The invention relates to the field of detection, measurement and emission of electromagnetic radiation and to the devices allowing detection, measurement or emission of electromagnetic radiation.
The past ten years have seen many developments in optoelectronics and the devices deriving from it. Such devices use semiconductor structures which are suitable for detection, measurement or emission of electromagnetic radiation.
Among these structures, nanowire-based semiconductor structures show great potential as regards the achievable efficiencies, whether in terms of reception, in the case of detection and measurement, or of emission, of electromagnetic radiation. These efficiencies are also sufficiently substantial to envisage using such structures in photovoltaic applications.
Such structures, whether dedicated to detection, measurement or emission of electromagnetic radiation, or to photovoltaic applications, can be more generally called optoelectronic structures.
An optoelectronic structure, above and in the remainder of the document, is understood to mean every type of semiconductor structure suitable for converting from an electrical signal into electromagnetic radiation, or vice versa.
The invention relates more particularly to a method of manufacture of at least one semiconductor nanowire, and to an optoelectronic semiconductor structure.
The industrial development and sale of nanowire-based optoelectronic structures still remain very limited, due to a number of technological barriers.
Among these technological barriers, electrical losses relating to the connection and the polarisation of the nanowires may be mentioned.
Indeed, a nanowire-based optoelectronic semiconductor structure generally includes:
Thus, with such a structure, polarisation of the active zone of each of the nanowires is obtained by applying a difference of potential between the first and second contact. In operation, and for an optoelectronic structure, this polarisation of the active zone allows conversion from an electrical signal into electromagnetic radiation, or vice versa.
Although such a structure allows the means of the first and second electrical contact to polarise the active zone of each of the nanowires, it nonetheless involves non-negligible electrical losses in the substrate/nucleation layer/nanowires interfaces.
The materials forming the substrate, the nucleation layer and the base of the nanowires are indeed generally semiconductors of different natures, and form a heterostructure at each interface. Such a type of interface generally has high interface resistance.
This is particularly so when the nanowires have a base made from a semiconducting nitride. Indeed, for this type of nanowire, the nucleation layer is made from aluminum nitride (AlN), which is a wide-band gap semiconductor (where the energy of its forbidden band is higher than 6 eV), which has the properties of a “semi-insulator”. The substrate/nucleation layer and nucleation layer/nanowires layer therefore have a high interface resistance with such material forming the nucleation layer. The consequence is that the polarisation of the base of each nanowire by the substrate/nanowire interface leads to substantial electrical losses, principally relating to the presence of the nucleation layer.
Such a structure therefore requires higher polarisation voltages to compensate for the losses in this interface, and is less efficient since the voltages are reduced by the said losses.
It may be noted that in the case of a structure of the photovoltaic type, although the active zone does not require polarisation, the first and second contacts are present for connecting the structure in order to collect the energy produced in the active zone, and the problem of the losses in the substrate/nanowires interface is therefore also present for a structure of the photovoltaic type.
The present invention seeks to remedy this disadvantage.
One aim of the invention is therefore to provide a nanowire-based optoelectronic semiconductor structure including a nucleation layer, where the structure has an interface resistance between the substrate and each of the nanowires which is lower compared to a structure of the prior art.
One more particular aim of the invention is therefore to provide a nanowire-based optoelectronic semiconductor structure including a nucleation layer having a forbidden energy band higher than 5 eV, where the structure has an interface resistance between the substrate and each of the nanowires which is lower compared to a structure of the prior art including such a nucleation layer.
Another aim of the invention is to provide a nanowire-based optoelectronic semiconductor structure which optimises dissipation of the heat produced by the active zones of each of the nanowires while the structure is in operation.
To this end, the invention concerns an optoelectronic semiconductor structure including:
where the nucleation layer is formed from at least one pad and covers the first face of the substrate over a portion of the first face, called the “nucleation” face, where the portion of the first face which is not covered by the nucleation layer is called the “free” portion, where the structure also includes a conducting layer in contact with the free portion of the substrate, and where the said conducting layer is also in contact with the nanowire on the perimeter of the nanowire.
Due to its contact both with the substrate and the nanowire such a conducting layer enables the nanowire to be polarised in parallel with the contact provided by the nucleation layer. Thus, for a contact provided by the nucleation layer through substrate/nucleation layer/nanowire interfaces with high electrical losses, polarisation of the nanowire is essentially obtained through the conducting layer and the electrical losses relating to the substrate/conducting layer and conducting layer/nanowire interfaces are reduced accordingly. This results in lower electrical losses for the substrate/nanowire interface compared to a structure of the prior art in which polarisation is provided solely by the nucleation layer.
In addition, such a conducting layer has, due to the thermal conduction by these majority carriers, thermal conduction properties which enable a proportion of the heat produced by the active zones while the structure is in operation to be dissipated.
The invention concerns more particularly a structure in which the nucleation layer has a forbidden energy band higher than 5 eV. The nucleation layer can be a semiconductor layer.
The conductive layer can be in contact with the nanowire on its entire perimeter.
The free portion of the first face can be recessed relative to the nucleation portion, over a recess height which is between 1 nm and 5 μm, and where the said recess height is preferentially between 1 nm and 500 nm.
Such a recess of the free portion of the first face enables the portion of the conduction layer which can be in contact with the substrate to be increased, where this conduction layer can be in contact with the substrate over the free portion and over the walls created by the recess of the free portion. Thus, the electrical interface between the conducting layer and the substrate is optimised with a low contact resistance. As the contact resistance between the nanowire and the conducting layer is also low thanks to the contact of the conducting layer on the perimeter of the nanowire, the resulting electrical interface between the nanowire and the substrate is optimized and the corresponding access resistance is reduced in comparison to a semiconductor structure which does not comprise such recess of the free portion of the first face.
The nanowire can cover roughly the entire nucleation layer.
The area of the nucleation portion of the first face is thus reduced as far as possible, giving an area of the free portion which is maximised. By this means a maximum value for the area of the first face on which the conduction layer can be in contact is obtained.
Since the nucleation layer can be formed from a pad corresponding to the nanowire, the nanowire covers the said pad.
The nanowire can be in contact on the nucleation layer in a plane which is roughly parallel to the first face of the substrate, having a maximum lateral dimension of the zone of the nanowire which is in contact with the conduction layer, where the conducting layer is in contact with the nanowire over a contact height which is at least equal to the maximum lateral dimension divided by four.
Such a contact height enables it to be guaranteed that the area of the conducting layer which is in contact with the periphery of the nanowire is sufficient to provide an optimised reduction of the interface resistance between the nanowire and the substrate compared to a structure of the prior art.
The transverse section of the nanowire in its zone which is in contact with the conducting layer can be roughly circular, hexagonal, triangular, square or of any other shape, where the maximum lateral dimension of such a nanowire is the diameter or width of such a transverse section.
The conducting layer can be principally made from a refractory material or from a refractory alloy.
Such a refractory material enables the properties of the conducting layer at the different annealing steps required to manufacture the structure to be guaranteed, without affecting its conductivity characteristics, and without any requirement to modify the manufacturing steps.
The conducting layer can be principally made from a material selected from the group containing titanium (Ti), tungsten (W), nickel (Ni) and alloys containing the said metals.
Such materials have the qualities required to form a conducting layer of satisfactory quality, and also have the advantage that they are able to form a silicide with the substrate, when the latter is made from silicon, thereby reducing the interface resistance between the substrate and conducting layer.
The structure can be a structure of a type selected from the group including structures able to emit electromagnetic radiation, structures able to receive electromagnetic radiation and to transform it into an electrical signal, and structures of the photovoltaic type.
Such structures have optimised efficiencies since the electrical losses in the substrate/nanowire interface are limited by the presence of the conducting layer.
The semiconductor structure may be intended to emit an electromagnetic radiation, where the structure includes:
The semiconductor structure may be able to receive electromagnetic radiation, and to convert it into an electrical signal, where the structure includes:
where the structure also includes a conducting layer in contact with the first face of the substrate on its free portion, where the masking layer is in contact with the nanowire over a portion of its perimeter.
The structure may include means of connection of the nanowire, where a first connection means is fitted to connect electrically to at least a portion of the substrate including the free portion of the first face, where a second connection means is fitted to connect the nanowire electrically at least in the end of the nanowire which is opposite the first face of the substrate.
The invention also concerns a method of manufacture of an optoelectronic semiconductor structure including at least one semiconductor nanowire, where the said method includes the steps consisting in:
Due to the step of formation of the conduction layer, such a method enables a nanowire-based structure to be manufactured which includes a nucleation layer, which has a reduced operating voltage compared to a structure of the prior art not including a conduction layer.
A step of etching of the free portion of the first face may also be included, such that the free portion of the first face is recessed relative to the nucleation portion of this same first face, where the said recess height is between 1 nm and 5 μm and is preferentially between 1 nm and 500 nm.
Such a step of etching of the free portion enables a higher contact area to be provided when the conduction layer is formed, thus making it possible for the structure obtained by the method to have a lower interface resistance compared to a structure the manufacturing method of which does not involve such an etching step.
The step of formation of the nucleation layer may include the sub-steps consisting in:
Such sub-steps allow the formation of the nucleation layer over the entire first face of the substrate with an alteration of the free portion after the formation of the nucleation layer.
The step of etching of the free portion of the first face and the sub-step of selective etching of a portion of the nucleation layer can be undertaken during a single etching step.
Such an etching step allows, in a single step, firstly the nucleation layer to be shaped by releasing the free portion, and secondly the recess of the free portion to be formed, allowing the contact between the free portion and the conducting layer to be optimised during the step of formation of the conducting layer.
The step of formation of at least one nanowire may include the sub-steps consisting in:
Such a step of formation of the nanowire allows, for a conduction layer which is not suitable for selective growing of the nanowire, a nanowire to be formed by presenting a peripheral contact with the conduction layer.
The step of formation of at least one nanowire may include the sub-steps consisting in:
Such a step of formation of the nanowire enables a nanowire to be formed which has a peripheral contact with the conduction layer, without requiring the prior formation of a masking layer, and where the conduction layer is able to allow selective growing of the nanowire on the nucleation layer.
The step of formation of at least one nanowire may include the sub-steps consisting in:
forming a nanowire by selective growing on the portion of the buffer layer in which the aperture emerges.
Formation of a buffer layer on the nucleation layer before the step of formation of the nanowire, where the said nanowire includes the portion of the corresponding buffer layer, enables a nanowire of high quality to be provided. Indeed, such a nanowire has a base formed from the said portion of buffer layer which has the quality of a “2D” layer, where the remainder of the nanowire is also of high quality, since it has been formed from a particularly suitable layer, namely the buffer layer
The step of formation of the nanowire includes the sub-steps consisting in:
Since the step of formation of the nanowire is a step of formation of a micro- or nanowire made of semiconducting nitride, such as GaN, the said first zone may include silicon so as to modify the said first zone to inhibit the lateral growth of the materials intended to form the remainder of the nanowire.
The present invention will be better understood on reading the description of example embodiments given purely as an indication and in no way restrictively, making reference to the appended illustrations in which:
Identical, similar or equivalent parts of the various figures have the same numerical references, to make it easier to go from one figure to another.
The various parts represented in the figures are not necessarily represented at a uniform scale, in order to make the figures more readable.
The various possibilities (variants and embodiments) must be understood as not being mutually exclusive, and being able to be combined with one another.
The characteristics and values which are mentioned in the remainder of this document, when mention is made of the particular application, concern only this application and do not restrict in any sense the invention's fields of application.
Such a semiconductor structure 100 includes:
The term “semiconductor nanowires” is understood to mean, above and throughout this document, semiconductor structures having three dimensions, two of which are the same order of magnitude of between 5 nm and 2.5 μm, and where the third dimension is equal at least to 2 times, or 5 times, or more preferentially 10 times, the greater of the two other dimensions.
Radius Rwire of each of nanowires 130 can be defined as the maximum lateral dimension of apertures 143 divided by two.
Substrate 110 is a semiconductor substrate suitable for growing nanowires 130. It is roughly flat in shape.
Substrate 110 is a semiconductor substrate which allows conduction of the majority carriers, such as a substrate made of silicon Si, silicon carbide SiC, zinc oxide ZnO or germanium Ge, or is a metal substrate.
Substrate 110 has a first type of conductivity. To restrict the electrical losses relating to the electrical resistance between substrate 110 and nanowires 130, substrate 110 has a high concentration of majority carriers.
Thus, according to the particular application illustrated in
Substrate 110 has on its first face 111 the free portion 114 which is recessed relative to nucleation portion 113. Nucleation portion 113 and free portion 114 are, respectively, the portions of the first face 111 of substrate 110 which is in contact with nucleation layer 120, and those which are not.
The depth of recess hrecess, as illustrated in
The substrate has first electrical contact 151 on its second face.
First electrical contact 151 has the form of a metal layer able to polarise substrate 111. First electrical contact 151 is, for the particular application, made of a metal able to form a silicide with silicon. The first contact forms a first means of polarisation able to polarise the substrate.
To limit the concentration of crystalline faults of nanowires 130, structure 100 includes nucleation layer 120 which is formed from a material suitable for growing nanowires 130. Nucleation layer 120 enables a portion of the crystal lattice difference which may exist between the material constituting substrate 110 and the material of the portion of nanowires 130 in contact with first face 111 of substrate 110 to be reduced. Concerning the portion of nanowires 130 in contact with substrate 110 which is made of a semiconducting nitride, such a material is one such as gallium nitride (GaN) or aluminum nitride (AlN).
The nucleation layer 120 is formed from a material with a forbidden energy band higher than 5 eV such as a nitride or an oxide. For example, the nucleation layer 120 can be formed from aluminum nitride (AlN), boron nitride (BN), sapphire (Al2O3), an boron oxide (B2O3) or an oxidized nitride such as an oxidized aluminum nitride (AlON) or an oxidized boron nitride (BON). Such materials are particularly suited for the growth of nanowires in which the contact portion 131 is formed from a gallium nitride (GaN) or a zinc oxide (ZnO)
Nucleation layer 120 is formed of pads.
The term of “pads” is understood to mean, above and throughout this document, an area of the nucleation layer separate from the other area with lateral dimensions that are relatively low, regarding the ones of the surface on which the nucleation layer is, and that are on the same order of one each other.
Here, the lateral dimensions of each pads are adjusted for the growth a nanowire, and thus, corresponds to the two lowest dimensions of the nanowire. So, in the case of a 50 nm diameter nanowire, the nucleation layer pad is a 50 nm diameter pad.
Conducting layer 141 is in contact with first face 111 of substrate 110 on its free portion 114. Conducting layer 141 is roughly flat in shape, and apertures 143 are partially made through conducting layer hcontact.
Conducting layer 141 is a layer made of a conductive material. Conducting layer 141 is preferentially made of a refractory material.
If substrate 110 is made of silicon, such as, for example, the case of the particular application, the material of conducting layer 141 is preferentially a material forming a silicide with silicon. In this latter case the material from which conducting layer 141 is made may be chosen from the group including titanium (Ti), tungsten (W), nickel (Ni), cobalt, Pt, Pd and the alloys containing the said metals.
The thickness of conducting layer 141 is greater than the recess depth hrecess of free portion 114 of first face 111 of substrate 110; conducting layer 141 thus protrudes from first surface 111 over a height called the “contact” height hcontact, as illustrated in
The contact height is preferably greater than or equal to the nanowires radius Rwire divided by two. Such a dimension enables a height to be provided over which conducting layer 141 is in contact with each of nanowires 130, the area of which is equal to the area of the base of nanowires 130.
Masking layer 142 extends to the surface of conducting layer 141 which is opposite substrate 110. Masking layer 142 is roughly flat in shape, and the portion of each of apertures 143 which is not made in conducting layer 141 is made all the way through masking layer 142.
Masking layer 142 is produced from a material on which the element or elements comprising nanowires 130 are not deposited during epitaxial growth. The material forming masking layer 142 is preferentially an insulator. Masking layer 142 may be, for nanowires 160, made of gallium nitride (GaN), silicon nitride (Si3N2), or silicon dioxide (SiO2). Thickness hmask of the masking layer, as illustrated in
Thus, conducting layer 141 and masking layer 142 have apertures 143 each of which accommodates one of nanowires 130.
Each aperture 143 emerges at a pad of nucleation layer 120.
Each aperture 143 has a transverse section relative to the conducting layer which may be roughly circular, hexagonal, triangular, square or of any similar shape. The maximum lateral dimension of such an aperture, which is equal to that of the corresponding nanowire, is the diameter or width of such a transverse section.
Each of nanowires 130 is a semiconductor structure lengthened in the direction roughly perpendicular to first face 111 of substrate 110. Each micro- or nanowire 130 is of a general extended cylindrical shape. Radius Rwire, as illustrated in
The height of each of nanowires 130 is greater than at least 2 times, or possibly 5 times or 10 times, the diameter of nanowire 160. The height of each of nanowires 130 may be between 100 nm and 30 μm.
Each nanowire 130 includes a portion, called the “contact” portion, in contact with nucleation layer 120, an active zone 132 in contact with contact portion 131 and a portion 133, called the “polarisation” portion, in contact with active zone 132.
Contact portion 131 of each nanowire 130 is in contact with the first face of substrate 110. Contact portion 131 of each nanowire 130 is also in contact on its entire perimeter with the conducting layer 141. The electrical contact between the conducting layer 141 and the contact portion 131 of each nanowire 130 is performed, as already been explained, on the thickness of the conducting layer that corresponds to the contact height hcontact.
Contact portion 131, including the base of corresponding nanowire 130, as illustrated in
Each of contact portions 131 is principally made from a direct-band gap semiconductor material of the first type of conductivity. The semiconductor material comprising contact portion 131 of each of nanowires 130 is modified according to the application of semiconductor structure 100 including nanowires 130. Thus, depending on the sought applications, the material comprising each of contact portions 131 may be selected from the group including gallium nitride (GaN), aluminum nitride (AlN), indium nitride (InN), the indium-gallium nitrides of the InxGa1-xN type, and the zinc oxide (ZnO).
It is possible to notice, that the invention is particularly adapted for nanowires comprising a contact portion in aluminum nitride AlN or in zinc oxide ZnO.
For the particular application illustrated in
Thus, in the particular application illustrated in
Each of active zones 132 is in contact with contact portion 131 of corresponding nanowire 130. Each active zone 132 is a layer covering contact portion 131 over a portion of the perimeter and over the end of corresponding contact portion 131, where the said end of contact portion 131 is the one opposite nucleation layer 120. Such a configuration of active zones 132 in which they are in contact with, simultaneously, one end and the perimeter of corresponding contact portion 131, is called a “shell” configuration.
Each active zone 132 includes a semiconductor junction. Active zone 132, for an application in which structure 100 is suitable for the emission of electromagnetic radiation, may, in order to increase the emission efficiency of each of nanowires 130, include confinement means, such as multiple quantum wells.
In the particular illustration illustrated in
Since active zones 132 as such are well known to the skilled man in the art they will not be described in greater detail in this document.
Each active zone 132 is in contact at its external perimeter with polarisation portion 133 of corresponding nanowire 130.
Polarisation portions 133 enable corresponding nanowire 130 to be contacted.
Polarisation portions 133 are preferably comprised principally of a direct-band gap semiconductor material. Each of polarisation portions 133 has a conductivity of the second type.
For application of the invention illustrated in
Each polarisation portion 133, to allow polarisation of each of nanowires 130, is in contact with second contact 152.
Second contact 152 is able both to allow polarisation of each of nanowires 130 in their polarisation portion 133, and to allow the electromagnetic radiation emitted or received by nanowires 130 to pass through.
Second contact 152 is a layer of a transparent, or partially transparent, conductor material, of the wavelength emitted or received by the structure and which is able to provide a contact with a semiconductor material having the second type of conductivity. Thus, the layer of which second contact 152 is formed may be nickel-gold (Ni—Au), indium-tin oxide (ITO) or any stack of these materials (such as Ni/ITO).
Second contact 152 forms a second means of polarisation able to polarise a proportion of each of nanowires 130.
Structure 100 also includes, positioned between masking layer 142 and the layer constituting second contact 152, a reflecting layer 160. Such a reflecting layer 160 is a layer able to reflect the electromagnetic radiation at the wavelength for which structure 100 is intended to operate.
In the particular application illustrated in
In the step of deposition of the reflecting layer, the reflecting layer is preferentially deposited in a non-conformal manner. According to this possibility, the portion of layer 160 in contact with masking layer 142 is then protected with resin, in order to etch the portion of layer 160 deposited at the upper end of the nanowire.
The buffer layer is a layer formed prior to the growth on nucleation layer 120 made from a material which is particularly suitable both for growing contact portion 131 of nanowires 130 and forming an electrical interface with this same portion of nanowires 130 which has lower resistance. The material constituting buffer layer 134 is preferentially chosen to be roughly identical to that of the remainder of contact portion 131 of nanowires 130.
Buffer layer 134 is between 300 nm and 5 μm thick.
Free portion 114 of first face 111 is recessed relative to the remainder of first face 111 over a recess depth hrecess which is greater than the thickness of buffer layer 134.
In this second embodiment, contact height hcontact is equal to the height over which conducting layer 141 is in contact with zone 131a of the nanowire formed in the buffer layer.
A method of manufacture of a structure 100 according to this second embodiment is differentiated from a method of manufacture according to the first embodiment in that it includes, between the step of formation of the nucleation layer and the step of application of the photosensitive resin, a step of formation of the buffer layer.
Such active zones 132 are differentiated from an active zone according to the two embodiments described above in that they are extensions of corresponding contact portions 131, and in that the contact between the said active zones and corresponding contact portions 131 is only at the end of contact portion 131.
According to this same possibility, each polarisation portion 133 is also an extension of corresponding contact portion 131 and of corresponding active zone 132, where the contact between each polarisation portion 133 and corresponding active zone 132 is only at the end of active zone 132.
The method of manufacture of a structure 100 according to this possibility is differentiated from the method of manufacture of a structure 100 according to the first embodiment only by the steps of formation of the nanowires 130 which are suitable for the formation of nanowires 130 including an active zone 132 of the axial type.
In this embodiment nanowires 130 are principally formed from a semiconducting nitride. First zone 131b is a zone of each of nanowires 130 which includes on its perimeter an inhibition layer (not illustrated), as described in the French patent application registered as number 1152926, formed of silicon nitride. This inhibition layer several nanometres thick enables the lateral growth to be inhibited on the perimeter of the first zone of each nanowire, thus preventing the growth of active zone 132 and of polarisation portion 133 in this zone. Due to its small thickness, the inhibition layer does not significantly affect the contact between conduction layer 141 and the perimeter of the contact portion of nanowire 130.
Insulation layer 170 is a layer made from a dielectric material, such as silicon dioxide SiO2, which is traditionally used to electrically insulate conducting layers in the microelectronics field. The thickness of insulating layer 170 is such that it is able to insulate electrically from one another conducting layer 141 and reflecting layer 160, where the latter is in direct contact with second electrical contact 152.
The method of manufacture of a structure 100 according to this fourth embodiment is differentiated from the method of manufacture of a structure 100 according to the first embodiment in that it does not include the step of formation of masking layer 142, in that the step of formation of contact portion 131 includes a sub-step consisting in depositing a semiconducting nitride including a proportion of silicon so as to form first zone 131a of contact portion 131, and in that it includes a step consisting in forming insulation layer 170 on conducting layer 141 before the step of formation of reflecting layer 160.
Number | Date | Country | Kind |
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12 53011 | Apr 2012 | FR | national |
Number | Date | Country | |
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61642040 | May 2012 | US |