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    • 专利摘要:
    The invention relates to a method for producing a germanium tin (GeSn) -based stress-strain layer (12), comprising the following steps: - producing a semiconductor stack (10), comprising a layer based on tin germanium (GeSn) and having a non-zero initial voltage stress value; - structuring said semiconductor stack (10) to form: ○ a structured portion (20) and a peripheral portion (30), the structured portion (20) having a central portion (21) connected to the peripheral portion (30) by at least two side portions (22), the side portions (22) having an average width (b) greater than an average width (a) of the central portion (21); suspension of the structured part (20), the central portion (21) then having a final voltage stress value greater than the initial value.
    公开号:FR3055467A1
    申请号:FR1657987
    申请日:2016-08-26
    公开日:2018-03-02
    发明作者:Vincent Reboud；Jean Michel Hartmann；Vincent Calvo；Alexei Tchelnokov
    申请人:Commissariat a lEnergie Atomique CEA；Commissariat a lEnergie Atomique et aux Energies Alternatives CEA；
    IPC主号:
    专利说明:

    Holder (s): COMMISSIONER OF ATOMIC ENERGY AND ALTERNATIVE ENERGIES Public establishment.
    Extension request (s)
    Agent (s): INNOVATION COMPETENCE GROUP.
    (04) PROCESS FOR PRODUCING A TENSION-BASED LAYER BASED ON TIN GERMANIUM.
    FR 3 055 467 - A1 _ The invention relates to a process for producing a tensile stress layer (12) based on tin germanium (GeSn), comprising the following steps:
    - Production of a semiconductor stack (10), comprising a layer based on tin germanium (GeSn) and having a non-zero initial value of voltage stress;
    - structuring of said semiconductor stack (10) so as to form:
    O a structured part (20) and a peripheral part (30), the structured part (20) comprising a central portion (21) connected to the peripheral part (30) by at least two lateral portions (22),
    O the lateral portions (22) having an average width (b) greater than an average width (a) of the central portion (21); suspension of the structured part (20), the central portion (21) then having a final tension stress value greater than the initial value.

    PROCESS FOR PRODUCING A TENSION-CONSTRAINED LAYER BASED ON TIN GERMANIUM
    TECHNICAL FIELD [001] The field of the invention is that of producing a voltage-constrained layer based on tin germanium GeSn, with the particular aim of obtaining a structure of direct energy bands. The invention applies in particular to the production of a microelectronic or optoelectronic device comprising such a layer based on GeSn in voltage.
    STATE OF THE PRIOR ART In various microelectronic or optoelectronic applications, it may be advantageous to use a voltage-constrained layer produced on the basis of tin germanium. This is particularly the case for high performance transistors where the stress undergone by the material results in an increase in the speed of movement of the charge carriers, which improves the performance of such a transistor. This is also the case for light sources such as electrically pumped lasers, for which the emissive layer based on tin germanium can have a structure of direct energy bands by the application of a value voltage stress. sufficient.
    The article by Wirths et al entitled Tensely strained GeSn alloy os optical gain media, Appl. Phys. Lett. 103, 192110 (2013) describes an example of a process for producing a tensile stress layer based on tin germanium. This method comprises growing a thick intermediate layer Gei- y Sn y, partially or completely relaxed on a nucleation layer of germanium, and the growth on the intermediate layer a thin layer of Gei- x Sn x, so-called of interest, whose atomic proportion of tin xs n is lower than that ys n of the intermediate layer. The intermediate layer is said to be thick in the sense that its thickness is greater than the critical thickness from which the mechanical stresses undergone by the layer plastically relax. The thick intermediate layer of Gei- y Sn y has, at its upper surface, a lattice parameter greater than that of the layer of interest of Gei- x Sn x , which makes it possible to stress in tension the layer of interest. In this configuration, it is expected that a thin layer of Gei- x Sn x has a structure of direct energy bands when xs n is less than 10% and when ys n is greater than or equal to 12%. The authors do indeed obtain a thin layer with a direct band structure for xs n = 8% and ys n = 12%.
    However, this production method requires the production of an intermediate layer with a high atomic proportion of tin for the tensioning of the layer of interest Gei- x Sn x . However, the production of such a layer with a high atomic proportion of tin and of good crystalline quality is particularly difficult to obtain due, on the one hand, to the significant difference between the lattice parameter of germanium (aGe = 5.658Â ) and that of tin (as n = 6,489Â), and, on the other hand, the difference between the melting temperature of germanium (about 950 ° C) and that of tin (about 240 ° C) which can lead to tin demixing.
    PRESENTATION OF THE INVENTION The aim of the invention is to remedy at least in part the drawbacks of the prior art, and more particularly to propose a process for producing a so-called layer of interest, voltage stress, based on tin germanium, not requiring an intermediate layer based on germanium tin with a high proportion of tin. For this, the object of the invention is a process for producing a strained layer based on tin germanium, comprising the following steps:
    production of a semiconductor stack resting on a support layer by means of a sacrificial layer, said semiconductor stack comprising a nucleation layer and a so-called layer of interest based on tin germanium epitaxial from the nucleation layer, said stack having a non-zero initial value of voltage stress;
    structuring of said semiconductor stack so as to form:
    o a structured part and a peripheral part, the structured part comprising a central portion connected to the peripheral part by at least two lateral portions opposite one another with respect to the central portion, o the lateral portions having an average width greater than an average width of the central portion;
    suspension of the structured part by etching of the sacrificial layer located under the structured part, the so-called suspended central portion then having a final tension stress value greater than the initial value.
    Some preferred but non-limiting aspects of this process are as follows.
    The method may include the following steps:
    prior to step a) of realization, estimation of a value of atomic proportion of tin and of a first minimum value of stress in tension for which the layer of interest presents a structure of bands of direct energy; and determining a semiconductor stack comprising a nucleation layer and said estimated layer of interest, and having a second minimum voltage stress value;
    making said semiconductor stack so that it has said initial non-zero voltage stress value and the layer of interest has an initial value less than said first minimum value;
    determination of the structuring so that, after the suspension step, the central portion of the structured portion has a final tension stress value greater than or equal to said second minimum value, said layer of interest then having a final value of voltage stress greater than or equal to said first minimum value and then having a structure of direct energy bands.
    The nucleation layer can be made of a semiconductor compound having a lattice parameter, called natural, lower than that of the material based on tin germanium of the layer of interest.
    The semiconductor stack may comprise at least one layer located between the layer of interest and the nucleation layer produced from a semiconductor compound having a lattice parameter, called natural, less than or equal to that of the germanium-based material tin of the layer of interest.
    The semiconductor stack may have a thickness less than a so-called critical thickness.
    Each layer of the semiconductor stack may have a thickness less than a so-called critical thickness.
    The semiconductor stack may include upper and lower layers based on tin germanium, doped with different types of conductivity, located on either side of the layer of interest, the latter being unintentionally doped.
    Between the upper and lower doped layers on the one hand and the layer of interest on the other hand, there can be at least one so-called barrier layer based on germanium, or based on tin germanium, the atomic proportion of which tin is less than the value of the atomic proportion of tin in the layer of interest.
    The atomic proportion of tin in the layer of interest can be less than 10%.
    The method may further comprise a step of bringing the structured part into contact with a free surface of the support layer, so as to make the structured part of the support layer integral by molecular bonding.
    The method can also include the following steps:
    determination of a minimum value of molecular bonding energy of the structured part on the support layer, as well as a minimum value of bonded surface of the lateral portions, these minimum values being such that said molecular bonding energy is greater than an energy elastic of the structured part; consolidation annealing at an annealing temperature such that the molecular bonding energy has a value greater than or equal to said previously determined minimum value; then etching of a so-called distal part of the lateral portions with respect to the central portion, so that the bonded surface of the lateral portions has a value greater than or equal to said minimum value previously determined.
    The suspension step and the contacting step can be carried out by etching the sacrificial layer by HF in the vapor phase, optionally followed by the deposition and then the evaporation of a liquid between the suspended structured part and the support layer, and in which, during the annealing step, the annealing temperature is greater than or equal to 200 ° C.
    The method may include, during the suspension step, an oxidation or a nitriding of a free surface of the support layer as well as a lower surface of the structured part oriented towards the free surface, and in which, during the annealing step, the annealing temperature is greater than or equal to 100 ° C.
    Following the suspension step, dielectric layers, resulting from the oxidation or nitriding carried out, can be formed at the level of the structured part and of the support layer, which have a preferably greater thickness. or equal to Onm.
    The invention also relates to a method of producing a microelectronic or optoelectronic device comprising said layer of interest based on tin germanium obtained by the method according to any one of the preceding characteristics, in which a junction is made. PN in the layer of interest, or a PIN junction at the level of said layer of interest, the latter then being unintentionally doped.
    BRIEF DESCRIPTION OF THE DRAWINGS Other aspects, aims, advantages and characteristics of the invention will appear better on reading the following detailed description of preferred embodiments thereof, given by way of nonlimiting example, and made with reference to the accompanying drawings in which:
    Figures IA, IB and IC are schematic sectional views (fig.lA and IC) and from above (fig.lB), of a stack comprising a layer of interest based on tin germanium, for different stages d 'a method according to a first embodiment;
    Figures 2A, 2B, 2C are schematic sectional views (fig.2A and 2B) and from above (fig.2C), of a variant of the stack illustrated in Figures IA to IC;
    FIG. 3 illustrates a flow diagram of a method according to a second embodiment, making it possible to obtain a layer of interest with direct band structure;
    FIGS. 4A, 4B and 4C are schematic views, in section, of a semiconductor structure for different stages of a method according to a third embodiment;
    FIGS. 5A and 5B are schematic views, from above, of a semiconductor structure, respectively with and without the peripheral part; and FIG. 5C is an example of a relationship between the surface energy of bonding as a function of the annealing temperature, for hydrophilic bonding and for hydrophobic bonding;
    FIGS. 6A, 6B and 6C are schematic views, in section, of a semiconductor structure, for different stages of a method according to a fourth embodiment involving a hydrophilic bonding step;
    FIGS. 7A and 7B are schematic views, in section, of an optoelectronic device with non-coherent light emission comprising a semiconductor structure obtained from the method according to the fourth embodiment;
    FIGS. 8A and 8B are schematic views, in section, of an optoelectronic device with coherent light emission comprising a semiconductor structure obtained from the method according to the fourth embodiment;
    FIGS. 9A to 9F show, schematically and in section, different stages of an example of a method for producing a laser source comprising a semiconductor stack obtained by the method according to the first or the second embodiment.
    DETAILED DESCRIPTION OF PARTICULAR EMBODIMENTS In the figures and in the following description, the same references represent the same or similar elements. In addition, the various elements are not shown to scale so as to favor the clarity of the figures. Furthermore, the different embodiments and variants are not mutually exclusive and can be combined with one another. Unless otherwise indicated, the terms "substantially", "approximately", "of the order of" mean to within 10%.
    The invention generally relates to a process for producing a so-called layer of interest based on tension-stressed germanium tin, in particular for the purpose of obtaining a structure of direct energy bands.
    By strained layer means a layer made of a monocrystalline semiconductor material having a mechanical stress in tension or in compression, causing a deformation of the meshes of the crystal lattice of the material. The layer is stressed in tension when it undergoes a mechanical stress which tends to stretch the meshes of the network in a plane. This then results in the presence of a compressive stress oriented along an axis substantially orthogonal to the stretching plane. In the context of the invention, the layer of interest based on tin germanium is intended to be stressed in tension in the plane of the layer, which results in the fact that its lattice parameter has a so-called higher effective value at its so-called natural value when the material is relaxed, ie unstressed. In the following description, unless otherwise indicated, the stress considered is oriented in the plane of the layer.
    By layer of interest based on tin germanium GeSn, it is meant that the layer of interest is made of a Gei x Sn x alloy comprising germanium and tin. The tin germanium alloy can be a binary Gei- x Sn x , ternary, for example SiyGei- x - y Sn x , or even quaternary or more. We denote by x Sn the atomic proportion of tin in the alloy. The layer of interest based on tin germanium is preferably formed of a homogeneous alloy in terms of atomic proportion of the elements forming the alloy and in terms of values of a possible doping.
    By direct or substantially direct band structure is meant that the minimum energy of the valley L (or indirect valley) is greater than or substantially equal to the minimum energy of the valley Γ (or direct valley) of the conduction band, in other words: ΔΕ - Emin, L _ Emin, r 0. By substantially equal, we mean here that this energy difference is of the order of magnitude or less than kT, where k is the constant of
    Boltzmann and T the temperature of the material. In the context of the invention, the layer of interest is initially produced based on tin germanium, the structure of energy bands of which is indirect when the material does not have a sufficient voltage stress, in other words ΔΕ <0, and may then have a deformation in tension sufficient to make its strip structure direct.
    Figures IA, IB and IC illustrate different stages of a process for producing the layer of interest based on tension-germanium tin, according to a first embodiment.
    We define here and for the remainder of the description a three-dimensional direct coordinate system (Χ, Υ, Ζ), where the axes X and Y form a plane parallel to the plane of a support layer, and where the axis Z is oriented according to the thickness of the layers. In the following description, the terms “vertical” and “vertically” extend as being relative to an orientation substantially parallel to the axis Z. Furthermore, the terms “lower” and “upper” extend as being relating to an increasing positioning when one moves away from the support layer in the + Z direction.
    Referring to Figure IA, there is provided a semiconductor stack 10 comprising semiconductor layers, at least one nucleation layer 11 and the layer of interest 12 based on tin germanium, here made of binary germanium tin alloy Gei- x Sn x , the latter being epitaxial from the nucleation layer 11. The semiconductor stack 10 covers a sacrificial layer 2 resting on a support layer 1.
    The support layer 1 can be made of a semiconductor material, electrically conductive or dielectric. This material may have a thickness of the order of a few tens of nanometers to a few hundred microns, for example be between 10 nm and 700 pm, or even between 500 nm and 100 pm. It is here made of silicon, but it can more generally be chosen, among others, from silicon, sapphire, borosilicate, silica, glass, quartz.
    The sacrificial layer 2 can be made of a material capable of being selectively etched with respect to the material of the support layer 1 and to the materials of the semiconductor stack 10. It can be a silicon oxide (for example SiO2) or a silicon nitride (for example S13N4). The sacrificial layer 2 can have a thickness of the order of a few tens of nanometers to a few microns, for example being between 10 nm and 10 pm, or even between 500 nm and 5 pm. It is here made of silicon oxide SiO2.
    The nucleation layer 11 can be made of a monocrystalline semiconductor material suitable for nucleation, or germination, of the layer of interest 12 based on GeSn. The material of the nucleation layer 11 can be chosen from the elements or compounds of column IV of the periodic table, such as germanium, silicon, tin, and the alloys formed from these elements such as GeSn, SiGeSn, Headquarters. It can also be chosen from compounds comprising elements from columns III and V, such as GaP, AIP, AlAs, InGaAs, InP, AIGas, or even from compounds comprising elements from columns II and VI, such as ZnS, ZnSe, CdZnTe, CdTe.
    The layer of interest 12 is made of a monocrystalline semiconductor material based on tin germanium and is here made of a binary alloy of germanium tin Gei x Sn x . The atomic proportion of tin xs n is not zero and can be between 1% and 14%, preferably between 4% and 10%. It has a thickness of the order of a few tens of nanometers to a few hundred nanometers or even a few microns, for example being between lOnm and lpm.
    Preferably, each of the layers forming the semiconductor stack 10 has a thickness less than its so-called critical thickness from which the stresses undergone by the layer can relax and cause the appearance of structural defects, for example dislocations of mesh detuning, thus causing a potential degradation of the electronic and / or optical properties of the layer. Also preferably, the thickness of the semiconductor stack 10 is less than its critical thickness. This minimizes the degradation of the crystal quality of the semiconductor stack 10 and the layers which form it.
    According to one embodiment, the nucleation layer 11 can be made of a material having a lattice parameter lower than that of the layer of interest 12. This is the case in particular of germanium Ge, and of a germanium tin alloy with an atomic proportion of tin lower than that of the layer of interest 12. Thus, the layer of interest 12 may have a compressive stress with respect to the nucleation layer 11, in particular when '' it is in contact with the nucleation layer 11 or when an intermediate layer of the same material as the layer of interest 12 is situated between the latter and the nucleation layer 11. The nucleation layer 11 preferably has a thickness higher than that of the layer of interest 12.
    According to another embodiment, the nucleation layer 11 can be made of a material having a lattice parameter greater than that of the layer of interest 12. This is the case in particular of tin and a tin germanium alloy with an atomic proportion of tin higher than that of the layer of interest 12. Thus, the layer of interest 12 can have a stress in tension with respect to the nucleation layer 11. The nucleation layer 11 preferably has a thickness less than that of the layer of interest 12.
    In the context of the invention, the semiconductor stack 10 is produced so that it has a non-zero voltage stress, that is to say that the stress of the stack, in the plane (X, Y), has a non-zero and positive initial value. The stress of the stack 10 corresponds to the average of the stresses of each layer of the stack, according to the relationship:
    ΣΝ
    Fk £ k & k k = l where Ek is the Young's modulus of layer k belonging to the stack, of thickness ek, and s k is the value of the deformation undergone by layer k.
    For this, we choose the materials of the layers and their thicknesses so that the stress of the stack 10 in the plane (X, Y) is strictly positive, in other words that the stress af z along the Z axis is in compression, therefore negative, according to the following relation (1):
    ° s, z = <θ (!) Where 8 kz is the initial value of the deformation along the Z axis undergone by the layer k. This initial value 8 kz of the deformation can be estimated classically from the mesh parameter a 0 , k of the relaxed k layer and the mesh parameter a z , k of the constrained layer k from the relation 8 kz = ( a z , k - ao, k) / ao, k- It can also be classically estimated from the stiffness constants of layer k and the deformation in the plane (X, Y) undergone by layer k.
    For example, the nucleation layer 11 may be a germanium layer deposited or transferred onto a sacrificial layer 2 of silicon oxide resting on a support layer 1 of silicon. This set of layers is preferably produced using the method described in the publication by Reboud et al. titled Structural and optical properties of 200 mm germanium-on-insulator (GeOI) substrotes for Silicon photonics applications, Proc. SPIE 9367, Silicon Photonics X, 936714 (February 27, 2015) which notably implements Smart Cut ™ technology.
    For this, the epitaxial growth of a layer of crystalline germanium is first carried out on a thick layer of silicon. The germanium layer then exhibits, at room temperature, a residual voltage deformation of the order of 0.2%. A dielectric layer, for example a silicon oxide, is then deposited on the free surface of the germanium layer, then an H + ion implantation is carried out in the germanium layer. Next, the dielectric layer covering the germanium layer is joined to a handle substrate formed by a dielectric layer covering a silicon layer. The germanium layer is separated into two parts at the level of an area weakened by the implantation of ions. A layer of monocrystalline germanium 11 is thus obtained covering a sacrificial layer 2, here made of silicon oxide, which rests on a support layer 1, for example a silicon layer of an SOI substrate. This process is advantageous insofar as the crystalline quality of the nucleation layer 11 is particularly high and substantially homogeneous depending on the thickness of the layer. For example, the dislocation density can be less than 10 7 cm 2 over the entire thickness of the layer, in particular at the interface with the sacrificial layer 2.
    This gives a nucleation layer 11, voltage stress, germanium. Due to the difference in values between the thermal expansion coefficients of germanium and silicon, after cooling to room temperature, the nucleation layer undergoes a voltage deformation in the (X, Y) plane of the order of 0, 2%, which results in an effective lattice parameter of approximately 5.670 Å while the natural lattice parameter of relaxed germanium is 5.658 Å.
    Alternatively, one can realize the nucleation layer 11 under tension by epitaxial growth of a germanium layer on a substrate, the germanium layer then being covered with a layer of silicon oxide. This stack is joined by molecular bonding with a second stack formed by a layer of silicon covered with a layer of silicon oxide, the bonding being produced by bringing the layers of silicon oxides into mutual contact. The substrate is then completely removed, for example by grinding (in English), so as to thus obtain the germanium layer bonded to a support layer 1 of silicon by a sacrificial layer 2 of silicon oxide. This approach is described in particular in the publication by Jan et al. titled Tensile-strained germanium-on-insulator substrate for silicon-compatible optoelectronics, Opt. Mater. Express 1,1121-1126 (2011).
    We then proceed to the epitaxial growth of the layer of interest 12 based on GeSn from the exposed surface of the nucleation layer 11, for example by a chemical vapor deposition technique (CVD, for Chemical Vapor Deposition, in English), possibly at low pressure (LPCVD, for Low Pressure Chemical Vapor Deposition, in English) or by molecular beam epitaxy (MBE, for Molecular Beam Epitaxy, in English).
    The precursor gas flow ratios, for example Ge2H6 and SnCL, are controlled to obtain the value xs n of atomic proportion of tin in the layer of interest 12. As an illustration, the growth temperature can be understood between 300 ° C and 400 ° C and the growth rate can be of the order of 10 nm / min to lOOnm / min. The layer of interest 12 then has a compressive stress in the plane (X, Y) insofar as it has a natural mesh parameter greater than the effective mesh parameter of the nucleation layer 11.
    The thicknesses of the nucleation layer 11 and of the layer of interest 12 are chosen using the relation (1) so that the semiconductor stack 10 has a voltage stress <r s l > 0 in the plane (X, Y), in other words a compressive stress <rs l z <0 along the Z axis.
    It is thus possible, by way of illustration, to obtain a semiconductor stack 10, constrained in tension in the plane (Χ, Υ), and formed of:
    the germanium nucleation layer 11 with a thickness for example of lpm, having a voltage deformation of + 0.2% (effective lattice parameter of 5.670 Å for a natural lattice parameter of 5.658)), and
    the layer of interest 12 in Gei- x Sn x with an atomic proportion of tin xs n of 8%, with a thickness for example of 50 nm. The layer of interest 12 thus has an effective lattice parameter of 5.670 Å, equal to that of the nucleation layer 11, for a natural lattice parameter of 5.724 Å. It then presents a compression deformation in the plane (X, Y) of -0.94%.
    Referring to Figures IB, there is provided a structuring of the semiconductor stack 10 so as to form a structured part 20 and a peripheral part 30, the structured part 20 comprising a central portion 21 connected to the peripheral part 30 by at at least two lateral portions 22 opposite one another with respect to the central portion 21. The structured portion 20 here comprises a single pair of tensioning arms 22 intended to subsequently ensure an increase in the stress in uniaxial tension of the portion central 21, and therefore a tensioning of the layer of interest 12 located in the central portion 21. The structured part 20 is produced by conventional steps of optical and / or electronic lithography then engraving of the stack, which does not are therefore not detailed here.
    The central portion 21 may have a shape, in the plane (X, Y), substantially square or rectangular, of a few hundred nanometers to a few microns in width, and from a few hundred nanometers to a few hundred microns in length. . Other shapes are possible, such as polygonal shapes. The lateral portions 22, hereinafter called tensor arms 22, each connect an edge of the central portion 21 to the peripheral portion 30. They are arranged in pairs opposite the central portion 21 so as to define at least a substantially rectilinear deformation axis. Thus, an increase in the voltage deformation is able to be generated in the central portion 21 during the subsequent step of suspending the structured part 20, and therefore a tensioning of the layer of interest 12 located in the central portion 21.
    For this, the tensioning arms 22 and the central portion 21 are formed so that the average width "b" of the tensioning arms 22 is greater than the average width "a" of the central portion 21, preferably ten times greater than the latter. By width is meant the transverse dimension of a portion or of an arm, in the plane (X, Y), at its longitudinal axis. The central portion 21 here has an average width "a" oriented along the axis Y and substantially constant along the longitudinal axis X. The tensioning arms 22 have an average width "b" oriented here along the axis Y.
    In addition, the surface dimension in the plane (X, Y) is chosen so that the tensioning arms 22 have substantially no or little deformation at the end of the next step of suspension. More specifically, the local deformation decreases as one moves away from the central portion 21 and becomes negligible at a distance greater than or equal to one or twice an average dimension of the central portion 21. The average deformation of the tensing arms 22 , that is to say the deformation field integrated in the volume of the tensioning arms 22, has a value lower than that of the central portion 21, or even is negligible with respect to the average deformation in the central portion 21 In the example of FIG. 1B, the tensioning arms 22 have the shape of a trapezoid so that the width increases as one moves away from the central portion 21. Other shapes are possible, for example a form where the tensioning arms 22 have a sudden increase in width vis-à-vis the central portion 21 then a main zone of constant width.
    The structuring can be carried out so as to control the value of the amplification of the stress in tension of the central portion 21 of the semiconductor stack 10, obtained subsequently during the suspension of the structured part 20. For this, the dimensional parameters of the structured part 20 are predetermined, for example the widths and lengths of the central portion 21 and of the tensioning arms 22. By way of example, in the case of a rectangular central portion 21, of length A and of constant width a, and rectangular tensing arms 22 of length B / 2-A / 2 and constant width b, an amplification factor f relating the final stress in tension oj to the initial stress in tension can be expressed by the relation (2) formulated in the article by Süess et al entitled Analysis of enhanced light emission from highly strained germanium microbridges, Nature Photon. 7, 466-472 (2013):
    J B B — Aj Xb B-AJ (2) where L is the length of the sacrificial layer 2 removed under the structured part 20 during the subsequent suspension step. Thus, as a function of the dimensional parameters of the structured part 20 of the semiconductor stack 10, it is possible to control the value of the amplification of the voltage stress applied to the central portion 21 during the suspension. The amplification factor can also be estimated using digital simulation software such as COMSOL Multiphysics.
    Referring to Figure IC (sectional view along line AA shown in Figure IB), the suspension of the structured part 20 is carried out, which will cause an amplification of the stress in tension undergone by the central portion 21 of the semiconductor stack 10, and therefore a tensioning of the layer of interest 12 located in the central portion 21. For this, a cavity 3 is produced under the structured part 20 so as to suspend it above d a free surface 4 of the support layer 1.
    The cavity 3 is produced by etching, for example by wet etching, of the sacrificial layer 2 made accessible by openings obtained during the structuring of the semiconductor stack 10. The wet etching here uses hydrofluoric acid ( also called HF, for Hydrogen Fluoride in English) in the vapor phase. The HF vapor flow can be low so as to etch the sacrificial layer 2 at a moderate speed of the order of lOnm per minute. More specifically, the vapor flow can, for example, comprise hydrofluoric acid at 15 torr of partial pressure, alcohol at 0.01 torret of nitrogen at 60 torr. Thus, the part of the sacrificial layer 2 located under the structured part 20 is etched over its entire thickness. The structured part 20 is then suspended above the free surface of the support layer 1, thus forming a cavity 3. The cavity 3 is therefore located between the structured part 20 and the free surface 4 of the support layer 1.
    This gives a suspended structured part 20 whose tensor arms 22 hold the central portion 21 above the free surface 4 of the support layer 1 and generate in the central portion 21 an increase in the initial tension stress σ ^, along the axis or axes of deformation, due to the difference in average width between the tensioning arms 22 and the central portion 21. In this example, the deformation of the central portion 21 may be sufficient to obtain a strip structure d direct energy of the layer of interest 12 located in the central portion 21.
    The method thus allows to obtain an increase in the stress in tension of the central portion 21 of the semiconductor stack 10, and therefore the tensioning of the layer of interest 12 located in the central portion 21, this without having to produce an intermediate layer based on tin germanium with a high proportion of tin, as described in the article by Wirths et al 2013 mentioned above. The crystalline quality of the semiconductor stack 10, and in particular that of the layer of interest 12 based on GeSn can be preserved when the stack and its layers making it up have a thickness less than the respective critical thicknesses.
    FIGS. 2A and 2B are schematic views, in cross section, of different variants of the stack illustrated in FIG. IA, and FIG. 2C is a schematic view, in top view, of a variant of the structured part 20 illustrated in FIG. 1B.
    In Figure 2A, the stack 10 is distinguished from that illustrated in Figure IA in that it further comprises two layers 13A, 13B based on germanium tin GeSn between which is located the layer of interest 12 in touch. The layers 13A, 13B based on tin germanium can be made of a binary alloy of tin germanium, even ternary or quaternary, and can have an atomic proportion of tin identical or different to that of the layer of interest 12. In this example, the layers 13A, 13B are made of a material identical to that of the layer of interest 12, namely a binary alloy of germanium tin with the same atomic proportion of tin, and differ from it by doping. Indeed, the layer of interest 12 is here unintentionally doped while the lower layer 13A has doping according to a first type of conductivity, for example of type N, and the upper layer 13B has doping according to a second type of conductivity opposite to the first type, for example of the P type. The doped layers 13A, 13B can have different thicknesses, here smaller, than that of the layer of interest 12. For example, the thickness of the layer of interest 12 may be approximately 350 nm and those of the doped layers 13A, 13B approximately 100 nm. The doped layers 13A, 13B can form, with the layer of interest 12, a PIN type diode.
    The stack 10 may further comprise an upper layer 14 intended to balance the stresses along the axis Z of the semiconductor stack 10, in order to limit the risks of overall deformation of the stack along the 'Z axis, buckling type. This upper layer 14 has a thickness, a Young's modulus and a stress in tension in the plane (X, Y) such that the vertical distribution of the stresses along the axis Z is substantially symmetrical. Preferably, the upper balancing layer 14 is made of the same material as that of the nucleation layer 11 and has a product, thickness by tensile stress, substantially equal to that of the nucleation layer 11. In this example, the nucleation layer 11 is made of germanium with a thickness of approximately lpm and has a voltage deformation in the plane (X, Y) of approximately 0.2%. The upper balancing layer 14 is made of germanium with a thickness of 800 nm and has a voltage deformation of approximately 0.25%.
    In Figure 2B, the stack 10 differs from that illustrated in Figure 2A in that the layer of interest 12 is separated from the doped layers 13A, 13B by two intermediate layers called barriers 15A, 15B which have a band gap energy higher than that of the layer of interest 12, so as to improve the quantum confinement of the charge carriers in the layer of interest 12. The barrier layers 15A, 15B can be made of an unintentionally doped material, preferably germanium or a tin germanium alloy, with an atomic proportion of tin lower than that of the layer of interest 12. Of course, in general, the semiconductor stack 10 may have more semiconductor layers , based on tinium germanium or not, doped or not, and therefore may include several layers of interest 12.
    In FIG. 2C, the structured part 20 differs from that illustrated in FIG. 1B in that two pairs of tensing arms 22 of identical dimensions are shown, which makes it possible to generate a biaxial increase in the voltage deformation of the central portion 21, of intensity here substantially equal along the two deformation axes here respectively parallel to the axes X and Y. As a variant, each pair of tensioning arms 22 may have different dimensions, so as to deform the central portion with a different intensity along each of the axes of deformation.
    FIG. 3 illustrates a flow diagram of a method according to a second embodiment, making it possible to obtain a layer of interest 12 based on tin germanium with direct band structure.
    During a first step 110, the minimum value σ ^ ιτ η of voltage stress is estimated for a layer of interest 12 based on tin germanium Gei- x Sn x of tin atomic proportion x Sn making it possible to obtain a direct band structure, in other words ΔΕ - Emin, L _ Emin, rh 0. The minimum value σ © of stress in tension can be estimated from the article by Gupta et al. entitled Achieving direct band gap in germanium through integration of Sn alloying and externalstrain, J. Appl. Phy., 113, 073707 (2013) which illustrates an example of evolution of ΔΕ as a function of the value of the stress in tension undergone by the layer of interest 12 in Gei- x Sn x and the atomic proportion of tin . This evolution is estimated from an empirical method of non-local pseudo-potential (NLEPM for Non Local Empirical Pseudopotential Method, in English).
    In a second step 120, the semiconductor stack 10 is determined comprising such a previously determined layer of interest 12, with properties {x Sn ; σ ^ ιτιιη }, and thus presenting a stress in tension of value The values σ © and σ ^ ιτιιη are positive insofar as the stress in the plane (X, Y) is in tension.
    For this, we denote G the transfer function for determining the value CT © of the layer of interest 12 from the value CTg ' min of the semiconductor stack 10, in other words: σ ^ ιτιιη = G © '™ 1 ). The transfer function G is parameterized by the characteristics of different layers making up the semiconductor stack 10, namely the mesh parameters, the thicknesses of the layers and the respective Young and Poisson modules. The parameters of the transfer function G are therefore determined, for example by numerical simulation using the COMSOL Multiphysics software, or by checking the following relationship:
    σ, fv -, N f, min p;, z ~ /
    4 — lfc = lf, min k £ k, z e k During a third step 130, said semiconductor stack 10 is produced beforehand so that:
    - The semiconductor stack 10 has an initial stress in tension σ ' 5 > 0 less than the value aÎj' mm , and that
    - It comprises the layer of interest 12 of atomic proportion of tin xs n and of an initial stress value lower than σ ™ η so that the band structure is indirect, the initial value being able to be positive (in tension ), zero or negative (in compression).
    In a fourth step 140, a structuring of the semiconductor stack 10 is determined so as to form the structured part 20 described above. The structuring is determined so that the suspension of the structured part 20 causes the stress of the central portion 21 to increase, from the initial value σ ' 5 to the final value eÎj, the latter then being greater than or equal to [ For this, we denote by F the transfer function allowing to go from σ ' 5 to eÎj, in other words: eÎj = F (Cg). The transfer function F is parameterized essentially by the dimensions of the structured part 20, and in particular by the average width of the tensioning arms 22 and that of the central portion 21. The transfer function can be identical or similar to the amplification factor f previously mentioned with reference to relation (2). The parameters of the transfer function F are therefore determined, for example by numerical simulation using the COMSOL Multiphysics software or by checking the relation (2) mentioned above.
    In a fifth step 150, the structured part 20 is suspended by etching the sacrificial layer 2 located under the structured part 20. Thus, at the same time:
    - the central portion 21 of the stack passes from the initial value aj to the final value Og = F (a * s ) of stress in the plane (X, Y), the final value σ £ then being greater than or equal to Os 'min;
    - the layer of interest 12 goes from the initial value to a final value σ £ 4 = G (ag) of stress in the plane (X, Y), this final value then being greater than or equal to o ^ min .
    There is thus obtained a layer of interest 12 based on tin germanium, located at the central portion 21, which has a direct band structure, without having to make a high proportion tensioning layer. atomic tin as described in the Wirths 2013 article cited above. It is then possible to obtain a direct band structure for a layer of interest 12 based on GeSn having an atomic proportion of tin of less than 14%, or even less than 10%, even less than 8%, or even less. As before, the stack and the layers which form it can have a crystalline quality preserved when the respective thicknesses are less than the critical thicknesses.
    Figures 4A to 4C illustrate different steps of a method for producing a semiconductor structure 40 according to a third embodiment, the semiconductor structure 40 comprising the stack 10 with a layer of interest 12 based on tin germanium described above, and being secured by direct bonding to the support layer 1. This process is similar to that described in application FR1559283 filed on September 30, 2015. Furthermore, for the sake of clarity, only the semiconductor stack 10 is illustrated, and not the nucleation layer 11 and the layer of interest 12.
    After the suspension step described above, the central portion 21 of the semiconductor stack 10 is stressed in tension and has alqrs an elastic energy Ee, which, in the first order, can be written: Ee ~ σ ^. ε ^ .ν, where σ [is the mean value of the stress in tension in the plane (X, Y), cÎj the mean value of the deformation corresponding to the stress undergone, and V the volume of the central portion 21.
    By direct bonding, also called molecular bonding or bonding by molecular adhesion, is meant the joining of two surfaces of identical or different materials one against the other, without the addition of a sticky layer (of glue, glue, etc. type). ...) but through the attractive atomic or molecular interaction forces between the surfaces to be bonded, for example Van der Walls forces, hydrogen bonds, even covalent bonds. The semiconductor stack 10, secured by direct bonding to the support layer 1, then has a bonding energy which, in the first order, can be written: Ec ~ E s .S, where E s is the bonding surface energy (it is assumed here that the surfaces to be bonded have a substantially equal surface energy) and S the extent of the surfaces bonded.
    As detailed below, the molecular bonding used here can be of hydrophilic or hydrophobic type. Bonding is of hydrophilic type when it concerns the adhesion of hydrophilic surfaces, that is to say surfaces having the capacity to bind with water molecules by an adsorption mechanism. The bonding then brings into play hydrogen bonding forces whose interaction intensity is particularly high. For this, the hydrophilic surfaces are terminated by hydroxyl groups (-OH). Alternatively, the bonding can be of the hydrophobic type and then relate to surfaces which do not have the capacity to adsorb water. For this, the hydrophobic surfaces can be saturated with atoms such as hydrogen or fluorine.
    Described below, by way of illustration, a method for producing a semiconductor structure, comprising the stack with a layer of interest 12 based on tin germanium located in the structured part 20, the semiconductor structure 40 being bonded by molecular adhesion to a support layer 1 of silicon.
    In a first step, a semiconductor stack 10 is produced comprising the structured part 20 (not shown), resting on the support layer 1 by means of a sacrificial layer 2. The semiconductor stack 10 comprises the layer d interest 12 based on germanium tin (not shown), and is identical or similar to the semiconductor stacks described above.
    According to a second step illustrated in FIG. 4A, a cavity 3 is produced under the structured part 20 so as to suspend it above a surface made free of the support layer 1. The semiconductor stack 10 then passes from the initial value to the final value Îj of constraint in the plane (X, Y), the final value then being greater than or equal to The layer of interest 12 passes from the initial value to a final value oj.
    of stress in the plane (X, Y), this final value preferably being greater than or equal to σ ^ ” 111 , so that the layer of interest 12 has a direct band structure.
    According to a third step illustrated in FIG. 4B, the structured part 20 is brought into contact with the free surface 4 of the support layer 1. For this, the structured part 20 can be immersed in a liquid solution, for example alcohol or acidified deionized water (pH close to 2), then the liquid is evaporated. During the evaporation phase, the structured part 20 naturally comes into contact with the free surface 4 of the support layer 1. Thus, the structured part 20 rests on the support layer 1, so that the bottom surface of at least a part of the tensioning arms 22 is in contact with the free surface 4 of the support layer 1. The lower surface of the central portion 21 can be totally, partially, or not in contact with the free surface 4.
    The contacting of these surfaces ensures direct bonding of the structured part 20 with the support layer 1, here of the hydrophobic type insofar as the surfaces are joined to one another by means of connections hydrogen. At ambient temperature, as illustrated in FIG. 5C representing the evolution of the surface energy of hydrophobic bonding between the bonded surfaces, the hydrophobic bonding energy is here of the order of 5 mJ / m 2 .
    By contacting means the contact of the lower surface 23 of the structured part 20 with the free surface 4 of the support layer 1. These surfaces can be formed of the material mainly comprising the layers or of an intermediate material different from this main material. The structured part 20 and the support layer 1 can thus comprise a thin layer of an intermediate material obtained for example by deposition or by oxidation, preferably after formation of the cavity 3. In the process described here involving hydrophobic bonding, the structured part 20 and the support layer 1 do not comprise any intermediate material.
    Thus, a structured part 20 of the semiconductor stack 10 is obtained, bonded to the free surface 4 of the support layer 1. The bonded structured part 20 comprises the central portion 21 and part of the tensioning arms 22. The part the non-bonded tensioning arms 22 is located in the zone where these join the peripheral part 30 of the semiconductor stack 10, the latter resting on the non-etched part of the sacrificial layer 2.
    Alternatively, the step of suspending and bringing the structured part 20 into contact with the free surface 4 of the support layer 1 can be carried out at the same time. For this, the cavity 3 is for example produced by wet etching with liquid HF or even by high pressure steam HF. In the case of etching by HF steam, the vapor flow can comprise hydrofluoric acid at 60 torr of partial pressure, alcohol at 0.1 torr and nitrogen at 75 torr. The gas flow then leads to a higher etching speed than that mentioned above, for example of the order of 100 nm / min, during an out-of-equilibrium etching reaction. Also, drops of water and hydrofluoric acid, products of the chemical reaction, form in the cavity 3 and cause, by evaporating, the contacting of the structured part 20 with the free surface 4 of the support layer 1 .
    At the end of this step, the bonded structured part 20, formed by the central portion 21 and the tensioning arms 22 resting on the support layer 1, has:
    o a bonding energy Ec, resulting from hydrophobic molecular bonding on the support layer 1. It can be estimated, at the first order, by the relation:
    E c ~ E s (S bt + S pc ) where E s is the surface energy evaluated from the relation illustrated in FIG. 5C, and Sbt and Spc are the respective bonded surfaces of the tensing arms 22 and of the portion central 21. The bonding energy tends to stabilize the bonded structured part 20 and to avoid any relaxation of the stresses liable to modify its mechanical strength as well as its crystalline structure, and therefore to degrade its electrical and / or optical properties;
    o an elastic energy Ee, resulting from the stress in tension related to the deformation of the central portion 21 by the tensioning arms 22. It can be estimated, at the first order, by the relation:
    Ee ~ e (®s, bt · ^ s, bf $ bt + * ^ s, pc · ^ s, pc · Spc) where e is the average thickness of the semiconductor stack 10, Og bt and σ [ pc les average values of the stresses in tension undergone, respectively, by the tensioning arms 22 and the central portion 21, cîj bt and cÎjp C the average values of the corresponding deformations. The elastic energy tends to destabilize the glued central part so as to naturally relax the stresses.
    It may be noted that, in the first order, the bonding energy has a preponderant term linked to the bonded surface of the tensioning arms 22, the latter is generally greater than the bonded surface of the central portion 21. Furthermore, the elastic energy includes a predominant term linked to the deformation of the central portion 21, insofar as the tensioning arms 22 have an average deformation value close to the residual deformation value, the latter being less than the value of the deformation undergone by the central portion 21.
    In order to achieve a bonded semiconductor structure 40, the mechanical strength and therefore the electrical and / or optical properties are preserved, which can be separated from the peripheral part 30, the bonding energy must be greater than l elastic energy, which translates to the first order by the following inequality:
    pminAcmin, ς λ cmin, ff ς λ L sv a bt ' a pcy e V u s, bf fc s, bf a bt' u s, pc- fc s, pc- a pcy [0085] For this, we determine at both the minimum value of surface bonding energy E s min and the minimum value of bonded surface Sbt rr n of the tensing arms 22, necessary to verify this inequality. Of course, this inequality can be clarified by using more detailed expressions of bonding energy and elastic energy, for example by integrating the stress field throughout the volume of the bonded structured part 20.
    According to a fourth step, a molecular bonding of the structured part 20 is reinforced on the support layer 1, so as to obtain an Es value of bonding surface energy greater than or equal to the minimum value E s rr n determined beforehand. For this, a heat treatment is carried out, in the form of a consolidation annealing, in which the stack is subjected to an annealing temperature Tr for a few minutes to a few hours. By way of illustration, the annealing temperature can be 200 ° C. applied for 2 h, which here increases the surface energy of hydrophobic bonding from 5 mJ / m 2 to 100 mJ / m 2 . The annealing temperature is between a minimum value which depends in particular on the minimum bonded area Sbi 11 of tensioning arms 22 which one wishes to keep and a maximum value which depends in particular on the crystalline quality to be preserved of the semiconductor stack 10. The maximum value of the annealing temperature can thus be lower than the epitaxial growth temperature of the semiconductor stack 10. Thus, a structured part 20 is bonded to the support layer 1 with a bonding energy Ec whose value is greater or equal to the predetermined minimum value. We are then able to remove part of the tensioning arms 22 to separate the structured part 20 from the peripheral part 30.
    In a fifth step illustrated in FIGS. 4C, a distal portion 24 of the tensioning arms 22 is removed, by etching, so as to separate, or individualize, the structured part 20 from the peripheral part 30. By separating, making distinct or individualizing, it is meant here that the structured part 20 is no longer connected to the peripheral part 30 by the tensioning arms 22. In addition, by distal portion 24 of the tensioning arms 22 with respect to the central portion 21 means the area of the tensioning arms 22 remote from the central portion 21 and forming the connection with the peripheral portion 30. By conventional operations of optical and / or electronic lithography and etching, the distal portion of the tensioning arms 22 so that the bonded structured part 20 has a value of bonded surface area Sbt of the tensioning arms 22 greater than or equal to the minimum value Sbt min determined beforehand. Thus, the bonded surface of the tensioning arms 22 is sufficient for the bonded structured part 20 to have a bonding energy greater than its elastic energy. Thus, a semiconductor structure 40 is obtained with a central portion 21 bonded to the support layer 1, the mechanical strength of which is ensured, thus preserving its electrical and / or optical properties. The semiconductor structure 40 has a high crystal quality and the central portion 21 has a predetermined average deformation. It is joined to the support layer 1 by molecular bonding, the bonding energy and the bonded surface of the tensing arms 22 allow the stress field to be frozen. In the central portion 21, the layer of interest 12 based on GeSn has a direct band structure.
    FIG. 5A illustrates the semiconductor structure 40 with central portion 21, obtained by separating the structured part 20 from the peripheral part 30, by etching of the distal zone of the tensioning arms 22 making connection with the peripheral part 30. The FIG. 5B illustrates the semiconductor structure 40 obtained from the structured part 20 bonded by etching the zone of connection of the tensioning arms 22 to the peripheral part 30 (the latter also being deleted).
    FIG. 5C illustrates an example of a relationship between the surface bonding energy between a germanium surface of the nucleation layer 11 and a silicon surface of the support layer 1, as a function of the annealing temperature, in the case of a hydrophilic type bonding and a hydrophobic type bonding. Up to approximately 600 ° C., the surface bonding energy has a lower value in the hydrophobic case than in the hydrophilic case. The trend then reverses from around 600 ° C. In addition, in the hydrophilic case, the surface energy increases as soon as an annealing at approximately 100 ° C. is applied, and one passes from an energy of the order of 100 mJ / m 2 at ambient temperature to 1J / m 2 after annealing at around 200 ° C. In the hydrophobic case, the energy goes from around 5 mJ / m 2 at room temperature to 100 mJ / m 2 after annealing at around 200 ° C.
    Alternatively, according to a fourth embodiment described with reference to Figures 6A to 6C, it is possible to perform a molecular bonding of hydrophilic type of the structured part 20 on the support layer 1, according to a process identical or similar to that described in the application FR1559283 filed on September 30, 2015 cited above.
    Referring to Figure 6A, prior to contacting the structured part 20 suspended on the support layer 1, performing a step of surface treatment of the structured part 20 and the free surface 4 of the layer support 1, with the aim of subsequently ensuring the hydrophilic molecular bonding of these elements. During this step, the surface 23 of the structured part 20 facing the cavity 3 and the free surface 4 of the support layer 1 are treated so that they are each formed of a thin oxide layer 41A, 41B or nitride, with a thickness of a few nanometers to a few tens of nanometers.
    According to a variant, the structured part 20 and the support layer 1 are covered, at the level of the cavity 3, with a thin layer 41A, 41B known as an oxide interlayer produced by oxidation, for example obtained by placing air in this area of the stack for a sufficient time, for example 1 hour. They can also be obtained by an O3 plasma oxidation technique, for example at room temperature, or even by an O2 plasma oxidation technique, for example at a temperature of 250 ° C. According to another variant, the thin oxide or nitride layers are obtained by a thin layer deposition technique, for example of the ALD type (for Atomic Rent Deposition, in English) assisted or not by plasma.
    With reference to FIG. 6B, the structured part 20 is then brought into contact with the free surface 4 of the support layer 1, for example by immersing the structured part 20 suspended in a liquid solution, for example d 'acidified alcohol or deionized water (pH close to 2), then evaporating the liquid. The contacting of these surfaces ensures direct bonding of hydrophilic type of the structured part 20 on the support layer 1 at the level of the respective intermediate layers 41A, 41B. At ambient temperature, as illustrated in FIG. 5C, the hydrophilic bonding energy is here of the order of 100 mJ / m 2 . These intermediate layers 41A, 41B have a thickness of the order of a few tens of nanometers to one or more hundreds of nanometers, and are advantageously dielectric and can provide electrical insulation of the central portion 21 from the layer support 1.
    Then performs a step of determining the minimum value of surface bonding energy E s min , here hydrophilic, and the minimum value of bonded surface Sbt min of the tensing arms 22, necessary for the hydrophilic bonding energy of the structured part 20 is greater than the elastic energy of this same structured part 20.
    Then performs a step of strengthening the molecular bonding of the structured part 20 secured to the support layer 1, so as to obtain an Es value of surface energy of hydrophilic bonding greater than or equal to the minimum value E s min determined beforehand. For this, a heat treatment is carried out, in the form of a consolidation annealing, in which the stack is subjected to an annealing temperature Tr for a few minutes to a few hours. By way of illustration, the annealing temperature can be 200 ° C. applied for 2 h, which here increases the surface energy of hydrophilic bonding from 100 mJ / m 2 to 1 J / m 2 .
    With reference to FIG. 6C, a distal part 24 of the tensioning arms 22 is removed, by etching, so as to individualize the structured part 20 vis-à-vis the peripheral part 30. This step is similar to the step described previously with reference to FIG. 5C and is not detailed further here. Thus, a semiconductor structure 40 is obtained with a central portion 21 bonded by hydrophilic molecular adhesion to the support layer 1, the mechanical strength of which is ensured and the electrical and / or optical properties preserved. The central layer comprises the layer of interest 12 based on GeSn, the band structure of which is advantageously direct.
    The method according to this embodiment therefore differs from the method described above essentially by hydrophilic bonding, the intensity of which is greater than that of hydrophobic bonding up to annealing temperatures of the order of 500 ° C. 600 ° C, and by the presence of a layer 41A, 41B of an oxide or nitride interleaved at the interface between the structured part 20 and the support layer 1, the dielectric property of which provides electrical insulation between these elements. This intermediate material, in addition to an electrical insulation function, can also provide a function of evacuation of the heat possibly produced at the level of the central portion 21, in the case where the latter forms an emissive layer of a light source.
    Advantageously, a plurality of semiconductor structures 40 can be produced collectively and simultaneously, from the same semiconductor stack 10. The semiconductor structures are then adjacent and separated from each other. Thus, each semiconductor structure 40 is distinct from its neighbors, that is to say not attached to the corresponding peripheral part 30 of the same semiconductor stack 10.
    We will now describe the production of various optoelectronic devices comprising the semiconductor structure 40 with a layer of interest 12 based on voltage-stressed tin germanium, obtained by one or other of the methods described above.
    [ooioo] Figures 7A and 7B schematically show sectional views of two examples of an optoelectronic device with non-coherent light emission. The optoelectronic device is here a light-emitting diode.
    [Ooioi] In Figure 7A, the light emitting diode here comprises a semiconductor structure 40 obtained by the production method according to the fourth embodiment, that is to say involving a hydrophilic molecular bonding.
    The semiconductor structure 40 comprises a central portion 21 in tension in which the layer of interest 12 based on GeSn (not shown) preferably has a direct band structure. It is joined to the support layer 1 by hydrophilic molecular bonding, which results in the presence of an intermediate material 41A, 41B, here a silicon oxide, located at the interface between the germanium of the nucleation layer 11 ( not shown) of the semiconductor stack 10 and the silicon of the support layer 1. The support layer 1 is here an upper layer of silicon of a substrate, for example of the SOI type. It rests on an oxide layer 5 located between the support layer 1 and a thick lower layer 6 of silicon.
    The semiconductor structure 40 further comprises an encapsulation layer 42 which covers the central portion 21 and the tensioning arms 22. This encapsulation layer 42 may be made of a dielectric material having good thermal conductivity, such as ΙΆΙ2Ο3 or SÎ3N4. SÎ3N4 can also contribute to inducing a voltage stress in the semiconductor stack 10. The central portion 21 includes a PIN junction produced by implantation of dopants (phosphorus and boron) so as to form an N-doped zone 45 close to a zone 43 doped P. Here, an intrinsic zone 44 (not intentionally doped) separates the doped zones N and P. The junction PIN extends in a substantially vertical way through the central portion 21 and therefore of the layer of interest 12 based on GeSn (not shown), in the direction of the support layer 1. Furthermore, two pads 46A, 46B of an electrically conductive material are present at the doped zones, forming electrical contacts.
    The light emitting diode can be obtained in the following manner. First of all the semiconductor stack 10 is produced according to the second embodiment so that the layer of interest 12 based on GeSn has a direct band structure, then the semiconductor structure 40 is produced by the method according to the fourth embodiment (hydrophilic bonding). The doped areas 43.45 are then produced by implantation of impurities, for example phosphorus and boron. The electrical contacts 46A, 46B are then produced. An encapsulation layer 42 is then deposited and then flattened by a chemical mechanical polishing technique of the CMP (for Chemical Mechanical Polishing) type, then locally etched so as to make the electrical contacts accessible.
    [00105] FIG. 7B illustrates a variant of the light-emitting diode illustrated in FIG. 7A, which is essentially distinguished from it in that a PIN junction extends in a manner substantially parallel to the plane of the support layer 1.
    The central portion 21 is structured in its thickness, so as to have a lower part 43 based on GeSn doped with a first type of conductivity, here of type P, resting on the nucleation layer 11 (not shown). This P doped part 43 is connected to the tensioning arms 22 and has an average thickness substantially identical to that of the arms. On the lower P doped part rests an upper part 45 based on GeSn doped according to a second type of conductivity, here of type N. An intrinsic part 44 based on GeSn is located between the upper part 45 doped N and the lower part 43 doped P, and here has dimensions in the plane (X, Y) substantially identical to those of the upper part. The intrinsic part 44 advantageously corresponds to the layer of interest 12 with a structure of direct bands (not shown). Thus, the P and N doped parts 43, 45 and the intrinsic part 44 together form a PIN junction which extends along a plane substantially parallel to the plane (X, Y). Two pads 46A, 46B of an electrically conductive material, forming electrical contacts, are arranged on the upper part doped N and on a free area of the lower part doped P.
    Figures 8A and 8B schematically show a sectional view of examples of an optoelectronic device with coherent light emission. More specifically, the optoelectronic device is here a laser source with optical or electrical pumping.
    In Figure 8A, the laser source here comprises a semiconductor structure 40 obtained by the production method according to the fourth embodiment, that is to say involving hydrophilic molecular bonding. The laser source here comprises a semiconductor structure 40 formed by a central portion 21 of the stack 10 in tension with a layer of interest 12 based on GeSn (not shown) with advantageously direct band structure, and secured to the support layer 1 by hydrophilic molecular bonding.
    The layer of interest 12 of the semiconductor structure 40 is here intrinsic or even doped, for example with phosphorus to populate the indirect valley of the conduction band, and an optical cavity is produced inside which is located the central portion 21, which here forms a gain medium capable of emitting light. For this, and by way of illustration, two Bragg mirrors 47A, 47B are arranged on the upper face of the tensioning arms 22, preferably in an area where the deformation of the tensioning arms 22 is substantially equal to the residual value.
    FIG. 8B illustrates a variant of the light-emitting diode illustrated in FIG. 8A, which is essentially distinguished from it in that a PIN junction extends substantially parallel to the plane of the support layer 1 in the central portion 21. The central portion 21 here comprises a stack of a first lower part 43 based on GeSn, located near the support layer 1 (and separated from the latter by the nucleation layer 11), doped according to a first type conductivity, for example of type P, covered with an intrinsic intermediate part 44 corresponding to the layer of interest 12 (not shown), itself covered with an upper part 45 based on GeSn doped according to a second type of conductivity opposite to the first type, for example of type N. An optical cavity, similar to that described with reference to FIG. 8A, is produced at the level of the upper face of the tensioning arms 22. Furthermore, two co electrical contacts (not shown) are designed to be in contact, one with the N-doped upper part and the other with the P-doped lower part
    FIGS. 9A to 9F schematically represent in sectional view different stages of an example of a method for producing a laser source in which the optical cavity is produced at the level of the support layer 1.
    In this example, there is produced, for example by RP-CVD epitaxy (for Reduced Pressure Chemical Vapor Deposition, in English), a layer of a semiconductor material 8, here germanium, on a silicon substrate 7 (FIG. 9A). The germanium layer 8 is then covered with an oxide layer 9 and then H + ions are implanted in the germanium layer 8 (dotted line in FIG. 9B). A silicon layer 1 is then produced intended to form the support layer 1, here in the form of an SOI substrate, in which two Bragg mirrors 47A, 47B (or equivalent optical elements) are produced at its surface. to form an optical cavity. The surface of the support layer 1 is then covered with an oxide layer. The SOI substrate is joined to the surface of the oxide layer 9 (FIG. 9C). The germanium layer 8 is broken at the ion implantation zone and a set of germanium layers is thus formed, forming the nucleation layer of the stack 10, linked to a support layer 1 in silicon by means of a sacrificial layer 2 in silicon oxide. The two Bragg mirrors 47A, 47B are buried in the support layer 1 at the interface with the sacrificial layer 2 (FIG. 9D).
    The semiconductor stack 10 is then produced according to the first or the second embodiment, comprising a layer of interest 12 based on GeSn (not shown) preferably with direct band structures. A semiconductor structure 40 is then obtained from the method according to the second embodiment. The Bragg mirrors are thus arranged facing the tensioning arms 22, or even facing the central portion 21, and surround the central portion 21 so as to form an optical cavity (FIG. 9E). Next, an encapsulation layer 42, for example made of silicon oxide, is deposited which covers the semiconductor structure 40. Finally, a PIN junction 43, 44, 45 is made through the central layer 21 and therefore the layer of interest.
    12 (not shown), then electrical contacts 46A, 46B are produced (FIG. 9F). Furthermore, the support layer 1 may have been previously structured so as to form the core of a waveguide surrounded by a sheath formed by silicon oxide, the core extends substantially opposite the central portion. 21.
    Specific embodiments have just been described. Different variants and modifications will appear to those skilled in the art.
    Thus, the optoelectronic devices described above are for illustrative purposes only. Other optoelectronic devices can be produced, for example laser sources with optical or electrical pumping, with PN, PIN or not junctions, or even light-emitting diodes or photodetectors.
    权利要求:
    Claims (15)
    [1" id="c-fr-0001]
    1. Method for producing a tensile stress layer (12) based on tin germanium (GeSn), comprising the following steps:
    a) production of a semiconductor stack (10) resting on a support layer (1) by means of a sacrificial layer (2), said semiconductor stack (10) comprising a nucleation layer (11) and a so-called layer of interest (12) based on tin germanium (GeSn) epitaxially grown from the nucleation layer (11), said stack (10) having an initial value (σ ^) of non-zero voltage stress;
    b) structuring said semiconductor stack (10) so as to form:
    a structured part (20) and a peripheral part (30), the structured part (20) comprising a central portion (21) connected to the peripheral part (30) by at least two lateral portions (22) opposite each other 'other vis-à-vis the central portion (21), the side portions (22) having an average width (b) greater than an average width (a) of the central portion (21);
    c) suspension of the structured part (20) by etching of the sacrificial layer (2) located under the structured part (20), the central portion (21) said to be suspended then having a final value (oÎj) of stress in tension greater than the initial value (σ ^).
    [2" id="c-fr-0002]
    2. Method according to claim 1, comprising the following steps: prior to step a) of realization, estimation (110) of a value (x Sn ) of atomic proportion of tin and of a first minimum value (σ ^ ” Ιη ) voltage stress for which the layer of interest (12) has a structure of direct energy bands; and determining (120) a semiconductor stack (10) comprising a nucleation layer (11) and said estimated layer of interest (12), and having a second minimum value (oÎ; ' min ) of voltage stress;
    realization (130) of said semiconductor stack (10) so that it has said initial value (σι;) not zero of voltage stress and that the layer of interest (12) has an initial value (σ ^) lower than said first minimum value (σ ^ ιτ η ); determination (140) of the structure so that, after the suspension step (150), the central portion (21) of the structured part (20) has a final value (Og) of stress in tension greater than or equal to said second minimum value (Os' min ), said layer of interest (12) then having a final value (σ ^) of stress in tension greater than or equal to said first minimum value (σ ^ ιτιιη ) and then having a band structure direct energy.
    [3" id="c-fr-0003]
    3. Method according to claim 1 or 2, wherein the nucleation layer (11) is made of a semiconductor compound having a lattice parameter, called natural, lower than that of the material based on tin germanium of the layer of interest (12).
    [4" id="c-fr-0004]
    4. Method according to any one of claims 1 to 3, wherein the semiconductor stack (10) comprises at least one layer located between the layer of interest (12) and the nucleation layer (11) and produced in a semiconductor compound having a lattice parameter, called natural, less than or equal to that of the material based on tin germanium of the layer of interest (12).
    [5" id="c-fr-0005]
    5. Method according to any one of claims 1 to 4, wherein the semiconductor stack (10) has a thickness less than a thickness called critical.
    [6" id="c-fr-0006]
    6. Method according to any one of claims 1 to 5, wherein each layer of the semiconductor stack (10) has a thickness less than a thickness called critical.
    [7" id="c-fr-0007]
    7. Method according to any one of claims 1 to 6, in which the semiconductor stack (10) comprises upper (13B) and lower (13A) layers based on tin germanium, doped according to different types of conductivity, located on either side of the layer of interest (12), the latter being unintentionally doped.
    [8" id="c-fr-0008]
    8. Method according to the preceding claim, in which, between the upper (13B) and lower (13A) doped layers on the one hand and the layer of interest (12) on the other hand, there is at least one so-called barrier layer. (15A, 15B) based on germanium, or based on germanium tin whose atomic proportion in tin is lower than the value of the atomic proportion of tin in the layer of interest (12).
    [9" id="c-fr-0009]
    9. Method according to any one of claims 1 to 8, wherein the atomic proportion of tin of the layer of interest (12) is less than 10%.
    [10" id="c-fr-0010]
    10. Method according to any one of claims 1 to 9, further comprising a step of bringing the structured part (20) into contact with a free surface (4) of the support layer (1), so as to render secured by molecular bonding to the structured part (20) of the support layer (1).
    [11" id="c-fr-0011]
    11. The method of claim 10, further comprising the following steps:
    determination of a minimum value of molecular bonding energy of the structured part (20) on the support layer (1), as well as a minimum value of bonded surface of the lateral portions (22), these minimum values being such that said molecular bonding energy is greater than elastic energy of the structured part (20);
    consolidation annealing at an annealing temperature such that the molecular bonding energy has a value greater than or equal to said previously determined minimum value; then etching of a so-called distal part (24) of the lateral portions (22) with respect to the central portion (21), so that the bonded surface of the lateral portions (22) has a value greater than or equal to said minimum value previously determined.
    [12" id="c-fr-0012]
    12. The method of claim 10 or 11, wherein the suspension step and the contacting step are carried out by etching the sacrificial layer (2) by HF in vapor phase optionally followed by deposition and then evaporation of a liquid between the suspended structured part (20) and the support layer (1), and in which, during the annealing step, the annealing temperature is greater than or equal to 200 ° C.
    [13" id="c-fr-0013]
    13. The method of claim 10 or 11, comprising, during the suspension step, oxidation or nitriding of a free surface (4) of the support layer (1) as well as a lower surface (23 ) of the structured part (20) oriented towards the free surface (4), and in which, during the annealing step, the annealing temperature is greater than or equal to 100 ° C.
    [14" id="c-fr-0014]
    14. The method of claim 13, wherein, following the suspension step, dielectric layers (41A, 41B), resulting from the oxidation or nitriding carried out, are formed at the level of the structured part ( 20) and of the support layer (1), which have a thickness preferably greater than or equal to lnnm.
    [15" id="c-fr-0015]
    15. Method for producing a microelectronic or optoelectronic device comprising said layer of interest (12) based on tin germanium obtained by the method according to any one of claims 1 to 14, in which a PN junction is produced (43 , 45) in the layer of interest (12), or a PIN junction (43, 44, 45) at the level of said layer of interest (12), the latter then being unintentionally doped.
    1/9
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    同族专利:
    公开号 | 公开日
    WO2018037189A1|2018-03-01|
    US10699902B2|2020-06-30|
    FR3055467B1|2018-09-21|
    US20190244813A1|2019-08-08|
    EP3504729A1|2019-07-03|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US20150102465A1|2013-10-10|2015-04-16|The Board Of Trustees Of The Leland Stanford Junior University|Material quality, suspended material structures on lattice-mismatched substrates|
    US20150372454A1|2014-06-23|2015-12-24|Commissariat A L'energie Atomique Et Aux Energies Alternatives|Device comprising a strained germanium membrane|
    EP3151266A1|2015-09-30|2017-04-05|Commissariat à l'énergie atomique et aux énergies alternatives|Method for forming a semiconductor portion by epitaxial growth on a stressed portion|
    FR3086800B1|2018-09-28|2020-10-02|Commissariat Energie Atomique|METHOD OF MANUFACTURING AN OPTOELECTRONIC DEVICE FOR EMISSION OF INFRARED LIGHT INCLUDING AN ACTIVE LAYER BASED ON GESN|
    US11031241B2|2018-12-20|2021-06-08|Applied Materials, Inc.|Method of growing doped group IV materials|
    FR3095893A1|2019-05-09|2020-11-13|Commissariat A L'energie Atomique Et Aux Energies Alternatives|optoelectronic device comprising a central portion tensioned along a first axis and electrically polarized along a second axis|
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1657987A|FR3055467B1|2016-08-26|2016-08-26|METHOD FOR PRODUCING A TENSION-CONTAINING LAYER BASED ON GERMANIUM TIN|
    FR1657987|2016-08-26|FR1657987A| FR3055467B1|2016-08-26|2016-08-26|METHOD FOR PRODUCING A TENSION-CONTAINING LAYER BASED ON GERMANIUM TIN|
    US16/327,520| US10699902B2|2016-08-26|2017-08-23|Process for producing a strained layer based on germanium-tin|
    EP17762163.8A| EP3504729A1|2016-08-26|2017-08-23|Process for producing a strained layer based on germanium-tin|
    PCT/FR2017/052261| WO2018037189A1|2016-08-26|2017-08-23|Process for producing a strained layer based on germanium-tin|
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