Method for growing parallel elongate elements (nanowires, microwires) from a substrate comprising, for each elongate element, a seed formed in a cavity of a nucleation layer or a nucleation pad
10781534 · 2020-09-22
Assignee
Inventors
Cpc classification
C30B29/40
CHEMISTRY; METALLURGY
C30B25/186
CHEMISTRY; METALLURGY
International classification
C30B25/00
CHEMISTRY; METALLURGY
C30B29/40
CHEMISTRY; METALLURGY
Abstract
The method for growing an elongate element (5), notably a wire of nanowire or microwire type, includes forming a nucleation surface (3) having at least one germination site adopting the form of a germination hollow (7) and delimited at least partly by a mask (2), the at least one germination hollow (7) being situated at a distance from the mask (2), performing nucleation of a seed (4) intended to participate in the growth of the elongate element (5) on the at least one germination hollow (7), and growing the elongate element (5) from the seed (4).
Claims
1. A method for growing an elongate element, comprising: forming a nucleation surface having at least one germination site adopting the form of at least one germination hollow and delimited at least partly by a mask, the at least one germination hollow being situated at a distance from the mask, performing nucleation of a seed intended to participate in the growth of the elongate element on the at least one germination hollow, growing the elongate element from the seed so that the elongate element extends away from the nucleation surface, wherein the forming of the nucleation surface comprises forming the mask on a nucleation layer, wherein an opening of the mask forms, with a part of the nucleation layer, a blind hole, wherein a bottom of the blind hole formed by the part of the nucleation layer corresponds to the nucleation surface.
2. The method as claimed in claim 1, comprising performing in succession: (i) in the formation of the nucleation surface, a modification of a topology of the nucleation layer so as to form the at least one germination hollow, (ii) the formation of the mask, (iii) the nucleation of the seed, and (iv) the growth of the elongate element.
3. The method as claimed in claim 1, further comprising supplying a substrate on which is formed a nucleation layer, wherein the formation of the nucleation surface comprises: etching the nucleation layer to the substrate so as to form a block, forming the mask on the substrate, the mask surrounding the block.
4. The method as claimed in claim 3, comprising performing, in succession: (i) in the formation of the nucleation surface, a modification of a topology of the nucleation layer so as to form the at least one germination hollow, (ii) the etching of the nucleation layer, (iii) the formation of the mask, (iv) the nucleation of the seed, and (v) the growth of the elongate element.
5. The method as claimed in claim 1, further comprising forming the at least one germination hollow so that the at least one germination hollow defines a seed nucleation zone exhibiting a variation of energy necessary for the formation of the seed, in the only nucleation zone, less than the variation of energy that would be necessary for the formation of an identical seed at a corner between the mask and the nucleation surface.
6. The method as claimed in claim 1, wherein the formation of the nucleation surface comprises determining a form of the at least one germination hollow taking into account a first wettability factor of a material intended to form the seed on a material used to form the nucleation surface and a second wettability factor of the material intended to form the seed on a material used to form the mask, and forming the at least one germination hollow according to the determined form.
7. The method as claimed in claim 6, wherein the germination hollow adopts, wholly or partly, the form of a cone, wherein a surface of the cone is defined by a generating straight line passing through a fixed point belonging to a main axis that is secant to a plane including a directing curve of the cone, and wherein the method comprises determining an angle /2 between the generating straight line and the main axis, the angle /2 being determined from the first and second wettability factors.
8. The method as claimed in claim 7, wherein the determination of
9. The method as claimed in claim 1, wherein the formation of the nucleation surface is so that the at least one germination hollow adopts, wholly or partly, the form of a cone, wherein a surface of the cone is defined by a generating straight line passing through a fixed point belonging to a main axis that is secant to a plane including a directing curve of the cone, a maximum angle /2 between the generating straight line and the main axis being less than 53 degrees.
10. A method for fabricating an electronic device comprising implementing the method for growing an elongate element as claimed in claim 1, and functionalizing the elongate element so that the elongate element participates in emission, or in reception, of photons.
11. A substrate functionalized for the growth of an elongate element, the substrate comprising a nucleation surface making it possible to grow an elongate element and a mask at least partly delimiting the nucleation surface, wherein the nucleation surface comprises at least one germination hollow situated at a distance from the mask, wherein the nucleation surface comprising the germination hollow is adapted for growing the elongate element from a seed so that the elongate element extends away from the nucleation surface, wherein an opening of the mask forms, with a part of the nucleation layer, a blind hole, wherein a bottom of the blind hole formed by the part of the nucleation layer corresponds to the nucleation surface.
12. The substrate as claimed in claim 11, wherein the at least one germination hollow adopts the form of a cone, wherein all or part of a surface of the cone is defined by a generating straight line passing through a fixed point belonging to a main axis that is secant to a plane including a directing curve of the cone, the maximum angle /2 between the generating straight line and the main axis being less than 53 degrees.
13. The method as claimed in claim 1, wherein the elongate element is a nanowire.
14. The method as claimed in claim 1, wherein the elongate element is a microwire.
15. The method as claimed in claim 3, wherein the mask formed on the substrate surrounds the block at a base of the block arranged at a corner formed by the block and the substrate.
16. The method as claimed in claim 7, wherein the cone is a cone of revolution or pyramidal, the main axis is secant at right angles to the plane including the directing curve of the cone, and the method comprises determining the maximum angle /2.
17. The method as claimed in claim 9, wherein the cone is a cone of revolution or pyramidal, and the main axis is secant at right angles to the plane including a directing curve of the cone.
18. The method as claimed in claim 1, wherein the elongate element extends substantially perpendicular to the nucleation surface.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) Other advantages and features will emerge more clearly from the following description of particular embodiments of the invention given as nonlimiting examples and represented in the attached drawings, in which:
(2)
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DESCRIPTION OF PREFERENTIAL EMBODIMENTS OF THE INVENTION
(10) The present invention differs from what has been described in the prior art in that it is proposed to control the surface topology of the nucleation layer (layer which will allow the growth of the wires, notably of GaN) in order to control the phenomenon of germination of the GaN and improve the verticality of said wires.
(11) As illustrated in
(12) In fact, as illustrated by
(13) Along this line, it has emerged that by modifying the topology of the nucleation surface, notably by forming therein a preferentially adapted germination hollow, the seed would have a greater tendency to form in the germination hollow and not at the corner between the mask 2 and the nucleation surface 3. To avoid the non-vertical growth, this germination hollow is formed at a distance from the mask 2.
(14) In the above explanation, reference is made to a wire. However, it is possible to expand this concept of wire to any elongate element. In particular, the elongate element can be a wire, for example of nanowire or microwire type.
(15) The term microwire or nanowire hereinbelow in the description preferentially means a three-dimensional structure of elongate form of which the longitudinal dimension is at least greater than one times the transverse dimension or dimensions, preferably at least five times and even more preferentially at least ten times. The transverse dimension or dimensions lie between 5 nm and 2.5 m. In some embodiments, the transverse dimensions can be less than or equal to approximately 1 m, preferably lie between 100 nm and 300 nm. In some embodiments, the height of each nanowire, or microwire, can be greater than or equal to 500 nm, preferably between 1 m and 50 m.
(16) In this sense, as illustrated in
(17) The expression germination hollow situated at a distance from the mask should be understood to mean that the germination hollow 7 is not situated at the corner between the mask 2 and the nucleation surface 3 but at a certain distance from said mask 2. A certain distance should be understood to mean that the germination hollow 7 is situated at a distance from the mask 2 at least equal to one times, two times, five times or ten times the width of the germination hollow 7. Preferentially, the germination hollow 7 is situated substantially at the center of the nucleation surface 3 of which the periphery is delimited by the mask 2.
(18) Nucleation surface should be understood to mean at least a part of an outer surface of an element such as a block, or a layer, formed in a material compatible with the formation of a seed 4 in order to allow the growth of the elongate element 5.
(19) The growth step is preferentially such that the elongate element extends, along its direction of elongation, from said nucleation surface 3 while moving away from said nucleation surface 3.
(20) According to a first implementation (
(21) Preferentially, in the context of this first implementation, the following steps are performed in succession: a modification of the topology of the nucleation layer 8 so as to form said at least one germination hollow 7, the step of formation of the mask 2, the step of nucleation of the seed 4, the step of growth of the elongate element 5.
(22) According to a second implementation illustrated in
(23) Alternatively, the substrate supplied can also directly comprise the block 10 (obtained in any way).
(24) Preferentially, in the context of this second implementation, the method comprises the following steps in succession: a modification of the topology of the nucleation layer 8 (
(25) In a way applicable to the first and second implementations, the nucleation layer can comprise, or consist of, aluminum nitride, or a nitride of a transition metal, for example chosen from TaN, ZrN, HfN, NbN, etc., the thickness of which can lie between 10 nm and 100 nm. Preferentially, this nucleation layer 8 (for example prepared ex-situ) can be formed in two steps: first of all the metal (Ta, Zr, Hf, Nb, etc.) is deposited on the substrate 9 (substrate visible in
(26) Preferentially, the substrate 9 is of n-doped silicon, notably n+ doped. It makes it possible, for example, to inject charge carriers via the silicon substrate into the active part of the device which will be located at the elongate element 5. The n+ doped substrates have a very low electrical resistance, of the order of a few m.Math.cm.
(27) Preferentially, the step of modification of the topology of the nucleation layer 8 so as to form said at least one germination hollow 7 is performed by indentation. Indentation should be understood to mean that the step implements the use of a point whose end is shaped so as to partially penetrate the nucleation layer 8 so that, after the point is removed, the germination hollow 7 obtained has a predetermined form.
(28) According to one embodiment, the method comprises, generally and in a manner applicable to all its embodiments, a step of modification of the topology of the nucleation layer, notably performed as described above, to form said at least one germination hollow. In particular, this step of modification of the topology of the nucleation layer is performed after formation of said nucleation layer. In this respect, it can be defined that the modification of the topology of the nucleation layer consists in forming a germination hollow, the properties of which make it possible for the seed to be formed automatically in said corresponding germination hollow. Notably, the step of modification of the topology is such that the germination hollow is of a depth approximating to the thickness of the nucleation layer but without exceeding it. According to a nonlimiting example, the thickness of the nucleation layer is of the order of 20 nm and the depth of the germination hollow lies between 5 nm and the thickness of the nucleation layer minus 1 nm. In other words, in this case, the germination hollow is not comparable to a simple surface roughness and can be such that it comprises a bottom delimited by a part of the nucleation layer.
(29) Preferentially, the seed 4 nucleated in the nucleation step is of gallium nitride.
(30) Advantageously, the step of nucleation of the seed 4 is performed according to the MOCVD technique, MOCVD being the acronym for Metalorganic chemical vapor deposition.
(31) Moreover, the elongate element 5 obtained at the end of the growth step can be of gallium nitride, preferentially n doped. The growth is perhaps performed according to the MOCVD technique.
(32) In the context of the first implementation, the mask 2 can be deposited on the nucleation layer 8. The deposition can be random (for example in situ using Si.sub.xN.sub.y for example) or organized (for example Si.sub.3N.sub.4, SiO.sub.2, etc.).
(33) In the context of the second implementation, after etching of the nucleation layer 8, the substrate 9, preferentially of silicon, exhibits zones revealed where the etching has been performed. These revealed zones delimit the block or blocks 10. In this case, it is possible to form the mask 2 by implementation of a step of nitriding under NH3 of the revealed zones of the substrate of silicon (the mask is then of Si.sub.xN.sub.y).
(34) It will be understood from what has been stated above that the presence of the germination hollow 7 makes it possible to promote the vertical growth of an elongate element relative to the plane in which the mask or the substrate 9 is formed.
(35) Vertical growth of the elongate element 5 should be understood to mean that the latter has two opposing longitudinal ends of which one is in contact with the nucleation layer 3 and the other is at a distance from said nucleation layer 3, the direction of elongation being substantially at right angles to the plane including the nucleation surface 3 and/or to a plane including the substrate 9.
(36) By adapting the form of the germination hollow 7, it is also possible to increase the probabilities of nucleation of the seed 4 at said germination hollow 7.
(37) According to a particular example, the phenomenon of nucleation of a seed of gallium nitride on a substrate, notably by the MOCVD technique, can be understood by a purely thermodynamic approach involving an energy budget of the surfaces and interfaces. The heterogeneous germination of GaN on a substrate 9 can be schematically represented by a crystalline embryo (corresponding to the seed 4 described above), the form of which is that of a spherical dome formed on a planar substrate as is represented in
.sub.SG=.sub.CG cos +.sub.SC where is the angle of contact of the embryo/seed 4 on the substrate 9.
(38) In the example which is given hereinbelow, corresponds to .sub.GaN/CN.
(39)
E.sup.IE.sup.II=cte(f1f22)
(40) Where cte is a positive constant, f1 represents the wettability factor of the gallium nitride on the nucleation layer 8 (Ta.sub.xN.sub.y in the case of the example) with 0f11, and f2 the wettability factor of GaN on the mask 2 (Si.sub.xN.sub.y in the case of the example) with 1f20.
(41) In the above equation, cte is a constant and positive prefactor which includes a reference distance r.sub.i.
(42) Notably, there is
(43)
where ri is the radius of the seed (notably visible in
(44) Furthermore, for solving purposes, the sign of E.sup.IE.sup.II needs to be known, and in this case, cte is a positive constant and the terms between parentheses above therefore need to be known.
(45) By taking f1=cos .sub.GaN/CN where .sub.GaN/CN is the contact angle of the embryo (the seed 4) of GaN on the nucleation layer. It is assumed that there is a strong interaction between GaN and the nucleation layer, that is to say that 0.sub.GaN/CN90. For example, when .sub.GaN/CN=0 (f1=1), there is total wetting of GaN on the nucleation layer.
(46) By taking f2=cos .sub.GaN/SixNy where .sub.GaN/SiNx is the contact angle of the embryo (the seed 4) of GaN on the mask 2 (Si.sub.xN.sub.y). It is assumed that there is a weak interaction between GaN and Si.sub.xN.sub.y, that is to say that 90.sub.GaN/SixNy180. When .sub.GaN/SixNy=180 (f2=1), there is total dewetting of GaN on the mask.
(47) The values of the parameters f1 and f2 can be estimated by drop angle measurements.
(48) It emerges that whatever the value of f1 and f2, the difference E.sup.IE.sup.II is always negative, which means that the germination of GaN on an edge of the mask (
(49) In other words, beyond the simple germination hollow 7 of any form, it is preferable for the method to comprise a step of formation of said at least one germination hollow 7 performed such that said at least one germination hollow 7 defines a seed 4 nucleation zone exhibiting a variation of energy necessary for the formation of said seed, in the only nucleation zone, less than the energy variation necessary for the formation of a same seed at the corner between the mask 2 and the nucleation surface 3.
(50) In particular, it will be understood that the step of formation of the nucleation surface 3 can be such that it comprises a step of determination of the form of said at least one germination hollow 7 taking into account a first wettability factor f1 of the material intended to form the seed 4 on the material used to form the nucleation surface 3 and a second wettability factor f2 of the material intended to form the seed 4 on the material used to form the mask 2, and a step of formation of said at least one germination hollow 7 according to the determined form.
(51) Preferentially, said at least one germination hollow 7 has a generally cone of revolution form, the method comprises a step of determination of an angle /2, notably maximum, of the generating straight line d1 of the cone relative to the axis of rotation A1 of said generating straight line d1 from the first and second wettability factors f1, f2. Thus, as illustrated in
(52) A germination hollow 7 has been described above that is of generally cone of revolution form, but this example is not limiting in as much as the germination hollow 7 can also have a pyramidal cone form.
(53) By definition, a cone exhibits a set surface defined by a generating straight line passing through a fixed point called vertex and a variable point describing a closed planar curve called directing curve. This directing curve can adopt the form of a circle (cone of revolution) of a square (pyramidal cone), any form, etc.
(54) In this respect, everything stated in the present description for a cone of revolution can be applied to these other forms, and more generally, the germination hollow 7 can adopt, notably wholly or partly, the form of a cone, notably of revolution or pyramidal, of which the surface is defined by a generating straight line passing through a fixed point belonging to a main axis that is secant, notably at right angles, to the plane including a directing curve of said cone. In particular, the method comprises a step of determination of an angle /2, notably maximum, between the generating straight line (d1) and said main axis, said angle /2 being determined from the first and second wettability factors f1, f2.
(55) Thus, by considering a structuring (that is to say a hollow) of the nucleation layer of which the morphology can be characterized by a reference distance r and an angle (
(56) The reference distance r is set as an arbitrary variable. In practice r can be of the order of a few nanometers to a few tens of nanometers.
(57) The difference between this energy variation E.sup.III and that associated with the formation of a seed of GaN when the latter is located at the corner between the mask and the nucleation layer (E.sup.I as defined above) makes it possible to access the values of the angle for which the difference E.sup.IIIE.sup.I is negative, in other words for which angles of the germination hollow 7 it becomes more probable from an energy budget viewpoint to promote the germination of GaN directly on the structured nucleation layer rather than on the edge of the mask. The graph of
(58)
(59) gives access to a threshold value .sub.threshold of the angle . Below .sub.threshold, E.sup.IIIE.sup.I0 and the nucleation of the seed of GaN is promoted on the structured nucleation layer. (Note: the value of the angle .sub.threshold for which E.sup.IIIE.sup.I0 is independent of the surface energy of GaN).
(60) In other words, the step of determination of the angle /2, notably between the generating straight line d1 of the cone and the axis of rotation A1 of said generating straight line d1, comprises the solving of the following equation
(61)
for which the result E.sup.IIIE.sup.I must be less than or equal to 0, with cte2 greater than 0, f1 the first wettability factor such that 0f11, and f2 the second wettability factor such that 1f20.
(62) Thus, it will be understood that the solving of the equation
(63)
will give a value of the angle and that it will preferentially be necessary to remain below if the aim is to best promote the nucleation of the seed in the germination hollow 7.
(64) In the above equations, cte2 is a constant and positive prefactor which preferentially includes the value of the reference distance r. More particularly, there is cte2=r.sup.2.sub.GaN where r is the radius of the seed and .sub.GaN the surface energy of the GaN when the seed is of GaN. Obviously, a person skilled in the art can adapt the formula to obtain cte2 when the seed is of a material other than GaN, the equation can then be written cte2=r.sup.2.sub.M where .sub.M represents the surface energy of the material M forming the seed. Here, there is a link between the distance r of
(65) It will be understood from what has been stated above that it is the sign of E.sup.IIIE.sup.I which is important for determining the angle /2. Now, as specified above, cte2 is a positive constant, only the terms of the parentheses make it possible to modify the sign.
(66) In
(67) In other words, the step of formation of the nucleation surface 3 is such that the germination hollow 7 has a generally cone of revolution form, the angle of the generating straight line of the cone of revolution relative to the axis of rotation of said generating straight line being less than 53 degrees. Alternatively, the germination hollow 7 adopts, notably wholly or partly, the form of a cone, notably of revolution or pyramidal, the surface of which is defined by a generating straight line passing through a fixed point belonging to a main axis that is secant, notably at right angles, to the plane including a directing curve of said cone, the maximum angle /2 between the generating straight line d1 and the main axis being less than 53 degrees.
(68) According to another formulation, it is considered that the formation of the seed 4 is promoted when all of the points delimiting the surface of the germination hollow 7 lie within a predetermined volume. In the present case, this volume corresponds to a cone of revolution of which the angle between the generating straight line d1 and the axis of rotation A1 of said generating straight line is less than 53 degrees.
(69) The value of 53 degrees advantageously makes it possible to guarantee that there will be a vertical growth whatever the wettability. In this respect, the notion of maximum angle is preferred but not essential.
(70) Generally, the cone of revolution comprises a radius dependent on the angle /2 and on the reference distance r.
(71) A method for growing an elongate element has been described above. Obviously, this method is not limited to the growth of a single elongate element. In this respect, it is possible to produce the growth, notably simultaneous, of a plurality of distinct elongate elements from a plurality of distinct growth sites, in particular each delimited by a same mask. In other words, all that has been stated above can be applied in the context of a method for growing a plurality of elongate elements comprising the following steps: a formation of a plurality of nucleation surfaces each delimited at least partly by a mask, each nucleation surface comprising at least one germination hollow situated at a distance from the mask, a nucleation of a seed, on each nucleation surface, intended to participate in the growth of said corresponding elongate element on said at least one germination hollow of said corresponding nucleation surface, a growth, of a corresponding elongate element from each nucleation surface.
(72) Furthermore, the method for growing one, or more, elongate element(s) as described above can be used in the context of a method for fabricating an electronic device, notably optoelectronic. In other words, the method for fabricating the electronic device, notably optoelectronic, can comprise a step of implementation of the method for growing an elongate element 5 and a step of functionalization of said elongate element 5 so that the latter participates in the emission, or in the reception, of photons (thus forming either a light-emitting diode, or a solar cell).
(73) The functionalization step can comprise a step of formation of a light detecting or emitting member comprising a junction provided with a first doped member of a first type and a second doped member of a second type distinct from the first type, said first member being formed by said elongate element. The first and second types will be chosen from a doping of n type or a doping of p type.
(74) It will be understood from what has been stated above that the invention can also relate to a substrate functionalized for the growth of an elongate element 5, notably a wire of nanowire or microwire type, this substrate comprises a nucleation surface 3 for a seed 4 making it possible to grow the elongate element, a mask 2 at least partly (even wholly) delimiting said nucleation surface. Said nucleation surface 3 comprises at least one germination hollow 7 situated at a distance from the mask 2. The germination hollow can be filled with a corresponding seed configured so as to allow the growth of said elongate element. Preferably, the germination hollow 7 is shaped according to one of the manners described above.
(75) This functionalized substrate is then advantageously used in the context of the growth method for performing the step of nucleation of the seed 4 and the step of growth of the elongate element 5. In other words, in the context of the growth method targeted above, the step of formation of the nucleation surface 3 (and potentially of nucleation of the seed) implements a step of formation of the functionalized substrate as described above.
(76) As illustrated in
(77) The device can comprise a photon emitting or receiving member 101, said member 101 comprising a P-N junction of which a part is formed by said elongate element 5. The elongate element is then doped of a P or N type. The other part of the P-N junction can be formed by another element 102 doped in an opposite way to the elongate element 5, said other doped element 102 covering a part of the elongate element, for example in the manner of a sheath as in
(78) The invention is not limited to the nucleation of a GaN seed on a nucleation layer of TaN, it can be applied to all the materials of nucleation layers CN (TiN, VN, CrN, ZrN, NbN, MoN, HfN, TaN) and to AlN since there can be heteroepitaxy of GaN on one of these materials. In this case, the parameter f1 which represents the wettability factor of GaN on the nucleation layer or of AlN always lies between 0 and 1 and the model remains true.
(79) With regard to the dimensions of the germination hollows, they can be extremely small, of the order of a few nanometers (depth/width between 1 and 10 nm) since only the germination phase is considered here.
(80) Regarding the approach by energy variation using E.sup.I, E.sup.II, E.sup.III, the energy calculation of the associated structure is within the scope of those skilled in the art. Notably, the principles of an approach by energy variation according to the invention can be derived from the book entitled Thermodynamique des matriaux: quilibres de phases et mtastabilit (Material thermodynamics: phase equilibriums and metastability) by Pierre Desr and Fiqiri Hodaj, EDP Scienceschapter 9, paragraphs 6-7.