METHOD OF MAKING A QUANTUM DEVICE
20220172093 · 2022-06-02
Assignee
Inventors
- Nicolas POSSEME (Grenoble Cedex 09, FR)
- Louis HUTIN (Grenoble Cedex 09, FR)
- Cyrille LE ROYER (GRENOBLE CEDEX 09, FR)
- François LEFLOCH (Grenoble Cedex 09, FR)
- Fabrice NEMOUCHI (GRENOBLE CEDEX 09, FR)
- Maud VINET (Grenoble Cedex 09, FR)
Cpc classification
G06N10/40
PHYSICS
G06N10/00
PHYSICS
H01L29/66977
ELECTRICITY
H10N60/128
ELECTRICITY
International classification
G06N10/00
PHYSICS
H01L29/66
ELECTRICITY
Abstract
A method for producing a quantum device comprising providing a substrate having a front face and carrying at least one transistor pattern on the front face thereof, said transistor pattern comprising, in a stack a gate dielectric on the front face of the substrate, and a gate on the gate dielectric, said gate having a top and sidewalls. The method further includes forming a protective layer at the front face of the substrate, said protective layer being configured to prevent diffusion of at least one metal species in the substrate, forming a metal layer that has, as a main component, at least one metal species, at least on the sidewalls of the gate, said at least one metal species comprising at least one superconducting element, and forming a superconducting region in the gate by lateral diffusion of the at least one superconducting element from the sidewalls of said gate.
Claims
1. A method for producing a quantum device, comprising: providing a substrate having a front face and carrying at least one transistor pattern on the front face thereof, said transistor pattern comprising, in a stack: a gate dielectric on the front face of the substrate, and a gate on the gate dielectric, said gate having a top and sidewalls, forming a protective layer at the front face of the substrate, said protective layer being configured to prevent diffusion of at least one metal species in the substrate, forming a metal layer based on at least one metal species at least on the sidewalls of the gate, and forming a superconducting region in the gate by lateral diffusion of the at least one metal species from the sidewalls of said gate.
2. The method according to claim 1, wherein the transistor pattern provided further comprises a hard mask on the top of the gate, said hard mask being configured to prevent diffusion of at least one metal species in the gate from said top, such that the formation of the superconducting region only occurs by lateral diffusion from the sidewalls of the gate.
3. The method according to claim 1, wherein the metal layer formed comprises at least one metal species chosen from cobalt, platinum, and vanadium.
4. The method according to claim 1, wherein the metal layer is formed by conformal deposition of metal on the transistor pattern and on the protective layer on the front face of the substrate.
5. The method according to claim 1, wherein the gate has a width Lg and the metal layer formed has a thickness em≥Lg/5.
6. The method according to claim 1, wherein lateral diffusion is carried out by thermal annealing.
7. The method according to claim 1, wherein the protective layer formed at the front face of the substrate has a thickness greater than or equal to 2 nm when forming the superconducting region.
8. The method according to claim 1, wherein forming the protective layer comprises: oxidising, in a differentiated manner, the front face of the substrate and the sidewalls of the gate, such that the thickness ef of oxide formed at the sidewalls of the gate is strictly less than the thickness es of oxide formed at the front face of the substrate, such that ef≤k.Math.es where k≤0.8 and preferably k≤0.5, and removing the oxide formed at the sidewalls of the gate, said removal being configured to retain at least some of the oxide formed at the front face of the substrate so as to form the protective layer.
9. The method according to claim 8, wherein the differentiated oxidation is carried out using at least one plasma comprising oxygen-based species and hydrogen-based species.
10. The method according to claim 9, wherein the hydrogen-based species are chosen from dihydrogen H2, ammonia NH3, and boron hydride HBr.
11. The method according to claim 8, wherein the removal of the oxide formed at the sidewalls of the gate is carried out by wet etching.
12. The method according to claim 1, wherein forming the protective layer comprises: depositing an oxide on the front face of the substrate and on the sidewalls of the gate, and partially removing the oxide deposited so as to leave an oxide layer on the front face of the substrate, said oxide layer having a thickness e′s greater than or equal to the thickness eg of the gate dielectric of the transistor pattern.
13. The method according to claim 12, wherein the sidewalls of the gate are exposed over at least 90% of the height thereof, after the deposited oxide has been removed.
14. The method according to claim 12, wherein the oxide is deposited by spinning.
15. The method according to claim 1, wherein the substrate carries a plurality of transistor patterns and wherein a subset of the plurality of transistor patterns is masked prior to the formation of the metal layer so as to prevent the formation of superconducting regions in the gates of the transistor patterns of said subset.
Description
BRIEF DESCRIPTION OF THE FIGURES
[0030] The aims, purposes, features and advantages of the invention will be better understood upon reading the detailed description of embodiments thereof, which are shown by means of the following accompanying drawings, in which:
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[0042] The drawings are provided by way of example and are not intended to limit the scope of the invention. They constitute diagrammatic views intended to ease the understanding of the invention and are not necessarily to the scale of practical applications. In particular, the relative dimensions of the different layers, portions and elements of the device (for example the spacer, the active layer, the protective layer, the source/drain region, the gate, or the hard mask) are not representative of reality.
DETAILED DESCRIPTION
[0043] Before giving a detailed review of embodiments of the invention, optional features are set out below, which can be used in combination with or in replacement of one another.
[0044] According to one example, the transistor pattern provided further comprises a hard mask on the top of the gate, said hard mask being configured to prevent diffusion of at least one metal species in the gate from said top, such that the formation of the superconducting region only occurs by lateral diffusion from the sidewalls of the gate. This results in a relatively planar diffusion front progressing from each of the sidewalls to a median plane in the centre of the gate. This improves the quality of the superconducting region thus formed.
[0045] According to one example, the metal layer formed comprises at least one metal species chosen from cobalt, platinum and vanadium.
[0046] According to one example, the metal layer is formed by conformal deposition of metal on the transistor pattern and on the protective layer on the front face of the substrate.
[0047] According to one example, the metal layer is formed by CVD (Chemical Vapour Deposition) or ALD (Atomic Layer Deposition). This allows the at least one metal species to be deposited on the sidewalls of the gate.
[0048] According to one example, the metal layer is formed by PVD (Physical Vapour Deposition) with conditions that allow for redeposition or sputtering (resputtering) from the bottom of the patterns to the sidewalls of the gate, typically by plasma treatment. According to one example, the metal layer is formed by low directional PVD. This allows the at least one metal species to be deposited on the sidewalls of the gate.
[0049] According to one example, lateral diffusion is configured so as to propagate the at least one metal species from each of the sidewalls of the gate at least to the centre of the gate, such that the superconducting region is formed across an entire width L.sub.g of the gate. The gate is thus entirely superconducting. This improves the control of the quantum device thus formed.
[0050] According to one example, the gate has a width L.sub.g≤40 nm, preferably L.sub.g≤30 nm, more preferably L.sub.g≤25 nm, most preferably L.sub.g≤20 nm. This reduces the total number of entangled qubits in the device.
[0051] According to one example, the gate has a width L.sub.g and the metal layer formed has a thickness e.sub.m≥L.sub.g/5. This ensures that there is a sufficient amount of metal species in the metal layer, such that the entire gate can be made superconducting as a result of the lateral diffusion. The thickness e.sub.m can also depend on the metal used and/or the nature of the gate.
[0052] According to one example, lateral diffusion is achieved by thermal annealing, for example by RCA (Rapid Thermal Annealing). The conditions for lateral diffusion or lateral silicidation can in particular depend on the metal used and the target phase. The table below gives examples of thickness ratios between different metals (Co, Pt and V) and silicon. The annealing environment can be in an Ar, He or N.sub.2 inert gas.
TABLE-US-00001 Silicide T ° C. range Time range Annealed Metal Silicon formed Advantageous Advantageous in (nm) (nm) (nm) range range Ar, He Pt Si PtSi 400° C. to 700° C. 10 s to 300 s A single 1.00 1.35 1.98 450° C. to 550° C. 60 s to 120 s RTA-type anneal 2 Co Si Co.sub.2Si 550° C. to 900° C. 10 s to 300 s 2 1.00 0.91 1.47 600° C. to 800° C. 60 s to 120 s RTA-type annealing steps V Si V3Si 600° C. to 1000° C. 10 s to 1000 s A single 1.00 0.48 1.26 750° C. to 850° C. 60 s to 500 s RTA-type anneal
[0053] In the case of lateral silicidation, the thickness of the Si consumed is preferably less than or equal to half the gate width. This prevents the formation of a polyphase superconducting zone.
[0054] According to one example, the protective layer formed at the front face of the substrate has a thickness e′.sub.s greater than or equal to 2 nm during the formation of the superconducting region. This improves the sealing of the protective layer against the diffusion of metal species.
[0055] According to one example, the formation of the protective layer comprises the following sub-steps of: [0056] Oxidising, in a differentiated manner, the front face of the substrate and the sidewalls of the gate, such that the thickness ef of oxide formed at the sidewalls of the gate is strictly less than the thickness es of oxide formed at the front face of the substrate, such that ef≤k.Math.es where k≤0.8 and preferably k≤0.5, [0057] Removing the oxide formed at the sidewalls of the gate, said removal being configured to retain at least some of the oxide formed at the front face of the substrate. [0058] Such differentiated oxidation is easily controlled.
[0059] According to one example, differentiated oxidation is carried out using at least one plasma comprising oxygen-based species and hydrogen-based species.
[0060] According to one example, the hydrogen-based species are chosen from dihydrogen H2, ammonia NH3 and boron hydride HBr.
[0061] According to one example, the at least one plasma comprises: [0062] a first anisotropic hydrogen-based plasma mainly directed in a direction normal to the front face of the substrate, said first plasma being configured to modify a substrate portion to a depth ds from the front face, and to modify a gate portion over a width df from the sidewalls, where df≤k.Math.ds, where k≤0.8 and preferably where k≤0.5, [0063] a second oxygen-based plasma configured to oxidise the modified substrate and gate portions. [0064] The substrate and gate portions are thus modified and then oxidised sequentially. This improves control of the differentiated oxidation, in particular in terms of depth ds and thickness df.
[0065] According to one example, the first plasma follows the second plasma.
[0066] According to one example, the first plasma is a hydrogen H2 plasma and the second plasma is an oxygen O2 plasma.
[0067] According to one example, the first and second plasmas are carried out simultaneously using HBr/O2 plasma chemistry. This reduces the number of steps. HBr/O2 plasma chemistry can also be used to etch and form the transistor pattern. The steps of providing the transistor pattern and of forming the protective layer can thus be partly combined.
[0068] According to one example, the oxide formed at the sidewalls of the gate is removed by wet etching.
[0069] According to one example, the formation of the protective layer comprises the following sub-steps of: [0070] Depositing an oxide on the front face of the substrate and on the sidewalls of the gate, [0071] Partially removing the oxide deposited so as to leave an oxide layer on the front face of the substrate, said oxide layer having a thickness es greater than or equal to the thickness eg of the gate dielectric of the transistor pattern. This prevents the subsequent formation of a recess in the substrate.
[0072] According to one example, the sidewalls of the gate are exposed over at least 90% of the height h.sub.g thereof, after the deposited oxide has been removed.
[0073] According to one example, the oxide is deposited by spinning.
[0074] According to one example, the substrate carries a plurality of transistor patterns.
[0075] According to one example, a subset of the plurality of transistor patterns is masked prior to the formation of the metal layer so as to prevent the formation of superconducting regions in the gates of the transistor patterns of said subset. This allows quantum devices to be co-integrated with transistors, for example FDSOI CMOS transistors, on the same substrate.
[0076] Unless specifically indicated otherwise, technical features described in detail for a given embodiment can be combined with the technical features described within the context of other embodiments described by way of example and in a non-limiting manner. In particular, the shape or number of the source and drain regions shown in the figures can be combined to form another embodiment which is not necessarily illustrated or described. It goes without saying that such an embodiment is not excluded from the scope of the invention.
[0077] It is specified that, within the scope of the present invention, the terms “on”, “overlying”, “covers” or “underlying” or the equivalents thereof do not necessarily mean “in contact with”. Thus, for example, a hard mask on a gate does not necessarily mean that the hard mask and the gate are directly in contact with one another, but rather means that the hard mask covers at least partially the gate while being either directly in contact therewith, or while being separated therefrom by at least one other layer or at least one other element.
[0078] Moreover, a layer can be constituted by a plurality of sub-layers made of the same material or made of different materials.
[0079] A substrate, layer, or device, “based on” a material M is understood to mean a substrate, a layer, or a device comprising this material M only or comprising this material M and optionally other materials, for example alloying elements, impurities or doping elements. Thus, a spacer having a silicon nitride SiN base can, for example, comprise non-stoichiometric silicon nitride (SiN) or stoichiometric silicon nitride (Si3N4), or even a silicon oxynitride (SiON).
[0080] Typically, but in a non-limiting manner, a spacer forms a ring around the gate with a closed contour; the description of a spacer preferably refers to this single spacer around the gate; however, illustrative sectional drawings, generally viewed along a plane parallel to the longitudinal direction of the channel, show two spacer parts on either side of the sidewalls of the gate. By extension, these two spacer parts are often referred to as “the spacers”. The latter terminology may be adopted in this application. Furthermore, the invention relates to embodiments wherein at least two discontinuous spacers cover a gate pattern.
[0081] The present invention in particular allows at least one quantum device or a plurality of quantum devices to be manufactured on a substrate. This substrate can be a “bulk” substrate, or even of the semiconductor on insulator type, for example a silicon on insulator (SOI) substrate or a germanium on insulator (GeOI) substrate.
[0082] The invention can also be implemented more widely for various microelectronic devices or components.
[0083] A microelectronic component, device or device element is understood to mean any type of element made using microelectronic means. In addition to devices intended for purely electronic purposes, these devices in particular include micromechanical or electromechanical devices (MEMS, NEMS, etc.) as well as optical or optoelectronic devices (MOEMS, etc.).
[0084] Several embodiments of the invention implementing successive steps of the manufacturing method are described hereinbelow. Unless specified otherwise, the adjective “successive” does not necessarily imply that the steps immediately follow on from one another, although this is generally preferred, and they can be separated by intermediate steps. Moreover, the term “step” is understood to mean the performance of a part of the method, and can denote a set of sub-steps.
[0085] In particular, the step of forming the protective layer can occur in part at the end of the step of providing the transistor pattern, such that these two steps are partly coincident. This is the case, for example, when a HBr/O2 plasma is used to etch and form the transistor pattern. This plasma can be extended, preferably by varying the conditions of said plasma, so as to form the protective layer.
[0086] The term “dielectric” qualifies a material whose electric conductivity is low enough in the given application to act as an insulator. In the present invention, a dielectric material preferably has a dielectric constant of less than 7. The spacers are typically made of a dielectric material.
[0087] The terms “gate pattern”, “gate stack” and “gate” are used synonymously.
[0088] “Etching selectively to” or “etching with selectivity to” are understood to mean an etch that is configured so as to remove a material A or a layer A from a material B or from a layer B, and having an etch rate of the material A that is greater than the etch rate of the material B. Selectivity is the ratio of the etch rate of the material A to the etch rate of the material B.
[0089] The present patent application preferentially employs the term thickness for a layer, height for a device (for example a gate) and depth for a recess or an etch. The thickness is considered in a direction normal to the main plane of extension of the layer, the height and the depth are considered in a direction normal to the base plane of the substrate. The main extension plane of the layer, respectively the base plane of the substrate, is generally parallel to a bottom face or top face of this layer, respectively of this substrate.
[0090] In the present patent application, a preferably orthonormal coordinate system formed by the axes x, y, z is shown in the accompanying drawings. The substrate, more specifically the bottom face and/or the top face thereof, extends in the basal plane xy.
[0091] In the description hereafter, the length is considered in the direction shown by the x-axis, referred to as the longitudinal axis, and the width is considered in the direction shown by the y-axis.
[0092] An element located “vertical to” or “in line with” another element means that these two elements are both located on the same line perpendicular to the basal plane, i.e. on the same line oriented along the z-axis in the figures.
[0093] “Horizontal” is understood to mean an orientation parallel to a plane xy. “Vertical” is understood to mean an orientation parallel to the z-axis.
[0094] The terms “substantially”, “about”, and “in the order of” mean “to within 10%” or, when referring to an angular orientation, “to within 10°”. Thus, a direction substantially normal to a plane means a direction having an angle of 90±10° relative to the plane.
[0095] The invention will now be described in detail by way of several non-limiting embodiments.
[0096] A first embodiment of the method is shown in
[0097] Two transistor patterns 2 each comprising a gate dielectric 21, a gate 22a and a hard mask 40 stacked on a substrate 1 are provided 100 (
[0098] According to another embodiment, the device is produced on a solid silicon substrate. In such a case, a dopant introduction step can be provided in order to ensure electron confinement, and/or dielectric materials, other than silicon oxide, can be provided. These dielectrics are, for example, nitride- or alumina-based.
[0099] The provision 100 of the two transistor patterns 2 corresponds, in this case, to the formation of these transistor patterns 2. In particular, the gates 22a are etched by conventional plasma etching, for example using HBr/O2 plasma. After this etching, a protective layer 111 (
[0100] In particular, the sidewalls 221 of each gate 22a are oxidised to a thickness e.sub.f to form the oxide 222 (
[0101] This over-etching step can be carried out using a hydrogen-based plasma and an oxygen-based plasma. According to one example, the HBr/O2 plasma used to etch the gates 22a is adapted to oxidise, in a differentiated manner, the sidewalls 221 and the front face 101 at the end of the etching of the gates 22a. For example, the HBr/O2 mixture is 40:1 (for example 200 sccm HBr to 5 sccm O2). The pressure is less than 50 mTorr, preferably less than 10 mTorr (for example 6 mTorr). The source power is greater than 200 W, preferably greater than 400 W (typically 500 W). The bias voltage is greater than 50 V, preferably greater than 60 V (typically 80 V). The temperature of the substrate is comprised between 50° C. and 70° C., preferably in the order of 60° C.
[0102] According to another example, the over-etching step is carried out sequentially by a first hydrogen-based plasma, for example having, as a main component, dihydrogen H2 or ammonia NH3, followed by a second oxygen-based plasma O2. The first plasma is used in this case to modify both the material of the active layer 11 to a depth d.sub.s from the front face 101, and the material of the gate 22a over a width d.sub.f from the sidewalls 221. The portions modified by this first plasma are not etched. This first plasma is configured such that the width d.sub.f is strictly less, for example at least 20% less and preferably at least 50% less, than the depth d.sub.s. The width d.sub.f can be comprised between 1 nm and 4 nm. The depth d.sub.s can be comprised between 3 nm and 10 nm.
[0103] The second plasma allows the portions of the active layer 11 and of the gate 22a modified by the first plasma to be oxidised. This forms the oxide 111 of thickness e.sub.s and the oxide 222 of thickness e.sub.f. In a known manner, the oxide formed by oxidation of silicon can be larger in volume than the silicon consumed during oxidation. Thus, the oxide 111 can typically extend beneath the front face 101 and above the front face 101, such that the depth d.sub.s is not necessarily equal to the thickness e.sub.s.
[0104] At the end of the over-etching step, a thin oxide 222 is formed on the sidewalls 221 of the gate 22a and a thick oxide 111 is formed on the front face 101 of the active layer 11. The next step involves removing 111b the thin oxide 222 from the sidewalls 221 of the gate 22a (
[0105] After removal 111b, the sidewalls 221 of the gate 22a are exposed again. Prior to the deposition of a metal layer 50, the sidewalls 221 can be cleaned, for example by argon or helium plasma. The metal layer 50 can be conformally deposited on the transistor patterns 2 and on the protective layer 111 (
[0106] The superconducting region 22b is formed 120 within the gate 22a by lateral diffusion of the metal species from the sidewalls 221, i.e. mainly along y. This lateral diffusion is preferably configured such that the superconducting region 22b is formed over the entire width L.sub.g of the gate 22a, (
[0107] Advantageously, the protective layer 111 prevents the metal species from diffusing in the active layer 11. After formation 130 of the superconducting region 22b, the metal residues are preferably cleaned, for example with a hydrogen peroxide H2O2-based solution, such as Caro's acid (H.sub.2O.sub.2:H.sub.2SO4), or aqua regia (HCl:HNO3) and/or with an SC1 (H.sub.2O:H.sub.2O.sub.2:NH.sub.4OH).
[0108] The protective layer 111 can then be removed 140a to expose the active layer 11 (
[0109] As shown in
[0110] Standard silicidation 401 of the source and drain regions 31 can then be carried out to form silicided portions 32 (
[0111] A second embodiment of the method is shown in
[0112] Two transistor patterns 2 each comprising a gate dielectric 21, a gate 22a and a hard mask 40 stacked on a substrate 1 are in this case provided 100 (
[0113] In this case, the formation 110 of the protective layer begins after the etching of the gates 22a. This formation 110 is typically carried out in two steps: an oxide layer 60 is firstly formed between the transistor patterns 2, on the front face 101, as shown in
[0114] Partial removal 112b of this oxide layer 60 is then carried out to form a protective layer 112 of thickness e.sub.s (
[0115] This partial removal 112b can be carried out by HF-based wet etching or by fluorocarbon plasma etching. A HF solution diluted to the order of 0.1% to 1% is preferably used. This procures good etch selectivity relative to the gate 22a and/or to the hard mask 40. Removal 112b can also be carried out by a SiCoNi™ type method, which typically comprises a delocalised plasma having, as a main component, an NF3/NH3 mixture followed by sublimation annealing.
[0116] The sidewalls 221 of the gate 22a are partially exposed after this removal 112b, over at least 80% of the height h.sub.g thereof, and preferably over at least 90% of the height h.sub.g thereof. The metal layer 50 is then deposited 120 on the exposed sidewalls 221 of the transistor patterns, as shown in
[0117] After the formation 130 of the superconducting region 22b, the metal residues are preferably cleaned and then the protective layer 112 is removed 140b so as to expose the front face 101 of the active layer 11 (
[0118] The subsequent steps of forming 200 the spacers 20 (
[0119] Other embodiments are also possible.
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[0122] The invention is not limited to the aforementioned embodiments, and includes all embodiments compliant with the general concept thereof.