PHOTOVOLTAIC DEVICE

Abstract

A photovoltaic diode comprising an emitter layer of doped Group III-V semiconductor material, having a first conductivity type and a first bandgap in at least part of the layer, an intrinsic layer of dilute nitride Group III-V semiconductor material having a composition given by the formula Ga.sub.1-zIn.sub.zN.sub.xAs.sub.ySb.sub.1-x-y, where 0<z<0.20, 0.01<x<0.05, and y>0.80 having a second bandgap, a base layer of semiconductor material having a third bandgap and a second conductivity type opposite to the first conductivity type. The emitter, intrinsic and base layers form a diode junction. The first bandgap is greater than the second bandgap.

Claims

1. A photovoltaic diode, comprising: an emitter layer of doped Group III-V semiconductor material, having a first conductivity type and a first bandgap in at least part of the emitter layer; an intrinsic layer of dilute nitride Group III-V semiconductor material having a composition given by a formula Ga.sub.1-zIn.sub.zN.sub.xAs.sub.ySb.sub.1-x-y, where 0<z<0.20, 0.01<x<0.05, and y>0.80 having a second bandgap; and a base layer of semiconductor material having a third bandgap and a second conductivity type opposite to the first conductivity type, wherein the emitter layer, intrinsic layer, and base layer form a diode junction, and wherein the first bandgap is greater than the second bandgap.

2. The photovoltaic diode of claim 1, wherein the base layer is a layer of dilute nitride Group III-V semiconductor material having a composition given by the formula Ga.sub.1-zIn.sub.zN.sub.xAs.sub.ySb.sub.1-x-y, where 0<z<0.20, 0.01<x<0.05, and y>0.80.

3. The photovoltaic diode of claim 1 wherein: the emitter layer comprises a wide bandgap emitter layer of Group III-V semiconductor material having the first bandgap and a narrow bandgap emitter layer between the wide bandgap emitter layer and the intrinsic layer, the narrow bandgap emitter layer having the first conductivity type and being of a dilute nitride Group III-V semiconductor material having composition given by the formula Ga.sub.1-zIn.sub.zN.sub.xAs.sub.ySb.sub.1-x-y, where 0<z<0.20, 0.01<x<0.05, and y>0.80, and the narrow bandgap emitter layer has a fourth bandgap that is smaller than the first bandgap.

4. The photovoltaic diode of claim 3, wherein the fourth bandgap is the same as the second bandgap.

5. The photovoltaic diode of claim 3, wherein the fourth bandgap is between the first and second bandgaps.

6. The photovoltaic diode of claim 3, wherein the narrow bandgap emitter layer is lattice matched to the wide bandgap emitter layer.

7. The photovoltaic diode of claim 3, wherein the narrow bandgap emitter layer is lattice matched to the intrinsic layer.

8. The photovoltaic diode of claim 3, wherein the narrow bandgap emitter layer is less in thickness than a diffusion length of a minority carrier.

9. The photovoltaic diode of claim 3, wherein the narrow bandgap emitter layer is less in thickness than 200 nm.

10. The photovoltaic diode of claim 9, wherein the narrow bandgap emitter layer is 100 nm in thickness.

11. The photovoltaic diode of claim 1, wherein the emitter layer comprises a graded dilute nitride Group III-V semiconductor material layer having a composition and bandgap graded through a thickness of the graded layer, the composition through the graded layer being within the formula Ga.sub.1-zIn.sub.zN.sub.xAs.sub.ySb.sub.1-x-y, where 0<z<0.20, 0.01<x<0.05, and y>0.80.

12. The photovoltaic diode of claim 1, wherein the emitter layer comprises a graded aluminium gallium arsenide semiconductor material layer having a composition and bandgap graded through a thickness of the graded layer.

13. The photovoltaic diode of claim 11, wherein the bandgap of the graded layer of the emitter layer has an interface with the intrinsic layer and at that interface has a bandgap equal to that of the intrinsic layer at that interface.

14. The photovoltaic diode of claim 11, wherein the bandgap of the graded layer of the emitter layer has an interface with the intrinsic layer and at that interface has a same composition to that of the intrinsic layer at that interface.

15. The photovoltaic diode of claim 11, wherein the graded layer of the emitter layer has an interface with or continues in a further compositional grade with a layer of gallium arsenide or aluminium gallium arsenide.

16. The photovoltaic diode of claim 1, wherein the intrinsic layer and base layer have the same composition of semiconductor material.

17. The photovoltaic diode of claim 1, wherein the intrinsic layer and base layer have the same band gap as each other.

18. The photovoltaic diode of claim 1, wherein the base layer comprises a graded dilute nitride Group III-V semiconductor material layer having a composition and bandgap graded through a thickness of the graded layer, the composition through the graded layer being within the formula Ga.sub.1-zIn.sub.zN.sub.xAs.sub.ySb.sub.1-x-y, where 0<z<0.20, 0.01<x<0.05, and y>0.80.

19. The photovoltaic diode of claim 18 wherein the bandgap of the graded layer of the base layer has an interface with the intrinsic layer and at that interface has a bandgap equal to that of the intrinsic layer at that interface.

20. The photovoltaic diode of claim 18, wherein the bandgap of the graded layer of the base layer has an interface with the intrinsic layer and at that interface has a same composition to that of the intrinsic layer at that interface.

21. The photovoltaic diode of claim 1, wherein the emitter layer comprises a layer of gallium arsenide.

22. The photovoltaic diode of claim 1, wherein the emitter layer comprises a layer of aluminium gallium arsenide.

23. The photovoltaic diode of claim 1, wherein the intrinsic layer has a bandgap in a range 0.7 to 1.4 eV.

24. The photovoltaic diode of claim 1, wherein the base layer has a bandgap in a range 0.7 to 1.0 eV.

25. The photovoltaic diode of claim 1, wherein the emitter layer, intrinsic layer, and base layer are lattice matched to each other.

26. A solar cell, comprising: a photovoltaic diode comprising: an emitter layer of doped Group III-V semiconductor material, having a first conductivity type and a first bandgap in at least part of the emitter layer; an intrinsic layer of dilute nitride Group III-V semiconductor material having a composition given by a formula Ga.sub.1-zIn.sub.zN.sub.xAs.sub.ySb.sub.1-x-y, where 0<z<0.20, 0.01<x<0.05, and y>0.80 having a second bandgap; and a base layer of semiconductor material having a third bandgap and a second conductivity type opposite to the first conductivity type, wherein the emitter layer, intrinsic layer, and base layer form a diode junction, and wherein the first bandgap is greater than the second bandgap.

27. A multijunction photovoltaic device, comprising a photovoltaic diode comprising: an emitter layer of doped Group III-V semiconductor material, having a first conductivity type and a first bandgap in at least part of the emitter layer; an intrinsic layer of dilute nitride Group III-V semiconductor material having a composition given by a formula Ga.sub.1-zIn.sub.zN.sub.xAs.sub.ySb.sub.1-x-y, where 0<z<0.20, 0.01<x<0.05, and y>0.80 having a second bandgap; and a base layer of semiconductor material having a third bandgap and a second conductivity type opposite to the first conductivity type, wherein the emitter layer, intrinsic layer, and base layer form a diode junction, and wherein the first bandgap is greater than the second bandgap.

28. A multijunction photovoltaic device, comprising a first photovoltaic diode, comprising: a first diode junction comprising a first photovoltaic diode, comprising: a first emitter layer of doped Group III-V semiconductor material, having a first conductivity type and a first bandgap in at least part of the first emitter layer; a first intrinsic layer of dilute nitride Group III-V semiconductor material having a composition given by a formula Ga.sub.1-zIn.sub.zN.sub.xAs.sub.ySb.sub.1-x-y, where 0<z<0.20, 0.01<x<0.05, and y>0.80 having a second bandgap; and a first base layer of semiconductor material having a third bandgap and a second conductivity type opposite to the first conductivity type, wherein the first bandgap is greater than the second bandgap; a second diode junction comprising a second photovoltaic diode, comprising: a second emitter layer of doped Group III-V semiconductor material, having a third conductivity type and a fourth bandgap in at least part of the second emitter layer; a second intrinsic layer of dilute nitride Group III-V semiconductor material having a composition given by the formula Ga.sub.1-zIn.sub.zN.sub.xAs.sub.ySb.sub.1-x-y, where 0<z<0.20, 0.01<x<0.05, and y>0.80 having a fifth bandgap; and a second base layer of semiconductor material having a sixth bandgap and a fourth conductivity type opposite to the third conductivity type, wherein the fourth bandgap is greater than the fifth bandgap, wherein the third bandgap of the first base layer of the first photovoltaic diode is different than the sixth bandgap of the second base layer of the second photovoltaic diode.

29. A method of generating electricity using a photovoltaic diode, wherein: the photovoltaic diode comprises: an emitter layer of doped Group III-V semiconductor material, having a first conductivity type and a first bandgap in at least part of the emitter layer; an intrinsic layer of dilute nitride Group III-V semiconductor material having a composition given by a formula Ga1-zInzNxAsySb1-x-y, where 0<z<0.20, 0.01<x<0.05, and y>0.80 having a second bandgap; a base layer of semiconductor material having a third bandgap and a second conductivity type opposite to the first conductivity type, wherein the emitter layer, intrinsic layer, and base layer form a diode junction, and wherein the first bandgap is greater than the second bandgap; the method comprising: directing light into the photovoltaic diode through the emitter layer in the direction of the intrinsic layer and base layer; absorbing the light in the intrinsic layer to generate photo carriers; and separating photo-carriers using the photovoltaic diode to generate electricity.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Embodiments will now be described, with reference to the accompanying drawings, of which:

[0024] FIG. 1 shows the layers and band diagram of a known n-i-p photovoltaic diode;

[0025] FIG. 2 shows the layers and band diagram of the junction of an exemplary heterostructure n-i-p photovoltaic diode;

[0026] FIG. 3 shows the layers and band diagram of the junction of another example of a heterostructure n-i-p photovoltaic diode;

[0027] FIG. 4 shows the layers and band diagram of the junction of an exemplary graded heterostructure n-i-p photovoltaic diode; and

[0028] FIG. 5 is a cross-section of a multi-junction photovoltaic device.

DETAILED DESCRIPTION

[0029] FIG. 2 shows the layers and a band diagram of a first example of a heterostructure n-i-p photovoltaic diode in accordance with the invention. This may form, for example, a sub-cell of a multi-junction photovoltaic device. In this diode 200, there are three layers 201, 202 and 203 forming the diode junction. The top, emitter layer 201 of the junction is an n-type layer of, in this example, GaAs (although alternatively AlGaAs may be used). The middle, intrinsic layer 202 and base layer 203 are both of a dilute nitride GaInNAsSb material. The base layer 203 is a p-type layer and the intrinsic layer 202 is undoped, or is significantly less actively doped than layers 201 and 203. The materials of all three layers are lattice matched, i.e. have the same lattice parameter or are close enough in lattice parameter not to cause dislocations to form (or not to plastically relax as this is sometimes known) when the materials are grown epitaxially. As is known, lattice matching with slightly differing lattice parameters can be achieved in both thick layers and in thin layers; for the latter the difference in lattice parameter can be greater as long as the critical thickness of the layer is not exceeded. The base layer and intrinsic layers preferably have the same bandgap.

[0030] The layers may be grown in turn epitaxially on a lattice matched substrate. This may be in the order base layer 203, then intrinsic layer 202, then emitter layer 201. However, as is known in the art, the layers could be grown on a substrate in the other direction, and then removed from that substrate and turned over before being mounted on another substrate.

[0031] A preferred range for the composition of dilute nitride GaInNAsSb layers are given by the formula Ga.sub.1-zIn.sub.zN.sub.xAs.sub.ySb.sub.1-x-y, where 0<z<0.20, 0.01<x<0.05, and y>0.80. The base layer 203 and the intrinsic layer preferably have the same composition, but may be of different compositions, which is also possible even in cases where they have the same band gap as well as being lattice matched to each other (given the number of different elements from which the material is formed).

[0032] Again, as is known in the art, the top layer 201 may be overlaid (i.e. to the left in the diagram) with other sub-cells (see FIG. 5 and the related description later below) and other layers of a solar cell, for example window and electrode layers. (The top layer is again meant in the sense of the layer of the junction which receives the incident light firstin FIG. 2 the light comes from the left).

[0033] As with the known example of FIG. 1, it is preferable that the active background doping concentration in the intrinsic layer 202 is sufficiently low to ensure the depletion width (again marked w in FIG. 2) is equal or greater than the absorption depth of photons in the semiconductor, i.e. that w>1/. A doping level of around 10.sup.15 cm.sup.3 is preferred in the example of FIG. 2; 10.sup.14 cm.sup.3 may be better still, although would be harder to achieve. The preferred doping levels for the emitter layer 201 and base layer 203 in the example of FIG. 2 are 510.sup.17 to 110.sup.19 cm.sup.3 and 510.sup.16 to 110.sup.18 cm.sup.3 respectively.

[0034] In the present example, i.e. that of FIG. 2, it is notable that the n-type emitter layer 201 has a bandgap greater than that of the intrinsic layer 202.

[0035] Now, with the known n-i-p homojunction described above with respect to FIG. 1, it was important that its n-type emitter layer 101 be kept thin, since in the absence of long range diffusive transport, carriers photo-generated in the n-type layer 101 would not be transported across the thickness of that layer without recombination. However, in this example, with the bandgap of the n-type emitter layer 201 being greater than that of the intrinsic layer 202, the n-type emitter layer 201 does not absorb a significant proportion of the photons that pass through it, so photo-carriers are not created, and the photons are instead absorbed in the intrinsic layer 202, which has a smaller bandgap. So one effect of the difference in bandgap is that it is no longer a requirement to keep the n-type layer thin; for example, thicknesses of over 100 nm may be used for the n-type emitter layer 201. In general, the fabrication and structure of many layered devices is usually beset by numerous and often competing requirements so the relaxation of this requirement in this device may have advantages when the device of FIG. 2 forms part of such a device. For example thicker layers often have better material properties, for example the bulk is not subject to diffusion of dopants from neighbouring layers.

[0036] Also, a useful advantage of having GaAs or AlGaAs for the material of the n-layer 201 is that those are compatible with having an overlying tunnel junction and barrier for minority carrier holes, which are typically be used between the sub-cells of a multijunction solar cell. In such one example of compatibility the next layer above the next later above 201 is formed of GaAs or AlGaAs.

[0037] It would also be possible to have a heterostructure p-i-n diode in accordance with the invention. An example would be similar to that of FIG. 2 with the emitter, intrinsic and base layers being respectively of the same materials as the those layers 201, 202 and 203 of n-i-p diode of FIG. 2, but with the emitter being doped p-type and the base layer being doped n-type, and indeed it functions in the same way. (i.e., in this example the conductivity types (n-type/p-type) of the emitter and base are opposite to those in the example of FIG. 2).

[0038] FIG. 3 shows the layers and a band diagram of a second example of a heterostructure n-i-p photovoltaic diode 300 in accordance with the invention. Again, this may form a sub-cell of a multi-junction photovoltaic device. The diode has an n-type emitter layer 301, and intrinsic layer 302 and a p-type base layer 303. These are generally of the same materials as the example of FIG. 2, but in this case the emitter layer 301 has two layers: a wide bandgap emitter layer 301a and a narrow bandgap emitter layer 301b, both of which are doped n-type. Layer 301b is between layers 301a and 302. As with the example of FIG. 2 in this example the wide bandgap emitter layer 301a is of GaAs, or AlGaAs, material. The narrow bandgap emitter layer 301b is of dilute nitride GaInNAsSb. It has a smaller bandgap than the wide bandgap emitter layer and preferably one that is equal to that of the intrinsic layer 302 (although alternatively it may have a bandgap between that of the main emitter layer 301a and the intrinsic layer 302). Preferably the narrow bandgap emitter layer 301b is lattice matched to the main emitter layer 301a and intrinsic layer 302.

[0039] The narrow bandgap emitter layer 301b, because it has a narrower bandgap than main emitter layer 301a absorbs photons passing on from the wide bandgap emitter layer that have an energy greater than the bandgap of the narrow bandgap gap emitter layer, to produce electron-hole pairs. Because the thickness c.sub.n (typically 10 nm) of the narrow bandgap emitter layer 301b is less than the absorption length for the photons, not all such photons are absorbed in the narrow bandgap emitter layer 301b and the remainder pass on to the intrinsic layer 302 where they are absorbed, as in the previous examples. Although the narrow bandgap emitter layer 301b is doped, its thickness in this example is equal to or thinner than the diffusion length of the photo carriers in the material of that layer, so quite quickly the electrons diffuse or drift into the wide bandgap emitter layer 301a and, importantly, the minority carrier holes diffuse into the depletion region (where they are transported by the electric field of the depletion region across the intrinsic region 302 to the base 303). The step in the valance band edge between the narrow bandgap emitter layer 301b to the wide bandgap emitter later 301a acts as a barrier to those holes diffusing into the wide bandgap emitter layer 301a, where of course they would recombine with the electrons. In this example then, the overall region that absorbs the photons is that of combined lengths c.sub.n and w (noting of course that c.sub.n and w overlap slightly). In practice this provides extra length for absorption, since as noted above, the practical length of w is limited by the background doping level of the intrinsic region that is achievable (which is the same as for the example of FIG. 2) and that length w is not very much longer than the absorption length of light in these materials, making the extra length c.sub.n significant.

[0040] FIG. 4 shows the layers and a band diagram of a third example of a heterostructure n-i-p photovoltaic diode 400 in accordance with the invention. Again, this may form a sub-cell of a multi-junction photovoltaic device. Again, the diode has an n-type emitter layer 401, and intrinsic layer 402 and a p-type base layer 403a/403b. However, in this example a grade 401, 403a in composition is provided in each of the emitter and/or base regions. A grade in doping may also be used, as is the case in this example.

[0041] In the example of FIG. 4 all the layers are of various compositions of GaInNAsSb. The composition of intrinsic layer is preferably as in the examples above, which gives the material a bandgap energy of 1.0 eV. The compositional grade 401 widens the bandgap with distance from the interface with the intrinsic later. As shown, there is preferably no step change in the bandgap at that interface. The bandgap preferably widens to equal that of the next later above, which for example may be of GaAs or AlGaAs. An alternative material for the emitter 401 is a compositional grade of AlGaAs.

[0042] Similarly the compositional grade 403a narrows the bandgap from its interface with the intrinsic later until it equals that of base layer 403b.

[0043] In this example, the grade layers also have grades in the dopant levels, increasing away from the respective interfaces with the intrinsic region. As there is active doping in these regions the depletion region terminates a short distance into each.

[0044] The compositional graded layers each further extend the collection length in the solar cell by inducing an electric field in the region of c.sub.n and c.sub.p, resulting in an active collection length of the combination of c.sub.n, w, and c.sub.p. (Note that there is a small overlap between w and c.sub.n, and between w and c.sub.p.) Conveniently, the compositional and doping grades 401 and 403a also provide an electric field to drift the minority carriers, leading to a higher photo-carrier collection efficiency.

[0045] The design constraints are that (1) that the thickness (c.sub.n & c.sub.p) of graded layers 401 and 403a should correspond to the combination of the graded semiconductor materials, doping grade and diffusion length of the doped semiconductor and (2) the intrinsic region 402 thickness t.sub.i is determined by the background impurity concentration level, to ensure that the intrinsic layer 402 remains depleted at the operating voltage.

[0046] The compositional grade of the base layer may also be used, for example, in the embodiments of FIGS. 2 and 3.

[0047] Note that in FIG. 2, the band diagram shows an ideal band alignment where a barrier is formed in the valance band but a barrier may also form in the conduction band, depending on the composition of the GaInAsSb material. In FIG. 3 some band-bending can be expected at the interface between 301a and 301b, with its spatial extent determined by the free carrier density in the n-type layer. In FIG. 4, the profile of the valance band can be controlled by simultaneously controlling the doping level and semiconductor composition. FIG. 4 shows the typical example with homogenous n-type doping in layer 401.

[0048] FIG. 5 shows an exemplary photovoltaic device 500 having several subcells. In this example there are four subcells connected in series (or tandem as this is often called for these devices). A first subcell 501 has an active light absorbing region of AlGaInP, which has a very wide bandgap and absorbs the incident light with energy >1.9 eV. A second subcell 502 has an active light absorbing region of Ga(In)As, which has a narrower bandgap than that of 501 and absorbs the incident light with energy from 1.4 eV to 1.9 eV passing through to that subcell from subcell 501. A third subcell 503 is a subcell according to the invention, for example, one of those described with reference to FIG. 2, 3 or 4, above. Here where the emitter 201/301a is also of GaAs it of course has the same bandgap as subcell 502. This means that light that would be absorbed by the GaAs emitter have already been absorbed by subcell 502 and 501. So no light is wasted by being absorbed in the emitter 201/301a. The fourth subcell 504 has an active light absorbing region of Ge which has the narrowest bandgap among all subcells and absorbs incident light with energy from 0.66 eV to 1.0 eV, which pass through to that subcell from subcell 503. An alternative for subcell 504 is having a second n-i-p diode as described above, but with a smaller bandgap in the intrinsic layer than for subcell 503.

[0049] The above devices may be fabricated by known techniques such as molecular beam epitaxy (MBE) or metal organic vapour phase epitaxy (MOVPE). The International patent application published as No. WO2009/157870 discloses a method of fabrication of the dilute nitride materials, and is incorporated herein by reference in its entirety.