligibly small, leaving only a finite intra-valley ECT Inline graphic. Thus, by analyzing the carrier type in the right LDGSL electrode, it is possible to ascertain whether the incident electron is a K or KInline graphic valley electron. These processes are clearly illustrated in Fig. 1b, offering a visual representation of the mechanisms discussed above. Furthermore, unlike the previous scenario where Inline graphic, the intervalley NR processes Inline graphic and Inline graphic occur alongside Inline graphic from both valleys, as demonstrated in Fig. 3a.

Fig. 3.

Fig. 3

Plots of the transmission probabilities for intra- and intervalley NR (a), LAR (b), ECT (c), and CAR (d) as a function of the incident electronic energy Inline graphic at an incident angle of Inline graphic, under the condition where Inline graphic. Inline graphic denotes the transmission probability of Inline graphic valley particles to Inline graphic valley particles. Aside from Inline graphic, all other parameters in the inset of panel (d) are consistent with those in panel (d).

To gain a more comprehensive understanding of the interplay between CAR and ECT as a function of the angle of incidence, we present the inter-valley and intra-valley CAR and ECT probabilities within the Inline graphic parameter space, as depicted in Fig. 4. When the energy of the incident electron at the left electrode falls within the energy gap of the corresponding hole and the angle of incidence is near Inline graphic, the probabilities for both intra- and inter-valley CAR and ECT exhibit minimal variation, with intra-valley scattering probabilities markedly surpassing those of inter-valley scattering, as illustrated by the comparisons between Fig. 4a–d. This phenomenon suggests that when electrons from the KInline graphic valley impinge upon the left electrode, nearly ideal CAR occurs at the right LDGSL electrode, while ECT is observed for electrons originating from the K valley. As the incident angle Inline graphic increases, the energy ranges favorable for intra-valley CAR and ECT broaden. This behavior is attributed to the critical angle for LAR, defined by Inline graphic , where Inline graphic represents the angular threshold beyond which LAR ceases to occur53. Concurrently, both intra-valley and inter-valley scattering probabilities increase with Inline graphic. The enhancement of inter-valley CAR and ECT scattering can be attributed to the reduced effective separation of the electronic states near the two valleys as Inline graphic becomes non-zero in the band structure of the right LDGSL electrode with increasing incident angle Inline graphic. The increase in intra-valley scattering with Inline graphic can be elucidated by the upward shift of the conduction band minimum in the left graphene, which facilitates a more effective alignment of the conduction band slopes between the two electrodes.

Fig. 4.

Fig. 4

(a) Intra-valley CAR probabilities for incident Inline graphic electrons, denoted as Inline graphic, in the Inline graphic space; (b) Inter-valley CAR probabilities for incident Inline graphic electrons, represented as Inline graphic, in the Inline graphic space; (c) Intra-valley ECT probabilities for incident Inline graphic electrons, denoted as Inline graphic, in the Inline graphic space; (d) Inter-valley ECT probabilities for incident Inline graphic electrons, represented as Inline graphic, in the Inline graphic space. The parameters are consistent with those presented in Fig. 3.

Finally, We examine both local and nonlocal conductance as shown in Fig. 5. The local conductance for incoming electrons from the K and KInline graphic valleys exhibits a notable reduction as the bias voltage increases from Inline graphic. Importantly, within the energy interval Inline graphic, where no holes are present, the local conductance does not converge to zero, as typically observed in two-terminal graphene/superconductor junctions; rather, it indicates the contribution of nonlocal processes. Furthermore, the LAR within the energy range Inline graphic corresponds to retro-Andreev reflection, whereas the LAR within the energy range Inline graphic is associated with specular Andreev reflection. Regarding nonlocal conductivity, for incident electrons in the KInline graphic valley, the conductivity remains relatively constant within the energy gap, facilitating nearly ideal CAR. However, as the energy of the incident electrons deviates from the energy gap, the CAR decreases towards zero. Conversely, for electrons originating from the K valley, the nonlocal conductivity remains largely stable both inside and outside the energy gap. Within the energy gap, the total conductivity is low due to the cancellation between CAR and ECT, while outside the energy gap, it approaches a value determined primarily by ECT.

Fig. 5.

Fig. 5

Normalized local (a) and non-local (b) conductance spectra are presented for the Inline graphic electrons (blue dotted line), Inline graphic electrons (red dash-dot line), and the total conductance (black solid line).

Conclusion

In conclusion, this investigation presents an new approach for achieving valley-dependent dominant CAR in straggered graphene/superconductor/LDGSL junctions. By employing a staggered pseudospin potential and the valley-filtering effect of the LDGSL, we effectively suppress LAR and ECT, thereby facilitating exclusive intra-valley CAR. The results indicate that intra-valley CAR scattering is predominantly unaffected by the angle of incidence and is considerably greater than inter-valley CAR scattering. These findings make a important contribution to the understanding of electron transport phenomena in defect-based junctions and highlight the potential for harnessing valley-dependent physics within quantum information technologies.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Grant No. 12264059), and the Natural Science Foundation of Shandong Province (Grant No. ZR2023MA027).

Author contributions

C.Ren.: Formal analysis, investigation and writing-original draft preparation; S.Wang.: Formal analysis and validation; M.Sun.: Data curation and validation; H.Tian: Formal analysis; All authors have read and agreed to the published version of the manuscript. All authors reviewed the manuscript.

Data availability

The data that support the plots within this paper and other findings of this study are available from the corresponding author upon reasonable request.

Declarations

Competing interests

The authors declare no competing interests.

Footnotes

Publisher’s note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

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Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Data Availability Statement

The data that support the plots within this paper and other findings of this study are available from the corresponding author upon reasonable request.


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