AU2006258893B2

AU2006258893B2 - Carbon ribbon to be covered with a thin layer made of a semiconductor material and method for depositing a layer of this type

Info

Publication number: AU2006258893B2
Application number: AU2006258893A
Authority: AU
Inventors: Christian Belouet
Original assignee: Solarforce
Current assignee: Solarforce
Priority date: 2005-06-17
Filing date: 2006-06-07
Publication date: 2010-08-19
Anticipated expiration: 2026-06-07
Also published as: EP1897149A2; AU2006258893C1; EP1897149B1; WO2006134292A3; CN101199061A; JP5046163B2; ES2438018T3; JP2008544515A; CN100530703C; AU2006258893A1; FR2887262B1; WO2006134292A2; FR2887262A1

Description

1 A CARBON RIBBON FOR COVERING IN A THIN LAYER OF SEMICONDUCTOR MATERIAL, AND A METHOD OF DEPOSITING SUCH A LAYER The present invention relates to a carbon ribbon for 5 covering in a thin layer of semiconductor material, and to a method of depositing such a layer on a substrate constituted by a carbon ribbon. Photovoltaic cells comprise thin plates of semiconductor material, with the most commonly used 10 material presently being polycrystalline silicon. The invention applies most particularly to pulling silicon ribbons for use in fabricating photovoltaic cells, with the description below thus relating to silicon, it being understood that the invention applies equally to other 15 semiconductor materials such as germanium and type III-V semiconductor compounds of the GaAs family with congruent or quasi-congruent melting. The silicon plates are preferably obtained from a layer of silicon that forms a film deposited on a carbon substrate by pulling the 20 substrate through a bath of molten silicon. The substrate has the form of a ribbon. Figure 1 is a general diagram showing the prior art method referred to as the ribbon on temporary substrate (RTS) method. A crucible 10 fitted with heater means 25 (not shown) contains a bath 12 of molten silicon in liquid form. The bottom of the crucible has a slot 14. Using pulling means (not shown), a carbon ribbon 16 of small thickness (of the order of 200 micrometers (sm) to 350 pm) is pulled substantially vertically upwards in the 30 direction of arrow 18 through the silicon bath 12 at substantially constant speed. The two faces 20 and 22 of the ribbon are initially covered in a thin layer of pyrolytic carbon 24 (thickness about 1 pm to 5 sm). The molten silicon wets the two faces 20 and 22 of the 35 ribbon, and a meniscus 26 of liquid silicon forms on each face of the ribbon, with a solid-liquid connection line 28 that is situated at about 6.8 mm from the surface of 2 the bath in the central portion of the ribbon. A thin layer of silicon 30-32 then forms on each of the two faces 20 and 22 of the carbon ribbon. The shape and the dimensions of the slot 14 are adapted firstly to allow 5 the carbon ribbon 16 to penetrate into the crucible, and secondly to avoid molten silicon from flowing out through the slot. Although it is advantageous to obtain two silicon films 30 and 32 simultaneously, one film on each face of the ribbon, it is possible to use a technique in 10 which only one film is obtained by preventing silicon from becoming deposited on one of the two faces. The RTS method is described for example in patents FR 2 386 359 and FR 2 561 139. That pulling method is nevertheless confronted with 15 the problem of the liquid silicon meniscus being unstable in the proximity of each edge 34-36 of the carbon ribbon 16. It has been found that the solid-liquid connection line 28 tends to drop from typically about 6.8 mm to 2 mm to 4 mm relative to the surface of the silicon bath at 20 the edges of the ribbon, over a width of about 5 mm from each edge. As a result the thickness of the silicon layer 30 or 32 that is deposited on each face of the carbon ribbon decreases going towards the edges 34 and 36 down to a value of practically zero. 25 Figure 2 is a diagram showing the progressive thinning on the edges of the semiconductor layers obtained by the prior art method shown in Figure 1. The section of the carbon ribbon 16 shown in cross-section and without the layers 24 of pyrolytic carbon is 30 substantially rectangular in shape. The two semiconductor layers 30 and 32 are deposited simultaneously on the two faces 20 and 22 respectively of the ribbon. In the zones 38-40 and 42-44 adjacent to the two edges 34 and 36 respectively of the ribbon, the 35 thickness of the layers decreases progressively over a distance that is typically about 5 mm. Semiconductor films made in this way are therefore particularly fragile 3 at the edges. In addition, it is found that nucleation from grains of small dimensions propagates in the side portions of the film, thereby decreasing the photovoltaic performance of the silicon film. 5 Solutions to the above problem are proposed in patents FR 2 568 490 and FR 2 550 965. Those solutions consist in raising the level of the solid-liquid line at the edges of the carbon ribbon with the help of external means placed close to the edges of the ribbon. Thus, the 10 first above-mentioned patent makes use of plates that locally raise the level of the bath of molten silicon by capillarity, and the second above-mentioned patent proposes placing a trough in register with each edge of the silicon ribbon, likewise for locally raising the 15 level of the bath of molten silicon. Those solutions complicate fabricating the pulling structure and the pulling operation itself. The present invention provides a solution to the above problem that does not make use of external means. 20 It consists in adapting the shape of the edges of the carbon ribbon used as a temporary support for the semiconductor layers, so as to increase the thickness of the semiconductor layers that are deposited on said edges. 25 More precisely, the invention provides a method of depositing a layer of semiconductor material on at least one of the two faces of a carbon ribbon, said ribbon having two edges, in which method the ribbon is pulled progressively upwards, substantially vertically, 30 lengthwise through the horizontal equilibrium surface of a bath of molten semiconductor material, which becomes deposited by wetting said face as the carbon ribbon is pulled. The method is characterized in that it consists in changing the shape of the edges of the ribbon so as to 35 increase the thickness of the layer of semiconductor material that is deposited on the edges of the ribbon.

4 In a particular implementation, each of the edges of the ribbon is given a projecting shape, which shape may, for example, be flared, rectangular, or triangular. In a preferred implementation, a layer of 5 semiconductor material is deposited simultaneously on both faces of the ribbon, and each of the two edges of the ribbon is given a double rim shape. For example, the change in shape is obtained by forming, by continuously upsetting the edges of the 10 ribbon towards each other. When the semiconductor material is silicon, the carbon ribbon is advantageously covered in a layer of pyrolytic carbon on which the silicon layer is deposited. The invention also provides a carbon ribbon having 15 two edges, with at least one of its two faces being designed to be covered in a layer of semiconductor material by causing said ribbon to pass substantially vertically upwards through a bath of molten semiconductor material. According to the invention, each of its two 20 edges on at least one of its two faces projects to form a rim. In an embodiment, each of the two edges of the carbon ribbon flares so as to form a half-round shape, or a rounded shape depending on whether only one face of the 25 ribbon or both faces are considered. In another embodiment, each edge of the ribbon forms a shoulder that is substantially perpendicular to the face of the ribbon that is to receive the layer of semiconductor material, the rim then being rectangular. 30 In another embodiment, each edge of the ribbon forms a shoulder that slopes relative to the face of the ribbon that is to receive the layer of semiconductor material, the rim then being triangular. Both of the edges of the ribbon advantageously 35 include a respective external portion substantially perpendicular to the face of the ribbon that is to receive the layer of semiconductor material, said 5 external portion possibly including a portion that is set back into the ribbon or being in the form of a half-drop of tallow or in the form of a drop of tallow. In an embodiment, the semiconductor material is 5 deposited on both faces of the ribbon, each edge of the carbon ribbon then forming a double rim. The semiconductor material is selected from silicon, germanium, and type III-V semiconductor compounds of the GaAs family with congruent or quasi-congruent melting. 10 Other characteristics and advantages of the invention appear from the following description given purely by way of example and made with reference to the accompanying drawings, in which: - Figure 1 is a diagram showing the prior art method 15 for obtaining one or two semiconductor films by pulling a carbon ribbon through a bath of molten semiconductor; - Figure 2 shows the thinning of the semiconductor layers obtained by the conventional, prior art method; and 20 Figures 3a, 3b, 3c, and 3d are diagrams in section showing shapes obtained for the edge of a carbon ribbon in accordance with the invention. In the invention, the edges of the carbon ribbon are of a shape that is modified so as to modify the shape of 25 the wetting surface of the molten semiconductor material on the two edges of the ribbon, for the purpose of increasing the thickness of the layer of semiconductor material deposited on the edges of the ribbon. Figures 3a, 3b, 3c, and 3d are diagrammatic cross 30 sections showing a plurality of embodiments of the carbon ribbon in accordance with the present invention. To simplify writing and reading the text below, when a reference, e.g. R, relates to the embodiments of Figures 3a, 3b, 3c, and 3d, then it is written Ra,b,c,d 35 instead of Ra, Rb, Rc, Rd. If the reference R applies for example only to the embodiments of Figures 3b, 3c, and 3d, then it is written 3b,c,d.

6 In the figures, the ribbon is shown coated in two layers of semiconductor, each of them forming a semiconductor film after the carbon ribbon has been eliminated. The midplane 50a,b,c,d passing through the 5 middle of the ribbon and perpendicularly to the two faces of the ribbon constitutes a plane of symmetry. Thus, in these Figures 3, only the left-hand end of the ribbon is shown, the right-hand end being identical to the left hand end and symmetrical about said midplane 50a,b,c,d. 10 In Figures 3a to 3d, the carbon ribbons are identical except for the shape of the edges of the ribbons. Ignoring the edges, the cross-sections 52a,b,c,d of the carbon ribbons 54a,b,c,d are generally rectangular in shape possessing a longitudinal axis of 15 symmetry 56a, 56b, 56c, or 56d parallel to the two faces of the ribbon respectively 58a-60a, 58b-60b, 58c-60c, and 58d-60d. The two edges of each of the two faces of the ribbons are terminated in projecting manner so as to form a rim. The projecting shape serves to increase the 20 thickness of the layer of semiconductor material deposited on the edges of the ribbon. Thus, in Figure 3a, the two ends or edges of each of the faces 58a and 60a is terminated by a respective wall 62 or 64 forming a shoulder that is substantially 25 perpendicular to the faces 58a and 60a. If the length of the shoulder is equal to X, the thickness of the carbon ribbon at its edges is 2X greater than the thickness in the center of the ribbon. The side face of the ribbon is formed by a wall 66 that is substantially perpendicular 30 to the longitudinal axis of symmetry 56a. The edge of the ribbon situated above the longitudinal axis of symmetry 56a co-operates with the face 58a and the wall 62 to form a rectangular rim 68 that projects relative to the face 58a. Similarly, the edge of the ribbon situated 35 beneath the longitudinal axis of symmetry 56a co-operate with the face 60a and the wall 64 to form a rectangular 7 rim 70 that projects relative to the face 60a. Together the two rims 68 and 70 constitute a double rim. Two semiconductor layers 72 and 74 can be deposited on the faces of the carbon ribbon, using the method 5 descried above with reference to Figure 1, after previously depositing a layer of pyrolytic graphite on the two faces of the carbon ribbon. The thickness of the semiconductor layers varies as a function of the speed with which the ribbon is pulled. The height X of the rim 10 is advantageously selected to be equal to or less than the thickness of the semiconductor layer. In Figure 3a, three layer thicknesses are shown so as to illustrate the profile of the outside faces 76, 78, and 80 of the layers in the vicinity of the rims 68 and 70. It can be seen 15 that regardless of their thickness, the layers join the rim 68 or 70 at the end 82 or 84. As a result the thickness of the margins of the semiconductor layers no longer diminishes to tend towards a thickness close to zero as in the prior art. Furthermore, practically no 20 semiconductor becomes deposited on the outside face of the carbon ribbon constituted by the wall 66. This absence of semiconductor on the wall 66 facilitates a subsequent operation of the RTS method that consists in burning off the carbon ribbon in a furnace so as to 25 separate the two semiconductor layers 72 and 74. In Figures 3b, 3c, and 3d, the edges of the ribbons have projecting shapes, so as to form a double rim that is triangular. The edges of the faces 58b,c,d, and 60b,c,d of the ribbons are each constituted by two walls 30 90b,c,d and 92b,c,d sloping outwards from the faces of the ribbon and by a wall 94b,c,d that is substantially perpendicular to the longitudinal axis of symmetry 56b,c,d. The walls 94b,c,d form side faces of the ribbons. The shapes of these faces differ in the various 35 figures: in Figure 3b, the wall 94b is plane in shape; in Figure 3c, the wall 94c has a setback 96c; and in Figure 3d, the wall 94d is in the shape of a drop of 8 tallow (or a half-drop of tallow if only one face 58d or 60d is considered together with the respective walls 90d or 92d). Each of the walls 90b,c,d co-operates with the faces 5 94b,c,d to form a triangular rim 98b,c,d. Likewise, each of the walls 92b,c,d co-operates with the faces 94b,c,d to form a triangular rim 100b,c,d. The rims 98b and 100b together form a double rim that is triangular. The same applies to the rims 98c and 100c and also to the rims 98d 10 and 100d. The walls 90b,c,d and 92b,c,d need not be plane and could be flared in shape going towards the outside of the ribbon. Under such circumstances, the cross-section of the edges of the ribbons would have a rounded shape. 15 The semiconductor layers 72b,c,d and 74b,c,d are deposited on the respective faces 58b,c,d and 60b,c,d after the faces of the ribbon have been coated in pyrolytic carbon. Two thicknesses e, and e 2 of semiconductor layers are shown in each of Figures 3b,c,d 20 so as to show how the layers meet the ends 102b,c,d and 104b,c,d of the rims. It should be observed that the thicknesses of the layers are practically constant, including at the edges of the ribbon. As in the embodiment shown in Figure 3a, the 25 deposition of semiconductor on the side faces 94b,c,d can be minimized or eliminated, thus facilitating the subsequent operations of opening up the edge of the carbon ribbon to enable the carbon ribbon to be eliminated by combustion. 30 The carbon ribbon used in the RTS method is relatively soft and plastic. It is flexible, of low density, and made by cold rolling expanded natural graphite. The weight per unit area of the ribbon lies typically in the range 150 grams per square meter (g/m2) 35 to 200 g/m2, and its thickness is about 250 pm. Because of this soft and plastic nature of the carbon ribbon, the shape of its edges (naturally in the form of a 9 rectangular parallelepiped) can be modified without difficulty. This can be done by any appropriate means, in particular by a forming method relying on continuous upsetting using mechanical means that exert pressure on 5 the two edges of the ribbon, which pressure is directed towards the inside of the ribbon along the axis of symmetry 56a,b,c,d. It is also possible to modify the shape of the edges by controlled flattening, depending on the shape that is to be given. 10 Once the shape of the edges of the ribbon has been modified, the faces of the ribbon (including the edges) are advantageously covered in a layer of pyrolytic carbon having thickness lying in the range 1 ym to 5 pm. After this operation, the carbon ribbon is rolled 15 simultaneously with a film of recoverable plastic or paper of thickness selected so as to avoid flattening the double rim during rolling. With a rim of height k (see Figure 3a), the thickness of the plastic or paper film should be not less than k. During the operation of 20 pulling the carbon ribbon through the semiconductor bath, the plastic or paper film is separated from the carbon ribbon and recovered to be used again. It should be observed that the double rim on each edge of the carbon ribbon does not make it any more 25 difficult to cause the ribbon to travel through the slot 14 in the crucible 10 (Figure 1) since the slot generally includes at each of its two ends, respective holes of diameter greater than the width of the slots, as described in patent FR 2 561 139. 30 The invention thus provides a solution that is technically simple and inexpensive to the problem of the reduced thickness of the edges of semiconductor layers obtained by pulling a carbon ribbon. This improves the efficiency with which the area of the ribbon and the area 35 of semiconductor are used. The projecting shape, in particular the rim, given to the profile of the edges of 10 the ribbon makes the ribbons less fragile and thus improves the manufacturing yield of semiconductor films. Embodiments other than those described and shown can be devised by the person skilled in the art without going 5 beyond the ambit of the present invention, the embodiments shown in Figures 3a,b,c,d being merely example embodiments amongst other possible embodiments.

Claims

1. A method of depositing a layer of semiconductor material on at least one of the two faces of a carbon ribbon, said ribbon having two edges, in which method the ribbon is pulled progressively upwards, substantially vertically, lengthwise through the horizontal equilibrium surface of a bath of molten semiconductor material, which becomes deposited by wetting said face as the carbon ribbon is pulled, the method being characterized in that it consists in changing the shape of the edges of the ribbon so as to increase the thickness of the layer of semiconductor material that is deposited on the edges of the ribbon.

2. A method according to claim 1, characterized in that each of the edges of the forms a rim.

3. A method according to claim 2, characterized in that said rim is of flared shape, of substantially rectangular shape, or of substantially triangular shape.

4. A method according to any preceding claim, characterized in that, when a layer of semiconductor material is deposited simultaneously on both faces of the ribbon, each of the edges of the ribbon is given the shape of a double rim.

5. A method according to any preceding claim, characterized in that the shape is modified by forming the two edges of the ribbon by upsetting them continuously towards each other.

6. A method according to any one of claims I to 3, characterized in that the shape is modified by flattening the edges. 12

7. A method according to any preceding claim, characterized in that said semiconductor material is selected from silicon, germanium, and type Ill-V semiconductor compounds of the GaAs family presenting congruent or quasi-congruent melting.

8. A method according to any preceding claim, characterized in that the semiconductor material is silicon, and the carbon ribbon is covered in a layer of pyrolytic carbon on which the silicon layer is deposited.

9. A carbon ribbon having two edges, with at least one of its two faces being designed to be covered in a layer of semiconductor material by causing said ribbon to pass substantially vertically upwards through a bath of molten semiconductor material, the carbon ribbon being characterized in that each of its two edges on at least one of its two faces projects to form a rim.

10. A ribbon according to claim 9, characterized in that each of said edges flares so as to form a half-round shape.

I1. A ribbon according to claim 9, characterized in that each of said edges forms a shoulder substantially perpendicular to said face of the ribbon that is to receive the layer of semiconductor material, said rim then being substantially rectangular.

12. A ribbon according to claim 9, characterized in that each of said edges forms a shoulder that slopes relative to said face of the ribbon that is to receive the layer of semiconductor material, said rim then being substantially triangular.

13. A ribbon according to any preceding claim, characterized in that each of its edges has an outside portion substantially perpendicular to said face of the ribbon that is to receive the layer of semiconductor material.

14. A ribbon according to claim 13, characterized in that said outside portion includes a portion that is set back towards the ribbon. 13

15. A ribbon according to claim 13, characterized in that said outside portion is in the form of a half-drop of tallow.

16. A ribbon according to any one of claims 9 to 15, characterized in that said semiconductor material is deposited on both faces of the ribbon, and each of the two edges of the carbon ribbon forms a double rim.

17. A ribbon according to claims 10 and 16, characterized in that each of the two edges forms a rounded shape.

18. A ribbon according to claims 15 and 16, characterized in that said outside portion is in the form of a drop of tallow.

19. A ribbon according to any preceding claim, characterized in that said semiconductor material is selected from silicon, germanium, and type Ill-V semiconductor compounds of the GaAs family with congruent or quasi-congruent melting.

20. A carbon ribbon being substantially as herein described with reference to the accompanying figures.