EP4069883A1

EP4069883A1 - Device comprising nanowires

Info

Publication number: EP4069883A1
Application number: EP20812360.4A
Authority: EP
Inventors: Xavier Baillin; Vincent CONSONNI; Stéphane Fanget; Bassem Salem; Raluca Tiron
Original assignee: Centre National de la Recherche Scientifique CNRS; Commissariat a lEnergie Atomique CEA; Institut Polytechnique de Grenoble; Universite Grenoble Alpes; Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Current assignee: Centre National de la Recherche Scientifique CNRS; Institut Polytechnique de Grenoble; Universite Grenoble Alpes; Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Priority date: 2019-12-02
Filing date: 2020-12-01
Publication date: 2022-10-12
Also published as: US20230340672A1; WO2021110701A1; FR3103828A1; FR3103828B1

Abstract

The present invention relates to a method for forming nanowires, comprising the formation of a DNA origami (430) having through-openings (435), and the formation in the through-openings of portions (210) constituting all or part of the nanowires.

Description

DESCRIPTION

Device comprising nanowires

The present patent application claims the priority of the French patent application FR19 / 13617 which will be considered as forming an integral part of the present description.

Technical area

The present description relates generally to nanostructures, in particular nanowires, and electronic devices using nanowires.

Prior art

[0002] The nanowires are defined by elongated structures having nanometric dimensions in their transverse directions, that is to say dimensions less than one micrometer, preferably less than 500 nm. Nanowires are used in particular in sensors measuring physical quantities, such as pressure or stresses, causing deformation of the nanowires. In particular, nanowires are used in pressure sensors, gas sensors, piezoelectric generators, etc. The more the nanowires have small transverse dimensions and are numerous, the higher the resolution of the sensor and its sensitivity can be.

Summary of the invention

There is a need for methods of manufacturing nanowires having smaller transverse dimensions than those of nanowires obtained by usual methods.

There is a need for nanowires manufacturing processes making it possible to obtain a higher number of nanowires per unit area than that obtained by usual processes.

There is a need for manufacturing processes making it possible to obtain nanowires that are more regularly distributed. on a surface, in other words periodically, with respect to nanowires obtained by usual methods.

[0006] One embodiment overcomes all or part of the drawbacks of the known processes for forming nanowires.

According to a first aspect, an embodiment provides a method of forming nanowires, comprising the formation on a metallic region of a layer having through openings, and the formation in the through openings of portions deposited in a chemical bath, constituting all or part of the nanowires and extending from the metallic region.

[0008] According to one embodiment, the chemical bath for forming said portions comprises, in solution:

- a first compound defining a source of metal cations; and

- a second compound comprising a source of hydroxide, sulphide or selenide ions,

the concentrations of the first and second compounds and / or their ratio being below a concentration threshold of said chemical bath, said threshold being such that, when the concentrations are below said threshold, a growth of said portions parallel to said layer is favored by with respect to a growth of said portions in a thickness direction of said layer, said threshold preferably being of the order of 10 mM; and or

the chemical bath comprising one or more additives suitable for promoting a growth of said portions parallel to said layer with respect to a growth of said portions in the direction of thickness of said layer, preferably citrate or chloride ions; and or

- the first compound being in a surstoichiometric concentration relative to the second compound. [0009] According to one embodiment:

- Said metal cations are cations of at least one metal from the group consisting of Zn, Cd, Ni, Ag, and Cu; and or

- the first compound comprises at least one component from the group consisting of nitrates, acetates, chlorides and sulphates; and or

- the second compound comprises at least one component from the group consisting of HTMA, ammonia, sodium hydroxide, thiourea, selenourea, and sodium selenite.

[0010] According to one embodiment, said portions constitute first parts of the nanowires, the method comprising the deposition in a chemical bath of second parts of the nanowires extending from the first parts.

According to one embodiment, the composition of the chemical bath is different for the formations of the first and second parts.

According to one embodiment, the chemical bath to form the second parts comprises, in solution:

- a first compound defining a source of metal cations; and

- the concentrations of the first and second compounds and / or their ratio being greater than a concentration threshold of the chemical bath to form the second parts, the concentration threshold of the chemical bath to form the second parts being so that, when the concentrations are greater than this threshold, a growth of the second parts orthogonally to said layer is favored with respect to a growth of the second parts parallel to said layer, the concentration threshold of the chemical bath to form the second parts preferably being of the order of 20 mM; and or

the chemical bath for forming the second parts comprising one or more additives suitable for promoting a growth of the second parts orthogonally to said layer with respect to a growth of the second parts parallel to said layer, preferably polyethyleneimide or 1'ethylenediamine; and or

- the first compound being in substoichiometric concentration relative to the second compound.

[0013] According to one embodiment:

- Said metal cations of the chemical bath to form the second parts are cations of at least one metal from the group consisting of Zn, Cd, Ni, Ag, and Cu; and or

the first compound of the chemical bath to form the second parts comprises at least one component from the group consisting of nitrates, acetates, chlorides and sulphates; and or

- the second compound of the chemical bath to form the second parts comprises at least one component from the group consisting of HTMA, ammonia, sodium hydroxide, thiourea, selenourea, and sodium selenite.

[0014] According to one embodiment, the method comprises forming, at one end of the nanowires opposite to said metallic region, an electrically conductive region in contact with the nanowires.

[0015] According to one embodiment, the method comprises forming a polymer matrix between the nanowires.

[0016] According to one embodiment, the method comprises removing said layer. [0017] According to one embodiment, the metallic region comprises at least one of the materials from the group consisting of gold, nickel, copper, palladium and platinum.

[0018] According to one embodiment, the metallic region has a thickness greater than 100 nm.

[0019] According to one embodiment, said layer is obtained by lithography from a layer comprising a block copolymer or from a layer sensitive to electrons or to ultraviolet radiation.

[0020] According to one embodiment, said layer is defined by a DNA origami.

According to one embodiment:

the nanowires have a transverse dimension less than 300 nm, preferably less than 50 nm;

the nanowires have a length greater than 500 nm, preferably greater than 1 μm; and or

- Said layer has a thickness less than 100 nm, preferably less than 50 nm.

According to a second aspect, an embodiment provides a method of forming nanowires, comprising the formation of a DNA origami having through openings, and the formation in the through openings of portions constituting all or part of the nanowires .

According to one embodiment, said portions are deposited in a chemical bath.

[0024] According to one embodiment, the origami and the openings it comprises are made before fixing the origami on a substrate.

[0025] According to one embodiment, said portions constitute first parts of the nanowires, and second parts of the nanowires extending from the first parts are deposited in a chemical bath.

[0027] According to one embodiment, the method comprises forming a polymer matrix between the nanowires.

[0028] According to one embodiment, the method comprises removing at least part of the DNA origami.

One embodiment provides a device obtained by a method as defined above, in which the origami comprises folded DNA strands having parts attached to each other by staples.

According to one embodiment, the DNA origami is located on a layer made of the same material as that of the nanowires, said portions extending from said layer.

According to one embodiment, the DNA origami is located on a metallic region and, preferably:

- Said metallic region has a thickness greater than 100 nm; and or

- Said portions extend from said metallic region.

[0032] According to one embodiment, the device comprises, at one end of the nanowires opposite to said metallic region, an electrically conductive region in contact with the nanowires.

[0033] According to one embodiment:

- the metallic region comprises at least one of the materials from the group consisting of gold, nickel, copper, palladium and platinum; and or

- the nanowires are piezoelectric, preferably the Nanowires having a wurtzite-like crystal structure and / or comprise at least one of the materials from the group consisting of zinc oxide, cadmium sulfide, cadmium selenide, and nickel selenide.

[0034] One embodiment provides a device in which:

the nanowires have a transverse dimension less than 40 n, preferably less than 20 n;

the nanowires have a density greater than 10 nanowires per square micrometer, preferably greater than 50 nanowires per square micrometer; and or

- DNA origami has a thickness between of the order of 2 nm and of the order of 100 nm, preferably of the order of 10 n.

[0035] One embodiment provides for a sensor pixel, comprising a device as defined above.

One embodiment provides a sensor, preferably fingerprints, comprising several pixels as defined above.

According to one embodiment, the pixels are located on the side of a face of a substrate comprising, directly above each pixel, at least part of a circuit associated with this pixel.

Brief description of the drawings

These characteristics and advantages, as well as others, will be explained in detail in the following description of particular embodiments given without limitation in relation to the accompanying figures, among which: Figure 1 is a sectional view, partial and schematic, showing a step of a first embodiment of a process for manufacturing nanowires;

Figure 2 is a sectional view, partial and schematic, showing another step of the first embodiment;

Figure 3 is a sectional view, partial and schematic, showing another step of the first embodiment;

FIG. 4 is a partial and schematic sectional view showing a step of a second embodiment of a method for manufacturing nanowires;

Figure 5 is a sectional view, partial and schematic, showing another step of the second embodiment;

Figure 6 is a sectional view, partial and schematic, showing another step of the second embodiment;

FIG. 7 is a partial and schematic sectional view showing a step of an example of a method for manufacturing a sensor comprising nanowires, implementing the embodiments of FIGS. 1 to 6;

Figure 8 is a sectional view, partial and schematic, showing another step of the example process; and

Figure 9 is a sectional view, partial and schematic, showing another step of the example process.

Description of the embodiments

The same elements have been designated by the same references in the various figures. In particular, the structural and / or functional elements common to the different embodiments may have the same references and may have identical structural, dimensional and material properties.

For the sake of clarity, only the steps and elements useful for understanding the embodiments described have been shown and are detailed. In particular, steps of forming and / or removing various parts of structures are not described in detail, the described embodiments being compatible with the usual steps of forming / removing such parts.

Unless otherwise specified, when referring to two elements connected together, this means directly connected without intermediate elements other than conductors, and when referring to two elements connected or coupled together, it means that these two elements can be connected or be linked or coupled through one or more other elements.

In the following description, when reference is made to absolute position qualifiers, such as the terms "up", "down", "left", "right", etc., or relative, such as the terms "above", "below", "upper", "lower", etc., or to qualifiers of orientation, such as the terms "horizontal", "vertical", etc., reference is made unless specified contrary to the orientation of the figures.

Unless otherwise specified, the expressions "approximately", "approximately", "substantially", and "of the order of" mean within 10%, preferably within 5%.

Figures 1 to 3 are sectional views, partial and schematic, showing successive steps of a first embodiment of a manufacturing process of nanowires. More precisely, the nanowires are formed by chemical bath deposition. During such a deposition, a priming surface is placed in contact with a solution defining the chemical bath. The nanowires grow on the priming surface. The material of the nanowires forming from the dissolved contents of the solution.

In the step of Figure 1, there is provided a support 110. By way of example, the support 110 is a semiconductor wafer, preferably in silicon. Preferably, the semiconductor wafer has a front face (upper face in the figures) covered with an insulating layer, not shown.

The support 110 is covered with a metallic layer 120. The metallic layer thus defines a metallic region. Alternatively, the support 110 is metallic and defines the metallic region. The upper face of the metallic layer 120, that is to say the free face of the metallic region, is intended to constitute an initiation surface on which the future nanowires will be formed in the remainder of the process. The thickness of the metal layer 120 is preferably greater than or equal to 40 nm or approximately 40 nm, for example greater than 50 nm, more preferably greater than 100 nm, even more preferably greater than 150 nm. Compared to a thinner layer, this makes it possible to improve the state of the priming surface presented by the layer 120.

The metallic region 120 can be of any metal. Preferably, however, the lattice parameter of the metal and the crystal orientation of the metal region 120 are suited to the formation of the crystal lattice of the nanowires. For this, the metallic region 120 is preferably in the group consisting of gold, nickel, copper, palladium, and platinum. More preferably, the metallic region is gold. Preferably, before forming the metal layer 120, the support 110 is covered with a bonding layer not shown, for example made of chromium or titanium. The tie layer makes it possible, compared to an embodiment in which this layer is omitted, to facilitate the formation of the metallic layer 120 and to avoid various problems of stability and / or of adhesion of the metallic layer 120 on the support 110.

A layer 130 is then formed on the free face of the metallic region 120. The layer 130 is a perforated layer, that is to say that it has, or has, through openings 135.

The openings 135 are preferably arranged in a network, more preferably in a regular network such as a network having, in top view (that is to say seen from the upper part of FIG. 1), a symmetry of order two, three, four or six. The openings 135 are preferably arranged in a matrix, the matrix having the same row and column pitches.

Each opening 135 has for example a shape of section, that is to say a shape in top view, rectangular or, preferably, square. The section can also have a rounded shape, for example circular. Preferably, all the openings 135 have the same cross-sectional shape and, more preferably, the same cross-section dimensions.

Preferably, the openings 135 have a transverse dimension A of less than 300 n, more preferably less than 50 nm, even more preferably less than 20 nm. The transverse dimension A is also preferably greater than 5 nm, more preferably greater than approximately 10 nm. Preferably, the network of openings 135 has a distance B between openings neighboring between 0.5 and 3 times the transverse dimension A of the openings 135. The distance between two openings is understood to mean the distance separating the edges closest to the two openings. In the case of a regular pattern, the pattern pitch is defined by the value A + B.

The perforated layer 130 can be obtained by electronic lithography from an electron sensitive layer, for example a layer of polymethylmethacrylate, PMMA. The perforated layer 130 can also be obtained by lithography by ultraviolet radiation, preferably by so-called deep ultraviolet radiation, that is to say of wavelengths less than 200 nm. The perforated layer then results from a layer sensitive to ultraviolet radiation.

The perforated layer 130 can also be obtained from a layer comprising a block copolymer. A block copolymer is defined by a combination of at least two immiscible and chemically bonded polymers. Each of the polymers defines a block of the copolymer. The immiscibility results in the formation of separate phases, and one of the phases is then removed to form the openings 135. The size of the blocks is then chosen so as to obtain the desired dimensions of the openings 135.

The perforated layer 130 can also be replaced by an origami of deoxyribonucleic acid (DNA) such as that of the embodiments described below in relation to FIGS. 4 to 6.

In the step of FIG. 2, the material of the nanowires is deposited by a chemical bath. Portions 210 of the deposited material are formed in the openings 135 on the metallic region 120. The portions 210 extend from the metallic region 120. More specifically, the portions 210 are in contact with the metallic region 120. The deposited material can be any material that can be formed by chemical bath deposition. The publication by Pawar et Al, entitled "Recent status of Chemical bath deposited metal chalcogenide and metal oxide thin films" in Current Applied Physics 11 (2011) 117-161, describes such materials and chemical bath compositions for depositing these materials. . The deposited material can be a metal oxide such as nickel oxide (NiO), silver oxide (AgO), copper oxide (CU2O), or for example cadmium oxide (CdO) . The material deposited can also be a metal hydroxide, preferably iron (III) hydroxide (FeOOH), or copper hydroxide (Cu (OH) ₂ ). The deposited material can also be a chalcogenide, such as cadmium sulfide (CdS), zinc sulfide (ZnS), lead sulfide (PbS), cadmium selenide (CdSe), zinc selenide (ZnSe) , or for example nickel selenide (NiSe). Preferably, the deposited material has piezoelectric properties, more preferably, the deposited material is zinc oxide (ZnO).

Preferably, the temperature of the chemical bath is between 60 ° C and 100 ° C. The deposit is preferably carried out for a period of between 1 minute and 60 minutes, more preferably between 5 minutes and 30 minutes.

Although the structure shown has its layer 130 facing the top of the figure, the deposition is preferably carried out with the layer 130 facing down. This makes it possible to protect the portions 210 against possible particles of the material which could precipitate in the chemical bath. The deposition is preferably carried out in the absence of an electric field in the solution, which makes it possible to simplify the deposition process. [0068] According to one embodiment, each portion 210 constitutes a nanowire. Preferably, the portions 210 completely fill the openings 135, and the length of the nanowires is then equal to the thickness of the perforated layer 130. According to another embodiment, described below in relation to FIG. 3, each nanowire is formed by deposition in a chemical bath on one of the portions 210.

Thus, the number and the positions of the nanowires correspond to the number and to the positions of the portions 210. However, the perforated layer 130 makes it possible to obtain a number of portions 210 greater than the number of portions that would be obtained by omitting the perforated layer 130. The perforated layer thus makes it possible to increase the number of nanowires per unit area.

In addition, due to the fact that the positions of the portions 210 obtained correspond to those of the openings 135, the perforated layer 130 makes it possible to obtain portions 210 more evenly distributed than portions that would be obtained without the perforated layer 130. The perforated layer 130 therefore makes it possible to increase the regularity of the positions of the nanowires.

The transverse dimensions of the nanowires are the transverse dimensions of the portions 210 (that is to say the lateral dimensions in the orientation of the figure), or are a function of the transverse or lateral dimensions of the portions 210. In addition, each portion 210 has lateral dimensions smaller, preferably equal, than the transverse dimensions of the openings 135. Thus, the perforated layer 130 makes it possible to obtain the desired dimensions of the nanowires more easily than in the absence of a perforated layer.

In the preferred case of formation of ZnO nanowires on a metal region 120 in gold, the chemical bath to form the portions 210 preferably comprises, in solution: - zinc nitrate, Zn (N0 ₃ ) ₂ , and hexamethylenetetramine, HMTA, in concentrations less than 10 mmol / L; and or

- Zn (N0 ₃ ) ₂ in a surstoichiometric concentration relative to a concentration of HMTA; and or

- one or more additives suitable for promoting transverse growth (parallel to the layer 130) of the portions 210, relative to a growth of the portions 210 in the direction of thickness of the layer 130. This or these additives preferably comprise ions. citrate or chloride.

The inventors have found that the compositions defined above of the chemical bath, in particular a concentration below the threshold of 10 mmol / L (unit often denoted mM) of Zn (N0 ₃ ) ₂ and of HMTA, make it possible to guarantee that 'a portion 210 is formed in each of the openings 135. These compositions further make it possible to ensure that, in each opening 135, the portion 210 entirely covers the bottom of the opening 135. In other words, the number of portions 210 is equal to that of the openings 135 and the transverse dimensions of each portion 210 may be equal to those of the openings 135. The nanowires resulting from such a chemical bath are therefore distributed more regularly and / or have more regular transverse dimensions than for baths chemicals with different compositions.

From the compositions defined above to form ZnO nanowires on a metal region 120 in gold, those skilled in the art are able to define, by routine tests, Zn concentration thresholds (N0 ₃ ) ₂ and HMTA for other metals of the metallic region.

A person skilled in the art is also able to define chemical bath compositions suitable for the deposition of materials other than ZnO, such as those defined above, or the materials of the nanowires of the example of the sensor described. hereinafter in relation to Figures 7 to 9. In particular, the Zn (N03) 2 and HMTA constitute, in the case of the formation of ZnO nanowires, first and second respective compounds which may be, in the case of formation of other materials, different from Zn (N0 ₃ ) ₂ and / or of HMTA.

The first compound presents, when it is in solution in the chemical bath, cations of at least one metal entering into the composition of the nanowires formed. In other words, the first compound constitutes a source of metal cations. This or these metals are preferably from the group consisting of zinc (Zn), cadmium (Cd), nickel (Ni), silver (Ag), and copper (Cu). the first compound comprises one or more components among the nitrate, the acetate, the chloride, or for example the sulphate, of the metal or metals considered. The first compound can therefore comprise or consist of one or more components from zinc nitrate (Zn (N0 ₃ ) ₂ ), zinc acetate (Zn (CH ₃ COO) 2), zinc chloride (ZnCl2 ), zinc sulfate (ZnSCy) and more generally the components of the form M (N0 ₃ ) ₂ , MN0 ₃ ,

M (CH ₃ COO) ₂ , M (CH ₃ COO), MC1 ₂ , MCI, MS0 ₄ , where M is a metal preferably included in the list described above.

In the case where the material formed is a metal oxide, the second compound comprises a source of hydroxide ions, OH. By way of example, the second compound may preferably comprise, preferably consist of an amine, more particularly hexamethylenetetramine (HTMA) and / or ammonia (NH ₃ ), and / or sodium hydroxide. (NaOH). The second compound can thus make it possible to adjust the pH of the solution to a value suitable for the deposit. In the case where the material formed is a metal sulphide, the second compound preferably comprises a source of sulphide, for example comprises thiourea (CS (N¾) 2) or sodium sulphide (Na2S). In the case where the material formed is a metal selenide, the second compound preferably comprises a source of selenide, for example comprises selenourea (CSe (N¾) 2), or sodium selenite (Na2SeS0 ₃ ).

A person skilled in the art is then able to define, by routine tests, a concentration threshold so that, when the concentrations of the first and second compounds are below this threshold, the transverse growth of the portions 210 is favored, with respect to a growth of the portions 210 in the thickness direction of the layer 130. This threshold may have a value of the order of 10 mM, for example equal to 10 mM. It is considered here that the concentrations of the first and second compounds correspond to their concentrations at the time of their introduction into the growth bath. The forecast of concentrations below the concentration threshold defined above makes it possible to form a portion 210 in each of the openings 135.

The step of Figure 3 is implemented when, at the end of the step of Figure 2, each portion 210 constitutes only a first part of a future nanowire. Second parts 310 of the nanowires are then deposited in a chemical bath. The parts 310 extend from the portions 210 away from the layer 130. The assembly of a portion 210 and of the part 310, formed on the portion 210, constitutes a nanowire 320.

Preferably, the temperature of the chemical bath is between 60 ° C and 100 ° C. The deposition is preferably carried out for a period of between 1 minute and 180 minutes depending on the length of the nanowires that it is desired to obtain. The nanowires 320 have a length greater than 500 n, preferably greater than 1 μm.

The step of FIG. 3 thus makes it possible to obtain nanowires 320 having a length greater than the thickness of the perforated layer 130. Preferably, the perforated layer 130 then has a thickness less than 100 nm, preferably less than 50 nm. Compared to a thicker perforated layer 130, this makes it possible to accelerate the step of FIG. 2 and makes it possible to increase the free length of the nanowires 320. By free length is meant a length over which the nanowires 320 are not. surrounded by solid material. The greater the free length, the more easily the nanowires are deformable, which advantageously increases the sensitivity of a sensor using deformations of nanowires.

An advantage of the step of FIG. 3 is that the nanowires 320 can have a form factor, defined by the ratio between the length of the nanowires and the smallest transverse dimension of the nanowires, greater than the aspect ratio of nanowires made up of the only portions 210.

The composition of the chemical bath used to form the parts 310 is different from that of the chemical bath used to form the portions 210. Thus, in the example of forming ZnO nanowires, the chemical bath comprises, in solution: Zn (NO3) 2 and HMTA, in concentrations greater than 20 mM; and or

- Zn (N0) ₂ in a substoichiometric concentration relative to a concentration of HMTA; and or

one or more additives suitable for promoting a growth of the parts 310 orthogonally to the layer 130 with respect to a transverse growth of the parts 310. Such an additive can comprise a polyethyleneimine PEI, or 1'ethylenediamine.

The composition of the chemical bath described above makes it possible to form, from the portions 210, parts 310 extending vertically, that is to say orthogonally to the surface of the metal region 120, in other words orthogonally to the layer 130. It is thus possible to obtain parts 310 whose transverse dimensions are substantially equal to the transverse dimensions of the portions. 210. This makes it possible to obtain nanowires the cross section of which is substantially constant over substantially the entire length of each nanowire. In other words, the nanowires are substantially cylindrical, of revolution or not, or substantially prismatic. Compared to nanowires having non-constant sections, constant section nanowires make it possible to improve the operation of a device using these constant section nanowires.

As for the chemical bath described in relation to FIG. 2, the chemical bath described in relation to FIG. 3 can be adapted to materials other than ZnO. For this, Zn (N0 ₃ ) ₂ and HMTA respectively constitute the first and second compounds described above, which may be different from Zn (N0 ₃ ) ₂ and HMTA. In particular, a person skilled in the art is able to determine, by routine tests: a concentration threshold so that, when the concentrations of the first and second compounds are below this threshold, the growth of the parts 310 orthogonally to the layer 130 is favored with respect to a transverse growth of the parts 310. This threshold can have a value of the order of 20 mM, for example equal to 20 mM; and / or additives also making it possible to promote the growth of the parts 310 orthogonally to the layer 130 with respect to a transverse growth of the parts 310.

Figures 4 to 6 are sectional views, partial and schematic, showing successive steps of a second embodiment of a nanowire manufacturing process.

At the step of Figure 4, there is provided a support 110 and a metal region 120, identical or similar to those described in relation to FIG. 1 and arranged in an identical or similar manner.

According to the embodiment shown, an initiating layer 410 is formed on the metal region 120. The future nanowires will be formed on and in contact with the free surface of the initiating layer 410. Preferably, the layer priming 410 comprises, for example consists of, the same material as that of the future nanowires. Preferably, the initiating layer 410 is made of ZnO. More preferably, the initiating layer is a layer of ZnO nanoparticles. By nanoparticles is meant particles whose largest dimensions are less than one micrometer, preferably less than 500 nm. In an alternative (not shown), the metallic region 120 is omitted. In another variation (not shown), layer 410 and metallic region 120 are omitted and the upper surface of support 110 defines an initiation surface.

According to another embodiment, the layer 410 is omitted and the surface of the metallic region 120 constitutes an initiation surface, as described in relation to FIGS. 1 to 3.

A deoxyribonucleic acid origami DNA 430 is formed on the priming surface. The term DNA origami is understood to mean a three-dimensional structure formed by a set of folded DNA strands. Parts of the different DNA strands are attached to each other by staples. The staples are preferably pieces of DNA. The bases of the DNA strands are chosen, for example using standard software, so that the folding of the DNA strands in aqueous solution in the presence of the staples forms the desired three-dimensional structure.

The DNA origami 430 is in contact with the priming surface and covers all or part of the priming surface Thus, the DNA origami 430 is preferably located on the layers 120 and 410. In the case where the layer 410 is omitted and the metallic layer 420 is gold and defines the priming layer, one can provide thiol groups to hang DNA origami 430 on the priming surface.

The DNA origami 430 has through openings 435. The DNA origami 430 has an average thickness C, defined outside the openings. The mean thickness C is preferably uniform over the entire priming surface or over the part of the priming surface covered by the DNA origami. Thus, DNA origami has the three-dimensional structure of a perforated layer. Preferably, the average thickness C is between a few nanometers, that is to say between of the order of 2 nm to 10 nm, and a few tens of nanometers, that is to say between order of 20 nm and 100 nm. more preferably, the average thickness C is of the order of 10 nm, for example equal to 10 nm.

The openings 435 are preferably arranged in a network, more preferably in a regular network such as a network having, in top view, a symmetry of order two, three, four or six. The openings 435 are preferably arranged in a matrix, the matrix having the same row and column pitches. By way of example, the row and column pitch is between 15 nm and 30 nm, preferably equal to 20 nm or to 25 nm.

Each opening 435 has for example the shape of a rectangular or, preferably, square section. The section of each opening 435 can also have a rounded shape, for example substantially circular. Preferably, all of the openings 435 have the same sectional shape and the same section dimensions.

The openings 435 have for example a transverse dimension Al of less than 100 nm, preferably less than 40 nm, more preferably less than 20 nm, even more preferably less than 15 nm. The transverse dimension Al is also preferably greater than 5 nm. More preferably, the transverse dimension Al is of the order of 10 nm. Preferably, the array of openings 435 has a distance B1 between neighboring openings of between 0.5 and 3 times the transverse dimension Al of the openings 435.

In the step of FIG. 5, the openings 435 are filled with the material of the nanowires. Portions 210 of the material are thus formed in the openings 435. Portions 210 extend from the initiating surface. More precisely, the portions 210 are in contact with the initiating layer 410, or, if the latter is omitted, with the metallic layer 120. The material of the portions 210 can be any material that can be formed by deposition in a chemical bath, as described in relation to FIG. 2. Thus, the material of the portions 210 can be a metal oxide such as NiO, AgO, CU2O, or for example CdO. The deposited material can also be a metal hydroxide, preferably FeOOH or Cu (OH) 2- The deposited material can also be a chalcogenide, CdS, ZnS, PbS, CdSe, ZnSe, or for example NiSe. Preferably, the deposited material has piezoelectric properties, more preferably, the material of the portions 210 is zinc oxide (ZnO).

Preferably, the portions 210 are formed by deposition in a chemical bath, in the manner described in relation to FIG. 2. This is not limiting, and the portions 210 can be formed by any usual process making it possible to form portions in through openings of a perforated layer. By way of example, the deposition can be carried out in the presence or in the absence of an electric field, or by electrolysis. The deposit can also be made on any the surface of the structure obtained in the step of FIG. 4, the parts located above the upper level of the DNA origami 430 then being optionally removed, in part or in whole, for example by polishing.

Preferably, in the step of FIG. 6, the DNA origami (430, FIG. 5) is removed. This removal is for example carried out by a plasma suitable for etching the DNA origami selectively with respect to the material of the portions 210.

According to one embodiment, each portion 210 constitutes a nanowire. Preferably, the portions 210 completely fill the openings (435, FIG. 5), and the length of the nanowires is then equal to the thickness C (FIG. 4) of the DNA origami (430, FIG. 5).

[0100] According to another embodiment, each nanowire is formed by depositing in a chemical bath on one of the portions 210, in the manner described above in relation to FIG. 3. The nanowires then preferably have a greater length. at 500 n, more preferably greater than 1 μm. The step of FIG. 6 can then be omitted.

[0101] As a variant, one could think of replacing the origami of DNA with a perforated layer such as layer 130 of the method of FIGS. 1 to 3, this perforated layer being obtained by electron lithography, by ultraviolet radiation, or by a from a block copolymer. However, compared to such a variant, DNA origami makes it possible to obtain nanowires of smaller diameter and / or to achieve a greater density of nanowires on the surface. By way of example, the diameter of the nanowires can be less than 10 nm. In addition, the density of the nanowires is preferably greater than 10 nanowires per pm ² , for example greater than 50 nanowires per pm ² , preferably equal to or greater than 625 per pm ² , or even equal to, or greater than, 1600 per. pm ² . DNA origami thus makes it possible to improve the precision and the sensitivity of a sensor using the nanowires obtained.

[0102] FIGS. 7 to 9 are partial and schematic sectional views showing steps of an example of a method for manufacturing a sensor comprising nanowires. This method implements the steps of Figures 1 to 3 or the steps of Figures 4 to 6. The sensor is for example a fingerprint sensor. In particular, the sensor comprises a matrix of pixels. A single pixel has been represented, the other pixels being similar or identical to the pixel represented.

In the step of FIG. 7, a support 110 is provided consisting of a semiconductor substrate, for example made of silicon. Preferably, for each pixel, the sensor comprises a circuit, not shown, for controlling / reading the pixel, comprising transistors, for example MOS type transistors. The circuit is preferably of the CMOS type.

Preferably, all or part of the transistors of the circuit associated with each pixel are located in and on the substrate 110, directly above a location 710 in which the nanowires will be formed. The location 710 of each pixel typically has a square shape when viewed from above. For example, the side dimensions of location 710 are between 0.8 µm and 1.5 µm, preferably are about 1 µm, more preferably are 1 µm.

Each pixel comprises two electrically conductive regions 720 and 722 located on the side of the front face of the substrate 110 (that is to say in the upper part of the substrate). Electrically conductive regions 722 are electrically connected to the circuit associated with the pixel. The front face of the substrate 110 is covered with an electrically insulating layer 730, typically made of silicon oxide. The insulating layer 730 is crossed right through by a conductive via 732 located on the conductive region 722.

Next, a metallic layer 740 covering the insulating layer 730 is formed. The metallic layer 740 constitutes a metallic conductive region. The conductive via 732 puts the metal layer 740 in electrical contact with the conductive region 722. An opening 742 is provided in the metal layer 740 in line with, that is to say opposite, the region. conductive 720. The metallic layer 740 is identical or similar to the metallic layer 120 of the embodiments described in relation to FIGS. 1 to 6.

Nanowires 750 are formed on the metal layer 740 in the manner described above in relation to FIGS. 1 to 3 and / or with FIGS. 4 to 6 to form the nanowires 210 or 320. Preferably, the nanowires 750 are in contact with the metal layer 740.

Preferably, the nanowires 750 are formed only at the location 710. For this, in the case where the nanowires 750 are formed in an aqueous solution such as a chemical bath, the surface of the metal layer 740 can be hydrophobic outside of location 710.

In the step of FIG. 8, a polymer layer 810 is formed, filling the space between the nanowires 750. The layer 810 thus forms an electrically insulating polymer matrix. More precisely, the polymer is more flexible than the material of the nanowires 750, that is to say that it has a lower modulus of elasticity, for example more than 10 times lower, than that of the nanowires 750. Preferably, the layer 810 is formed such that the upper end of the nanowires 750, i.e. the end of the nanowires 750 opposite the region metal 740, is flush with the upper surface of the layer 810. Preferably, the layer 810 covers the front face of the structure obtained in the step of FIG. 7 outside the location 710. The layer 810 is in contact with the insulating layer 730 in the opening 742 of the metal layer 740.

In the step of FIG. 9, a conductive via 910 is formed passing through the layer 810 right through and located directly above the conductive region 720. The conductive via 910 passes through the opening 742 of the conductive layer 740. The conductive via 910 is isolated from the side walls of the opening 742 by portions of the layer 810.

An electrically conductive region 920 covering the nanowires 750 is also formed. The conductive region 920 is in contact with the upper ends of the nanowires 750. The conductive region 920 can be made of the same material as the via 910. The regions 920 and the material of via 910 can then be formed simultaneously. The conductive region 920 can also be formed after the material of the via 910, and the conductive region 920 and the conductive via 910 can then be of different materials. Alternatively, the material of the conductive layer 920 is transparent over a range of wavelengths. By way of example, the wavelength range corresponds to visible radiation, that is to say between approximately 400 nm and approximately 800 nm. By transparent layer is meant that more than 50%, preferably more than 90%, of any radiation in the wavelength range entering the layer perpendicularly through one of the main faces of the layer (parallel to the plane of the layer) emerges from the layer by the other of the main faces. In this variant, the layer 810 is also transparent. When the sensor is subjected to radiation passing through the conductive layer 920, this radiation can thus be detected thanks to its interaction with the nanowires.

Preferably, the conductive regions 920 of the neighboring pixels are isolated from each other. For this, the conductive regions 920 are preferably obtained by steps consisting in: forming a conductive layer comprising the future conductive regions 920; covering this conductive layer with a lithographed layer, not shown, having openings outside the locations of the conductive regions 920; and etching the parts of the conductive layer located directly above the openings of the lithographed layer.

In each pixel thus obtained, the nanowires 750 are arranged parallel to each other and have their ends in respective contact with the conductive regions 740 and 920. The conductive regions 740 and 920 are in electrical contact with the respective regions 722 and 720 via the respective vias 732 and 910. The regions 722 and 720 constitute electrodes of the pixel.

The fact that the substrate 110 comprises, directly above each pixel, at least part of the circuit associated with this pixel, allows, with respect to a sensor in which the circuits are not directly above the pixels , to increase the compactness and / or the resolution of the sensor. In addition, the fact that the nanowires have transverse dimensions as defined above, makes it possible, compared to nanowires having higher lateral dimensions, to reduce the size of the pixels and thus to increase the resolution of the sensor. Thus, the resolution of the sensor obtained can be less than 50 μm, preferably of the order of 1 μm.

Preferably, the nanowires are piezoelectric, that is to say are made of a piezoelectric material. In operation, a pressure or a force exerted on the region 920, for example in the direction of the bottom of FIG. 9, deforms the nanowires and causes a potential difference measured by the circuit associated with the pixel. For this, by way of example, the material of the nanowires is chosen from among zinc oxide, ZnO, cadmium sulphide, CdS, and cadmium selenide, CdSe. The piezoelectric material can also be chosen from materials having a crystalline structure of the wurtzite type. Nanowires can also include several of these materials.

It is preferred that the metallic region 740 is directly in contact with the nanowires 750. An electrical contact of Schottky type is thus preferably formed between the metallic region 740 and the nanowires 750. The sensitivity of the sensor is then advantageously , greater than that of a similar sensor but also comprising a layer such as layer 410 (FIGS. 4 to 6) located between the metallic region 740 and the nanowires 750.

Various embodiments and variants have been described. Those skilled in the art will understand that certain features of these various embodiments and variants could be combined, and other variants will be apparent to those skilled in the art.

In particular, although we have more particularly described embodiments in which the formation of the origami 430 on the layer 120 or 740 is carried out while this layer is carried by the support 110, it is possible to provide, according to another embodiment, to form the origami 430 on the layer 120 before attaching the latter to the support or substrate 110.

[0120] Finally, the practical implementation of the embodiments and variants described is within the reach of man. of the trade based on the functional indications given above.

Claims

A method of forming nanowires (210; 750), comprising forming a DNA origami (430) having through openings (435), and forming in the through openings (435) portions (210) constituting all or part of the nanowires (210; 750).

2. The method of claim 1, wherein the origami and the openings it comprises are made before fixing the origami on a substrate.

3. The method of claim 1 or 2, wherein said portions (210) are deposited in a chemical bath.

4. A method according to any one of claims 1 to 3, wherein said portions (210) constitute first parts of the nanowires (320), and second parts (310) of the nanowires extending from the first parts are deposited. in a chemical bath.

5. The method of claim 4, wherein the composition of the chemical bath is different for the formations of the first (210) and second parts (310).

6. A method according to any one of claims 1 to 5, comprising forming a polymer matrix (810) between the nanowires (750).

7. A method according to any one of claims 1 to 6, comprising removing at least a portion of the DNA origami (430).

8. A device obtained by a method according to any one of claims 1 to 7, wherein the origami comprises folded DNA strands having parts attached to each other by staples.

9. The device of claim 8, wherein the DNA origami (430) is located on a layer (410) of the same material as that of the nanowires, said portions (210) extending from said layer ( 410).

10. Device according to claim 8 or 9, wherein the DNA origami (430) is located on a metallic region (120; 740) and, preferably:

- Said metallic region has a thickness greater than 100 nm; and or

- said portions (210) extend from said metallic region (120; 740).

11. Device according to claim 10, comprising, at one end of the nanowires (750) opposite to said metallic region (740), an electrically conductive region in contact with the nanowires (750).

12. Device according to claim 10 or 11, wherein:

- the metallic region (120; 740) comprises at least one of the materials from the group consisting of gold, nickel, copper, palladium and platinum; and or

- the nanowires (750) are piezoelectric, preferably, the nanowires (750) having a crystalline structure of the wurtzite type and / or comprise at least one of the materials from the group consisting of zinc oxide, cadmium sulphide, selenide cadmium, and nickel selenide.

13. Device according to any one of claims 8 to 12, wherein:

- the nanowires (210; 750) have a transverse dimension less than 40 nm, preferably less than 20 nm;

- the nanowires (210; 750) have a length greater than

500 nm, preferably greater than 1 µm; and / or the nanowires (210; 750) have a density greater than 10 nanowires per square micrometer, preferably greater than 50 nanowires per square micrometer; and or

- DNA origami (430) has a thickness (C) of between the order of 2 nm and the order of 100 nm, preferably of the order of 10 nm.

14. A sensor pixel, comprising a device according to any one of claims 8 to 13.

15. A sensor, preferably fingerprint, comprising several pixels according to claim 14.

16. Sensor according to claim 15, in which the pixels are located on the side of a face of the substrate (110) comprising, directly above each pixel, at least part of a circuit associated with this pixel.