Ferroelectric Tunnel Junction Device and Memory Cell

Abstract

Disclosed is a ferroelectric tunnel junction device and memory cell, and relates to the technical field of ferroelectric tunnel junction devices, comprising a ferroelectric tunnel barrier layer; a first electrode layer on one side of the ferroelectric tunnel barrier layer; a second electrode layer on the other side of the ferroelectric tunnel barrier layer; and a first interfacial layer at the interface between the first electrode layer and the ferroelectric tunnel barrier layer. The first electrode layer comprises a first antiperovskite material and the first interfacial layer comprises a second antiperovskite material that differs from the first antiperovskite material in composition, and preferably in at least the occupancy of corner sites or the centre sites. Also disclosed is a memory cell comprising the ferroelectric tunnel junction device, wherein the data is recordable as a direction of electric polarisation of the ferroelectric tunnel barrier layer.

Claims

1. A ferroelectric tunnel junction device, comprising: a ferroelectric tunnel barrier layer, having an electric polarisation; a first electrode layer on one side of the ferroelectric tunnel barrier layer; a second electrode layer on the other side of the ferroelectric tunnel barrier layer; and a first interfacial layer at the interface between the first electrode layer and the ferroelectric tunnel barrier layer, wherein the first electrode layer comprises a first antiperovskite material and the first interfacial layer comprises a second antiperovskite material that differs from the first antiperovskite material in composition, and in at least the occupancy of corner sites or centre sites of the respective antiperovskite lattice.

2. The device of claim 1, wherein the first and/or second antiperovskite materials are metallic antiperovskite materials.

3. The device of claim 1, wherein the first and/or second antiperovskite materials are antiperovskite nitride materials or antiperovskite carbide materials.

4. The device of claim 1, wherein the first antiperovskite material of the first electrode layer is an antiperovskite nitride of the form Cu.sub.3A.sub.1xN.sub.1u and the second antiperovskite material of the first interfacial layer is an antiperovskite nitride of the form Cu.sub.3B.sub.1yN.sub.1w, wherein A and B are a corner site element selected from a group comprising: Pd, Ru, Cu, Rh, Ag, Al, Au, Co, Cu, Fe, Ga, Ge, In, Ir, Mn, Ni, Pt, Sb, Si, Sn, and Zn, and where 0x1, 0y1, 0u<1, 0w<1.

5. The device of claim 4, wherein A and B are the same element and xy; and/or, wherein the first antiperovskite material comprises Cu.sub.3PdN and the second antiperovskite material comprises Cu.sub.3N.

6. The device of claim 1, wherein the first antiperovskite material is an antiperovskite nitride of the form Mn.sub.3+xD.sub.1xN.sub.1u, and the second antiperovskite material is an antiperovskite nitride of the form Mn.sub.3+yE.sub.1yN.sub.1w or Cu.sub.3A.sub.1zN.sub.1w, wherein D and E are a corner site element selected from a group comprising: Ag, Al, Au, Co, Cu, Fe, Ga, Ge, In, Ir, Ni, Pd, Pt, Rh, Sb, Si, Sn, and Zn, where A is a corner site element selected from a group comprising: Pd, Ru, Cu, Rh, Ag, Al, Au, Co, Cu, Fe, Ga, Ge, In, Ir, Mn, Ni, Pt, Sb, Si, Sn, and Zn, and where 0x1, 0y1, 0z1, 0u<1, 0w<1.

7. The device of claim 6, wherein D and E are the same element and xy; and/or wherein the first antiperovskite material of the first electrode layer comprises Mn.sub.3GaN and the second antiperovskite material of the first interfacial layer comprises Cu.sub.3N.

8. The device of claim 1, wherein the first antiperovskite material of the first electrode layer is an antiperovskite carbide of the form M.sub.3XC.sub.1x, and the second antiperovskite material of the first interfacial layer is an antiperovskite carbide of the form M.sub.3ZC.sub.1y, wherein M is a face-centre site element selected from a group comprising: Co, Fe and Ni, and X, Z is a corner site element selected from a group comprising: Al, Ta, Ti, Ga, In, Mn, and Sn, and where 0x<1, 0y<1.

9. The device of claim 1, wherein the first antiperovskite material of the first electrode layer is an antiperovskite nitride of the form Ma.sub.xN.sub.1x, and the second antiperovskite material of the first interfacial layer is an antiperovskite nitride of the form M.sub.3ZN.sub.1y, wherein M is a face-centre site element selected from a group comprising: Fe, Mn, Cu, and Ni, and X, Z is a corner site element selected from a group comprising: Sb, Pd, Rh, Ir, Ga, Ge, In, Mn, Pt, and Sn, and where 0x<1, 0y<1.

10. The device of claim 1, wherein the first interfacial layer has: a substantially uniform occupancy of corner or centre sites in a direction perpendicular to the interface; or a graded occupancy of corner or centre site atoms in the direction perpendicular to the interface; and/or a thickness of 10 nm or less.

11. The device of claim 1, wherein the ferroelectric tunnel barrier layer comprises a ferroelectric perovskite material, preferably wherein the ferroelectric perovskite material of the ferroelectric tunnel barrier layer has the form A.sub.xA.sub.1xB.sub.yB.sub.1yO.sub.3, wherein A and A are one or more elements selected from a group comprising: Ca, Sr, Ba, Bi, Pb, and La, and where B and B are one or more elements selected from a group comprising: Ti, Zr, Mo, W, Nb, Sn, Sb, In, Ga, Cr, Mn, Al, Co, Fe, Mg, Ni, Zn, Bi, Hf, and Ta.

12. The device of claim 11, wherein the ferroelectric perovskite material is or comprises BaTiO.sub.3.

13. The device of claim 1, wherein the second electrode layer comprises: a metallic material; and/or a third antiperovskite material.

14. The device of claim 1, wherein the second electrode layer comprises a third antiperovskite material and the device comprises a second interfacial layer at the interface between the second electrode layer and the ferroelectric tunnel barrier layer, wherein the second interfacial layer comprises fourth antiperovskite material that differs from the third antiperovskite material in composition, and in at least the occupancy of corner sites or centre sites of the respective antiperovskite lattice.

15. The device of claim 14, wherein the third antiperovskite material and/or fourth antiperovskite material comprise: metallic antiperovskite materials; and/or antiperovskite nitride materials or antiperovskite carbide materials.

16. The device of claim 14, wherein the third antiperovskite material of the second electrode layer is an antiperovskite nitride of the form Cu.sub.3A.sub.1xN.sub.1u and the fourth antiperovskite material of the second interfacial layer is an antiperovskite nitride of the form Cu.sub.3B.sub.1yN.sub.1w, wherein A and B are a corner site element selected from a group comprising: Pd, Ru, Cu, Rh, Ag, Al, Au, Co, Cu, Fe, Ga, Ge, In, Ir, Mn, Ni, Pt, Sb, Si, Sn, and Zn, and where 0x1, 0y1, 0u<1, 0w<1, and preferably, wherein A and B are the same element and xy; and/or, wherein the third antiperovskite material of the second electrode layer comprises Cu.sub.3PdN, and the fourth antiperovskite material of the second interfacial layer comprises Cu.sub.3N.

17. The device of claim 14, wherein the third antiperovskite material of the second electrode is an antiperovskite nitride of the form Mn.sub.3+xD.sub.1xN.sub.1u, and the fourth antiperovskite material of the second interfacial layer is an antiperovskite nitride of the form Mn.sub.3+yE.sub.1yN.sub.1w or Cu.sub.3A.sub.1zN.sub.1w, wherein D and E are a corner site element selected from a group comprising: Ag, Al, Au, Co, Cu, Fe, Ga, Ge, In, Ir, Ni, Pd, Pt, Rh, Sb, Si, Sn, and Zn, where A is a corner site element selected from a group comprising: Pd, Ru, Cu, Rh, Ag, Al, Au, Co, Cu, Fe, Ga, Ge, In, Ir, Mn, Ni, Pt, Sb, Si, Sn, and Zn, and where 0x1, 0y1, 0z1, 0u<1, 0w<1, and preferably, wherein D and E are the same element and xy; and/or wherein the third antiperovskite material of the second electrode layer comprises Mn.sub.3GaN, and the fourth antiperovskite material of the second interfacial layer comprises Cu.sub.3N.

18. The device of claim 14, wherein the third antiperovskite material of the second electrode layer is an antiperovskite carbide of the form M.sub.3XC.sub.1x, and the fourth antiperovskite material of the second interfacial layer is an antiperovskite carbide of the form M.sub.3ZC.sub.1y, wherein M is a face-centre site element selected from a group comprising: Co, Fe and Ni, and X,Z is a corner site element selected from a group comprising: Al, Ta, Ti, Ga, In, Mn, and Sn, and where 0x<1, 0y<1.

19. The device of claim 14, wherein the third antiperovskite material of the second electrode layer is an antiperovskite nitride of the form M.sub.3XN.sub.1x, and the fourth antiperovskite material of the second interfacial layer is an antiperovskite nitride of the form M.sub.3ZN.sub.1y, wherein M is a face-centre site element selected from a group comprising: Fe, Mn, Cu, and Ni, and X,Z is a corner site element selected from a group comprising: Sb, Pd, Rh, Ir, Ga, Ge, In, Mn, Pt, and Sn, and where 0x<1, 0y<1.

20. A memory cell comprising the device of claim 1, wherein data is recordable as a direction of electric polarisation of the ferroelectric tunnel barrier layer.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0058] In order that the invention can be well understood, embodiments will now be discussed by way of example only with reference to the accompanying drawings, in which:

[0059] FIG. 1 is a schematic diagram of a ferroelectric tunnel junction device according to the prior art illustrating the principle of operation;

[0060] FIG. 2 shows an example cubic antiperovskite structure in the case of Cu.sub.3PdN;

[0061] FIG. 3 is a schematic diagram of a ferroelectric tunnel junction device according to an embodiment of the present invention including a first interfacial layer on one side of the barrier layer;

[0062] FIG. 4 shows a schematic diagram of the variation in site occupancy with distance from the barrier;

[0063] FIG. 5 is a schematic diagram of a ferroelectric tunnel junction device according to another embodiment of the present invention including a first interfacial layer and a second interfacial layer on both sides of the barrier layer;

[0064] FIG. 6 shows a schematic diagram of a ferroelectric tunnel junction device according to another embodiment;

[0065] FIG. 7 shows the simulated density of states of the device structure of FIG. 6;

[0066] FIG. 8 shows the simulated transmission of the device structure of FIG. 6; and

[0067] FIG. 9 shows the simulated tunnelling electroresistance of the device of FIG. 6.

[0068] It should be noted that the figures are diagrammatic and may not be drawn to scale. Relative dimensions and proportions of parts of these figures may have been shown exaggerated or reduced in size, for the sake of clarity and convenience in the drawings. The same reference signs are generally used to refer to corresponding or similar features in modified and/or different embodiments.

DETAILED DESCRIPTION

[0069] FIG. 1 shows a schematic diagram of a conventional ferroelectric tunnel junction device 10 (FTJ) known in the art. The device 10 comprises a ferroelectric tunnel barrier layer 11 sandwiched between two electrodes layers 21, 22 formed of different electrode materials. The ferroelectric tunnel barrier layer 11 is sufficiently thin to exhibit quantum-mechanical tunnelling at low applied voltages, and exhibits a remnant ferroelectric polarisation P which can be switched between two directions (left and right in this example) by applying an electric field (voltage) between the electrodes 21, 22. The functionality of the device 10 is based on the dependence of the electrical resistance on the direction of polarisation P in the ferroelectric tunnel barrier layer 11, known as tunnelling electroresistance (TER) which can produce ON/OFF resistance ratios well in excess of 103. This functionality, combined with the fact that the ferroelectric tunnel barrier layer 11 can retain its polarisation for long periods of time when disconnected from a power source makes the FTJ device 10 an attractive candidate for non-volatile memory whereby information is stored/encoded in the polarisation direction of a ferroelectric tunnel barrier layer 11 and can be read via the different resistances in the ON/OFF states.

[0070] The main origin of the TER effect is the polarisation-induced modulation of the electronic states at the electrode-barrier interfaces h1, h2 and the change in electrostatic potential profile of the tunnel barrier 11 itself (due to asymmetry of screening length in the electrodes) which in turn modulates the quantum-mechanical transmission through the barrier 11. The electric field from the ferroelectric barrier layer 11 can penetrate a few atomic layers into the electrodes 21, 22 and change the population of the electronic band structure at the Fermi energy which has a significant impact on the electronic states available for tunnelling through the barrier 11. A basic requirement for tunnelling through the barrier 11 is alignment in reciprocal k-space (k.sub.x, k.sub.y) of filled electronic states in one electrode layer 21 and empty states in the other electrode layer 22. As such, in general, high TER requires good mutual alignment of electronic states in k-space (k.sub.x, k.sub.y) at the two electrode-barrier interfaces h1, h2 for one polarity of the ferroelectric barrier layer 11 (the ON state of the device), and very poor alignment for the opposite polarity of the ferroelectric barrier layer 11 (the OFF state of the device). In practice, this generally requires an asymmetry between the two electrode-barrier interfaces h1, h2.

[0071] A common approach in the prior art is to use different materials for the two electrode layers 21, 22 which exhibit a different change in electronic properties or density of states with the polarisation of the barrier 11. Specific electrode materials can be chosen to exhibit a large response to the polarisation of the barrier 11.

[0072] The present invention makes use of metallic antiperovskite electrode materials whose electronic (and magnetic) properties can be readily tuned through their composition and can be grown in ultrathin films with high crystalline quality. Antiperovskites are a family of alloys with a crystal structure similar to the perovskite structure which is cubic in the absence of strain, but with the positions of anion and cation constituent elements reversed in the unit cell.

[0073] The antiperovskite structure is typically represented by the composition formula M.sub.3BA, where M is a cation occupying the face-centre sites of the unit cell, B is an anion that occupies the corner sites of the unit cell, and A is an anion that occupies the body-centre site of the unit cell. Element A is usually Nitrogen (N) or Carbon (C), which are referred to herein as antiperovskite nitrides or carbides, respectively. FIG. 2 illustrates the ideal cubic unit cell (in the absence of strain) of a Cu-based metallic antiperovskite, in this case Cu.sub.3PdN. Other widely studied compositions include Mn.sub.3GaN which is magnetic.

[0074] The fundamental insight of the present invention is to engineer the occupancy of corner sites or centre sites of the antiperovskite crystal lattice in a thin isostructural interfacial layer at one or both electrode-barrier interfaces to tune the population of the electronic band structure and achieve high sensitivity of the interfacial layer to the electric field produced by the ferroelectric barrier layer. The lattice structure does not change through the interfacial and electrode sublayers, but the occupancy of corner sites or centre sites can change layer by layer at the electrode-barrier interface. This gives an extra degree of freedom for engineering the TER beyond the selection of the bulk electrode materials themselves. As such, the interfacial layer forms an additional electrode layer or sublayer which enhances the electronic properties of the overall electrode. In this context, the occupancy of the corner or face centre sites or body centre sites refers to the proportion or fraction of respective lattice sites averaged over the layer that are occupied by a given element (e.g. ranging from 0 to 100%, or from 0 to 1 in the context of a compositional parameter), and/or the specific element occupying the respective lattice site. Where the body centre site element A is Nitrogen or Carbon, the material has a Nitrogen or Carbon deficiency if the occupancy of the body centre site is less than 1 or less than 100%.

[0075] Changing the composition or occupation of corner/centre sites of the whole electrode can change the bulk lattice parameter and the overall band structure, which may be not desirable in certain cases. However, when this is done in a sufficiently thin interfacial layer, as in the present invention, the occupation of the band structure and the electronics states at the electrode-barrier interface available for tunnelling can be tuned independently from the properties of the bulk electrode and without changing the lattice parameter or the band structure in the interfacial layer (because the lattice parameter and band structure in the thin interfacial layer follows that in the bulk electrode layer).

[0076] In contrast to doping (e.g. in materials such as semiconductors) which involves substituting elements in the lattice with impurities at relatively low concentrations compared to that of the bulk lattice elements, the approach of the present invention is based on removing elements from the lattice, whereby the concentration of corner/centre site elements in the interfacial layer is very high and can change layer-by-layer.

[0077] FIG. 3 shows a schematic diagram of a ferroelectric tunnel junction device 100 (FTJ) according to an embodiment of the invention. The device 100 comprises a ferroelectric tunnel barrier layer 110 sandwiched between a first electrode layer 210 and a second electrode layer 220. The device 100 further comprises a thin first interfacial layer 212 at the interface h1 between the first electrode layer 210 and the barrier layer 110. The first electrode layer 210 comprises a first antiperovskite material and the first interfacial layer 212 comprises a second antiperovskite material that differs from the first antiperovskite material in at least the occupancy of corner sites or the centre sites to tune the electronic states at the electrode-barrier interface, as described above.

[0078] The first antiperovskite material and the second antiperovskite material are metallic (i.e. no band gap) and share the same lattice structure and space group, permitting high quality interfaces. The first electrode layer 210 and the first interfacial layer 212 form isostructural electrode sublayers of the device 100. The first electrode layer 210 is substantially thicker than the first interfacial layer 212 and can be considered a bulk electrode layer.

[0079] The first interfacial layer 212 has a thickness of at least one monolayer of the unit cell and less than 25 unit cells (the lattice parameter is approximately 0.4 nm). In practice, the first interfacial layer 212 will have a thickness of 10 nm or less, or less than 5 nm, preferably less than 2 nm or 1 nm.

[0080] FIG. 4 shows a schematic diagram illustrating the variation in the corner or centre site occupancy. Each individual site in the lattice can either be occupied by an element (occupancy of 1) or not occupied by an element (occupancy of 0). It will be appreciated that the occupancy or composition of the first electrode layer 210, the first interfacial layer 212 described herein refers to an average value over the respective layer volume which can vary (almost continuously) from 0 to 1 depending on the growth/deposition conditions, as is known in the art. The first interfacial layer 212 can have a substantially uniform occupancy of corner or centre sites in a direction perpendicular to the interface h1 with an abrupt change heterointerface as indicated by the bold line in FIG. 4, or a graded occupancy of corner or centre site atoms in the direction perpendicular to the interface which may be substantially smooth as indicated schematically by the dashed and dotted lines. In practice, because the first interfacial layer 212 is only a few monolayers thick, the variation in occupancy may be stepped, whereby the occupancy changes layer by layer (rather than a smooth transition), e.g. which is achievable by atomic layer deposition (ALD).

[0081] The ferroelectric barrier layer 110 preferably comprises a ferroelectric perovskite material, such as BaTiO.sub.3 (BTO). The use of a perovskite ferroelectric barrier layer 110 in combination with the antiperovskite materials of the first interfacial layer 212 and the first electrode layer 210 is particularly advantageous from a manufacturability and performance perspective, as the compatibility of the lattice structures and lattice parameters, sharing the same space group (space group 221 or space group 123 under strain), means they are substantially lattice matched and permits higher quality interfaces which in turn contributes to lower migration of oxygen anions from the barrier layer 110 into the first electrode layer 210 and thereby to higher endurance of the device 100. Preferably, the lattice mismatch between the layers 110, 212, 210 is less than 10% and preferably less than 1%.

[0082] Preferably, the ferroelectric barrier layer 110 has a thickness of at least 1 nm and less than 10 nm, more preferably less than 5 nm. In practice, there is a balance between the ferroelectric barrier layer 110 needing to be sufficiently thick to ensure good ferroelectric behaviour and TER (and thus stability of data), but not too thick so as to overly limit the tunnel current through the device 100 (making reading and writing more difficult).

[0083] The second electrode layer 220 can be a metal, such as Pt, or another (third) metallic antiperovskite material. The use of an antiperovskite material in combination with the perovskite ferroelectric barrier layer 110 has the same advantages described above in terms of device endurance. It also allows for some tuning of the TER through its composition or occupancy of corner/centre sites. On the other hand, Pt is widely used in FTJs and CMOS processes and has a cubic lattice structure compatible with the perovskite barrier layer 110. The main requirement in this embodiment is that the second electrode layer 220 is a different material to the first interfacial layer 212, such that there is a different change in the electronic states available for tunnelling transport at the two electrode-barrier interfaces h1, h2.

[0084] The first interfacial layer 212 and first electrode layer 210 can be antiperovskite nitrides or carbides.

[0085] The choice of which site occupancy (i.e. corner, body centre, or face centre sites) to vary will depend on the parent compound. All three types of substitution can in principle tune the occupation of electronic states at Fermi level. The invention covers all three types of substitutions, and the below embodiments focus on substitutions that have been shown by the inventors or others to provide thermodynamically stable materials.

[0086] In a first example embodiment, the first interfacial layer 212 and first electrode layer 210 are comprised of Cu-based antiperovskite nitrides. In this case, the first electrode layer 210 is comprised of an antiperovskite nitride material of the form Cu.sub.3A.sub.1xN.sub.1u, and the first interfacial layer 212 is comprised of an antiperovskite nitride material of the form Cu.sub.3B.sub.1yN.sub.1w, wherein A and B are a corner site element selected from a group comprising: Pd, Ru, Cu, Rh, Ag, Al, Au, Co, Cu, Fe, Ga, Ge, In, Ir, Mn, Ni, Pt, Sb, Si, Sn, and Zn, and where 0x1, 0y1, 0u<1, 0w<1. Preferably, A and B are the same element in which case xy.

[0087] Further, in a specific example, the first electrode layer 210 is comprised of Cu.sub.3PdN and the first interfacial layer 212 is comprised of Cu.sub.3N. With reference again to FIG. 2, in this case the corner sites in the first interfacial layer 212 are not occupied, whereas the corner sites in the first electrode layer 210 are occupied with Pd. Cu.sub.3PdN is a thermodynamically stable non-magnetic metallic antiperovskite nitride whose band structure and conductance can be varied through the Pd concentration during deposition. In particular, Cu.sub.3N in bulk form (e.g. for thicknesses greater than 50 nm) is a semiconductor with a small band gap, but metallic in thin film form, as in the present case.

[0088] In a second example embodiment, the first electrode layer 210 is comprised of Mn-based antiperovskite nitride, and the first interfacial layer 212 can be comprised of a Cu-based antiperovskite nitride or a Mn-based antiperovskite nitride. In this case, the first electrode layer 210 is comprised of an antiperovskite nitride material of the form Mn.sub.3+xD.sub.1xN.sub.1u, and the first interfacial layer 212 is comprised of an antiperovskite nitride material of the form Mn.sub.3+yE.sub.1yN.sub.1w or CusA.sub.1zN.sub.1w, wherein D and E are a corner site element selected from a group comprising: Ag, Al, Au, Co, Cu, Fe, Ga, Ge, In, Ir, Ni, Pd, Pt, Rh, Sb, Si, Sn, and Zn, where A is a corner site element selected from a group comprising: Pd, Ru, Cu, Rh, Ag, Al, Au, Co, Cu, Fe, Ga, Ge, In, Ir, Mn, Ni, Pt, Sb, Si, Sn, and Zn, and where 0x1, 0y1, 0z1, 0u<1, 0w<1. Wherein D and E are the same element, xy.

[0089] Further, in a specific example, the first electrode layer 210 is comprised of Mn.sub.3GaN and the first interfacial layer 212 is comprised of Cu.sub.3N.

[0090] In a third example embodiment, the first electrode layer 210 is comprised of an antiperovskite nitride material of the form M.sub.3XN.sub.1x, and the first interfacial layer 212 is comprised of an antiperovskite nitride of the form M.sub.3ZN.sub.1y, wherein M is a face-centre site element selected from a group comprising: Fe, Mn, Cu, and Ni, and X, Z is a corner site element selected from a group comprising: Sb, Pd, Rh, Ir, Ga, Ge, In, Mn, Pt, and Sn, and where 0x<1, 0y<1. Where X and Z are the same element, xy.

[0091] As such, whereas in the first example embodiment and the second example embodiment the occupancy of the corner site is varied, in the third example embodiment the occupancy of the centre site can be varied by introducing a nitrogen deficiency.

[0092] In a fourth example embodiment, the first electrode layer 210 is comprised of an antiperovskite carbide of the form M.sub.3XC.sub.1x, and the first interfacial layer 212 is comprised of an antiperovskite carbide of the form M.sub.3ZC.sub.1y, wherein M is a face-centre site element selected from a group comprising: Co, Fe and Ni, and X, Z is a corner site element selected from a group comprising: Al, Ta, Ti, Ga, In, Mn, and Sn, and where 0x<1, 0y<1. Where X and Z are the same element, xy. Similar to above, in this example the occupancy of the centre site can be varied via by introducing a carbon deficiency.

[0093] FIG. 5 shows a schematic diagram of a ferroelectric tunnel junction device 100 (FTJ) according to another embodiment of the invention. In addition to the features of the device 100 described above, the device 100 comprises a second interfacial layer 222 at the interface h2 between the second electrode layer 220 and the ferroelectric barrier layer 110. The second electrode layer 220 is comprised of a third antiperovskite material and the second interfacial layer 222 is comprised of a fourth antiperovskite material that differs from the third antiperovskite material in at least the occupancy of corner sites or the centre sites.

[0094] This embodiment provides additional control over the asymmetry of the electronic properties of the electrode-barrier interfaces h1, h2. It further provides an all-perovskite structure which, as described above, has advantages in terms of device interface quality, reproducibility and endurance.

[0095] The second antiperovskite material and the fourth antiperovskite material of the first interfacial layer 212 and the second interfacial layer 222 are different, such that there is a different change in the electronic states or density of states available for tunnelling transport at the two electrode-barrier interfaces h1, h2.

[0096] As with the embodiments described above, the third antiperovskite material and the fourth antiperovskite material are metallic and share the same lattice structure. Preferably, where a perovskite ferroelectric barrier layer 110 is used, all the layers of the device share the same space group with low lattice mismatch. Preferably, the lattice mismatch between the layers in the device 100 is less than 10% and more preferably less than 1%. The second electrode layer 220 and the second interfacial layer 222 form isostructural electrode sublayers of the device 100. The second electrode layer 220 is substantially thicker than the second interfacial layer 222 and can be considered a bulk electrode layer. The second interfacial layer 222 has a thickness of at least one monolayer of the unit cell and less than 10 unit cells (preferably, less than 5 nm, more preferably less than 2 nm or 1 nm).

[0097] In example embodiments, the second interfacial layer 222 and second electrode layer 220 can be antiperovskite nitrides or carbides.

[0098] In a first example embodiment, the second interfacial layer 222 and second electrode layer 210 are comprised of Cu-based antiperovskite nitrides. In this case, the second electrode layer 210 is comprised of an antiperovskite nitride material of the form Cu.sub.3A1xN.sub.1u, and the second interfacial layer 222 is comprised of an antiperovskite nitride material of the form Cu.sub.3B.sub.1yN.sub.1w, wherein A and B are a corner site element selected from a group comprising: Pd, Ru, Cu, Rh, Ag, Al, Au, Co, Cu, Fe, Ga, Ge, In, Ir, Mn, Ni, Pt, Sb, Si, Sn, and Zn, and where 0x1, 0y1, 0u<1, 0w<1. Preferably, A and B are the same element in which case xy.

[0099] In a second example embodiment, the second electrode layer 220 is comprised of Mn-based antiperovskite nitride, and the second interfacial layer 222 can be comprised of a Cu-based antiperovskite nitride or a Mn-based antiperovskite nitride. In this case, the second electrode layer 220 is comprised of an antiperovskite nitride material of the form Mn.sub.3+xD.sub.1xN.sub.1u, and the second interfacial layer 222 is comprised of an antiperovskite nitride material of the form Mn.sub.3+yE.sub.1yN.sub.1w or Cu.sub.3A.sub.1zN.sub.1w, wherein D and E are a corner site element selected from a group comprising: Ag, Al, Au, Co, Cu, Fe, Ga, Ge, In, Ir, Ni, Pd, Pt, Rh, Sb, Si, Sn, and Zn, where A is a corner site element selected from a group comprising: Pd, Ru, Cu, Rh, Ag, Al, Au, Co, Cu, Fe, Ga, Ge, In, Ir, Mn, Ni, Pt, Sb, Si, Sn, and Zn, and where 0x1, 0y1, 0z1, 0u<1, 0w<1. Wherein D and E are the same element, xy.

[0100] In a third example embodiment, the second electrode layer 220 is comprised of an antiperovskite nitride material of the form M.sub.3XN.sub.1x, and the second interfacial layer 222 is comprised of an antiperovskite nitride of the form M.sub.3ZN.sub.1y, wherein M is a face-centre site element selected from a group comprising: Fe, Mn, Cu, and Ni, and X,Z is a corner site element selected from a group comprising: Sb, Pd, Rh, Ir, Ga, Ge, In, Mn, Pt, and Sn, and where 0<x<1, 0<y<1. Where X and Z are the same element, x y. In this example, the occupancy of the centre site can be varied via by introducing a nitrogen deficiency.

[0101] In a fourth example embodiment, the second electrode layer 220 is comprised of an antiperovskite carbide of the form M.sub.3XC.sub.1x, and the second interfacial layer 222 is comprised of an antiperovskite carbide of the form M.sub.3ZC.sub.1y, wherein M is a face-centre site element selected from a group comprising: Co, Fe and Ni, and X,Z is a corner site element selected from a group comprising: Al, Ta, Ti, Ga, In, Mn, and Sn, and where 0x<1, 0y<1. Where X and Z are the same element, xy. Similar to above, in this example, the occupancy of the centre site can be varied via by introducing a carbon deficiency.

[0102] To illustrate the effect of the first interfacial layer 212 on the TER, simulations were performed of the example structure in FIG. 6 in which the second electrode layer 220 is comprised of Pt, the ferroelectric barrier layer 110 is comprised of BTO, the first interfacial layer 212 is comprised of two monolayers of Cu.sub.3N, and the first electrode layer 210 is comprised of Cu.sub.3PdN. The thickness of the BTO was 4.2 nm (10 unit cells) and the first interfacial layer 212 was two monolayers. In the simulation, the first interfacial layer 212 was terminated by a CuCuN layer at the interface h1 with the BTO barrier layer 110.

[0103] Simulations were performed using atomic-scale modeling tools from the QuantumATK package developed by Synopsys, in particular, Density Functional Theory (DFT) simulations with localized basis sets (LCAO-linear combination of atomic orbitals) were performed using the LDA exchange correlation potential and FHI-DZP basis set for calculation of the electronic structure. Transport properties were calculated using the formalism of non-equilibrium Green's functions (NEGF). These simulation techniques are described e.g. by Z. Dong et al. in Tunneling current in HfO.sub.2 and Hf.sub.0.5Zr.sub.0.5O.sub.2 based ferroelectric tunnel junction, Journal of Applied Physics, Vol. 123, pp. 094501-094501 (2018), and by B. Nikolic et al. in First-principles quantum transport modeling of spin-transfer and spin-orbit torques in magnetic multilayers. Handbook of Materials Modeling: Applications: Current and Emerging Materials (2020): 499-533.

[0104] FIG. 7 shows the projected density of states of the CuCuN layer of the Cu.sub.3N interfacial layer 212 which is in contact with the BTO barrier layer 110 as a function of energy for both polarisation states of the barrier layer 110. The dashed line shows the result for P.sub.L pointing towards to the Pt electrode layer 220 and the solid line shows the result (mirrored about the energy axis for clarity) for P.sub.R pointing towards to the CusN interfacial layer 212. It can be seen from the region labelled A, that there is a significant difference in the density of states at and near the Fermi energy (EEF=0) where electronic transport takes place, which is indicative of a large TER.

[0105] FIG. 8 shows the calculated transmission T across the BTO barrier layer 110 as a function of energy for both polarisation states of the barrier layer 110 (T.sub.L for P.sub.L and T.sub.R for P.sub.R). Similarly, there is significant difference in transmission at and near the Fermi energy (EEF=0) indicative of a large TER.

[0106] FIG. 9 shows the calculated TER for the structure as a function of energy, which is calculated as TER=(T.sub.RT.sub.L)/T.sub.L. The calculated TER at the Fermi energy is approximately 110.sup.5%. This is significantly greater than the corresponding calculated TER of approximately 3000% for the same structure without the first interfacial layer 212. The simulation results thus demonstrate the advantages of incorporating an interfacial layer 212 at the electrode-barrier interface h1.

[0107] The invention thus provides an easily implementable new solution and an extra degree of freedom for engineering the transmission across the ferroelectric tunnel barrier layer 110, in addition to the selection of specific bulk electrode materials.

[0108] The multiple layers of the device 100 of the present invention can be manufactured using any suitable thin film deposition method, optimised for the required layers, thicknesses and materials. For example, atomic layer deposition (ALD), pulsed laser deposition (PLD), physical vapour deposition or magnetron sputtering (PVD), or a combination of different techniques can be used. In order to obtain a thin layer with the designed or varied composition/occupancy one can employ various methods. The most common approach is to co-sputter the elements from two targets (PVD) and control the power on one target while keeping other constant. In the case of Cu.sub.3PdN the power on the Pd target is varied. Another approach is to grow a thin Cu.sub.3N layer at the interface h1 with the barrier layer 110, e.g. usually under 1 monolayer, and then continue with a stoichiometric Cu.sub.3PdN growth. To achieve atomically sharp and well-defined interfaces, it is necessary to control the temperature of the substrate to reduce the mobility of the adatoms so that the desired heterointerface is achieved. In one example, suitable temperatures for deposition of stoichiometric Cu.sub.3PdN are in the range between 100-400 C., and should preferably be kept on the lower side to achieve a gradient at the interface with the barrier layer 110. In addition, the desired interface for a given material combination can be produced using PVD techniques through an iterative and empirical process of controlling the deposition conditions such as the interface that is presented to adatoms, substrate orientation, substrate temperature, pressure, and power, as is known in the art. Desired interfaces can also be produced using atomically controlled deposition techniques such as ALD.

[0109] By way of reference only, examples of the preparation of various perovskite and antiperovskite materials is provided below. Synthesis and engineering of antiperovskite/perovskite heterostructures is described, e.g. by C. Quintela et al. in Epitaxial antiperovskite/perovskite heterostructures for materials design Science Advances 6, 30 (2020). An example of the preparation of Mn.sub.3GaN layers is described, e.g. by T Hajiri et al. in Electrical current switching of the non-collinear antiferromagnet Mn.sub.3GaN Applied Physical Letters 115, 05203 (2019). An example of the preparation of Mn.sub.4N layers is described, e.g. by K. Ito et al. in Perpendicular magnetic anisotropy in Co.sub.xMn.sub.4xN (x=0 and 0.2) epitaxial films and possibly of tetragonal Mn.sub.4N phase AIP Advances 6, 056201 (2016), and by J. Zeman in Collinear and noncollinear ferrimagnetic phases in Mn.sub.4N investigated by magneto-optical Kerr spectroscopy Journal of Applied Physics 134, 203902 (2023). An example of the preparation of Cu.sub.3PdN and Cu.sub.3N layers is described, e.g. by C. X. Quintela et al. in Epitaxial thin films of Dirac semimetal antiperovskite Cu.sub.3PdN APL Materials 5, 096103 (2017), and by A. Jiang et al. in Preparation, structure, properties and application of copper nitride (Cu.sub.3N) thin films: A Review Journal of Materials Science and Technology 34, 1467 (2018). An example of the preparation of SrTiO.sub.3 and BaTiO.sub.3 layers is described, e.g. by M. Vehkamaki et al. in Growth of SrTiO.sub.3 and BaTiO.sub.3 Thin Films by Atomic Layer Deposition Electrochemical and Solid State Letters 2, 504 (1999), and in I Marozau et al. in One-step preparation of N-doped strontium titanate films by pulsed laser deposition Applied Physics A 89, 933 (2007).

[0110] It will be understood that the present invention has been described above purely by way of example, and modifications of detail can be made within the scope of the invention. Each feature disclosed in the description, and (where appropriate) the claims and drawings may be provided independently or in any appropriate combination.

[0111] Although the appended claims are directed to particular combinations of features, it should be understood that the scope of the disclosure of the present invention also includes any novel feature or any novel combination of features disclosed herein either explicitly or implicitly or any generalisation thereof, whether or not it relates to the same invention as presently claimed in any claim and whether or not it mitigates any or all of the same technical problems as does the present invention. Reference numerals appearing in the claims are by way of illustration only and shall have no limiting effect on the scope of the claims.