Method for the production of a single-crystal film, in particular piezoeletric
11101428 · 2021-08-24
Assignee
Inventors
Cpc classification
H10N30/072
ELECTRICITY
H03H9/02574
ELECTRICITY
H10N30/8542
ELECTRICITY
H03H9/54
ELECTRICITY
C30B25/186
CHEMISTRY; METALLURGY
H01L21/76254
ELECTRICITY
International classification
H01L21/762
ELECTRICITY
Abstract
A method of manufacturing a monocrystalline layer, comprises the following successive steps: providing a donor substrate comprising a piezoelectric material of composition ABO.sub.3, where A consists of at least one element from among Li, Na, K, H, Ca; and B consists of at least one element from among Nb, Ta, Sb, V; providing a receiver substrate, transferring a layer called the “seed layer” from the donor substrate on to the receiver substrate, such that the seed layer is at the bonding interface, followed by thinning of the donor substrate layer; and growing a monocrystalline layer of composition A′B′O.sub.3 on piezoelectric material ABO.sub.3 of the seed layer where A′ consists of a least one of the following elements Li, Na, K, H; B′ consists of a least one of the following elements Nb, Ta, Sb, V; and A′ is different from A or B′ is different from B.
Claims
1. A method of manufacturing a monocrystalline layer, comprising the following successive steps: providing a donor substrate comprising a piezoelectric material of composition ABO.sub.3, wherein A consists of at least one element selected from the group consisting of Li, Na, K, and H; and wherein B consists of at least one element selected from the group consisting of Nb, Ta, Sb, and V; bonding the donor substrate onto a receiver substrate such that a seed layer of the donor substrate is at a bonding interface, the seed layer having the composition ABO.sub.3; thinning the donor substrate to expose the seed layer; growing, by epitaxy on the seed layer, a monocrystalline layer of composition A′B′O.sub.3, wherein A′ consists of at least one element selected from the group consisting of Li, Na, K, and H; wherein B′ consists of at least one element selected from the group consisting of Nb, Ta, Sb, and V; and wherein A′ is different from A or B′ is different from B.
2. The method of claim 1, wherein A′ includes at least one element in common with A, and/or B′ includes at least one element in common with B.
3. The method of claim 1, wherein A′ is identical to A and B′ is different from B, or B′ is identical to B and A′ is different from A.
4. The method of claim 1, wherein A consists of a single element and B consists of a single element.
5. The method of claim 1, further comprising: prior to bonding the donor substrate onto the receiver substrate, forming an embrittlement area in the donor substrate; and after bonding the donor substrate onto the receiver substrate and before thinning the donor substrate, detaching a portion of the donor substrate along the embrittlement area so as to leave a remaining portion of the donor substrate bonded onto the receiver substrate.
6. The method of claim 5, wherein thinning the donor substrate to expose the seed layer comprises thinning the remaining portion of the donor substrate to expose the seed layer.
7. The method of claim 1, wherein a thickness of the seed layer is less than 2 μm.
8. The method of claim 1, wherein the receiver substrate comprises a semiconductor material and includes a trap-rich intermediate layer between the seed layer and the receiver substrate.
9. The method of claim 1, wherein, after the step of growing the monocrystalline layer of composition A′B′O.sub.3, a thickness of the monocrystalline layer of composition A′B′O.sub.3 is less than 20 μm.
10. The method of claim 1, further comprising providing at least one electrically insulating layer and/or at least one electrically conducting layer at the interface between the receiver substrate and the donor substrate.
11. The method of claim 1, further comprising transferring at least a portion of the monocrystalline layer from the receiver substrate onto a final substrate.
12. The method of claim 1, further comprising forming a surface acoustic wave device or a bulk acoustic wave device using the monocrystalline layer of composition A′B′O.sub.3.
13. The method of claim 1, wherein A consists of at least one element selected from the group consisting of Na, K, and H; and wherein A′ consists of at least one element selected from the group consisting of Na, K, and H.
14. The method of claim 1, wherein A consists of at least one element selected from the group consisting of Li, K, and H; and wherein A′ consists of at least one element selected from the group consisting of Li, K, and H.
15. The method of claim 1, wherein A consists of at least one element selected from the group consisting of Li, Na, and H; and wherein A′ consists of at least one element selected from the group consisting of Li, Na, and H.
16. The method of claim 1, wherein A consists of at least one element selected from the group consisting of Li, Na, and K; and wherein A′ consists of at least one element selected from the group consisting of Li, Na, and K.
17. The method of claim 1, wherein B consists of at least one element selected from the group consisting of Ta, Sb, and V; and wherein B′ consists of at least one element selected from the group consisting of Ta, Sb, and V.
18. The method of claim 1, wherein: B, wherein B consists of at least one element selected from the group consisting of Nb, Sb, and V; and wherein B′ consists of at least one element selected from the group consisting of Nb, Sb, and V.
19. The method of claim 1, wherein B consists of at least one element selected from the group consisting of Nb, Ta, and V; and wherein B′ consists of at least one element selected from the group consisting of Nb, Ta, and V.
20. The method of claim 1, wherein B consists of at least one element selected from the group consisting of Nb, Ta, and Sb; and wherein B′ consists of at least one element selected from the group consisting of Nb, Ta, and Sb.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) Other characteristics and advantages of the disclosure will be seen clearly from the detailed description given below, with reference to the accompanying drawings, in which:
(2)
(3)
(4)
(5)
(6)
(7)
(8) For reasons of legibility of the figures, the illustrated elements are not necessarily represented at scale. Elements designated by the same reference signs in different figures are identical.
DETAILED DESCRIPTION
(9)
(10) The filter includes a piezoelectric layer 10 and two electrodes 12, 13, in the form of two interdigitated metal combs deposited on the surface of the piezoelectric layer. On the side opposite electrodes 12, 13, the piezoelectric layer rests on a support substrate 11. Piezoelectric layer 10 is monocrystalline; indeed, excellent crystalline quality is required in order that no attenuation is caused to the surface wave.
(11)
(12) The resonator includes a thin piezoelectric layer (i.e., generally less than 1 μm thick, preferably less than 0.2 μm thick) and two electrodes 12, 13 installed either side of the piezoelectric layer 10, which, due to the method of manufacture according to the disclosure, is monocrystalline. Piezoelectric layer 10 rests on a support substrate 11. To isolate the resonator from the substrate and, by this, means to prevent waves propagating in the substrate, a Bragg mirror 14 is interposed between electrode 13 and substrate 11. In an alternative manner (not illustrated), this isolation could be accomplished by making a cavity between the substrate and the piezoelectric layer. These various arrangements are known to those skilled in the art, and will not, therefore, be described in detail in the present text.
(13) In a general manner, the disclosure proposes the formation of the monocrystalline layer, in particular, a piezoelectric layer, by means of epitaxy on a material of a donor substrate, used as a seed for the epitaxy, until the desired thickness is obtained for the monocrystalline layer, and of a transfer to a receiver substrate, where the transfer can be accomplished before the epitaxy (in which case, a surface layer of the donor substrate, called the seed layer, is transferred on to the receiver substrate), or after epitaxy (in which case, at least a proportion of the epitaxial layer is transferred on to the receiver substrate).
(14) The donor substrate can be a homogeneous monocrystalline substrate of the material in question. Alternatively, the donor substrate can be a composite substrate, i.e., in the form of a stack of at least two layers of different materials, a surface layer of which consists of the monocrystalline material in question.
(15) Among the piezoelectric materials of particular interest are the perovskites and similar materials, of structure ABO.sub.3. However, the interest that these materials may hold is not limited to their piezoelectric character. In particular, for other applications, for example, applications relating to integrated optics, they may possibly also be of interest due to their dielectric permittivity, their refraction indices or, alternatively, their pyroelectric, ferroelectric or alternatively ferromagnetic properties, for example, as applicable.
(16) A large family emerges. It is derived, in particular, from binary materials, such as LiNbO.sub.3, LiTaO.sub.3, KNbO.sub.3, KTaO.sub.3, leading to a general formula of the ABO.sub.3 type, where A consists of one or more of the following elements: Li, Na, K, H, and where B consists of one or more of the following elements: Nb, Ta, Sb, V.
(17) To summarize, it will be considered that A consists of one or more of the following elements: Li, Na, K, H, and B consists of one or more of the following elements: Nb, Ta, Sb, V.
(18) The receiver substrate acts as a mechanical support of the seed layer. It can be of any kind suitable for implementation of epitaxy (in particular, in terms of stability of performance at high temperature), and advantageously, but not imperatively, suitable for the application in question. It can be homogeneous or composite.
(19) At least one intermediate layer can be inserted between the receiver substrate and the seed layer. For example, such an intermediate layer can be electrically conducting or electrically insulating. Those skilled in the art will be able to choose the material and the thickness of this layer according to the properties that they wish the radiofrequency device intended to include and the piezoelectric layer to have.
(20) Advantageously, the receiver substrate can be made of a semiconductor material. This can be, for example, a silicon substrate. This conducting material includes an intermediate layer of the “trap-rich” type, which can either be formed on the receiver substrate, or formed on the surface of the receiver substrate. The intermediate layer of the trap-rich type is thus located between the seed layer and the receiver substrate, and enables the electrical insulation properties of the receiver substrate to be improved. The intermediate layer of the trap-rich type can be formed by at least one of the materials of the polycrystalline, amorphous or porous types, in particular, polycrystalline silicon, amorphous silicon or porous silicon, although is not restricted to these materials. In addition, depending on the stability of performance at high temperature of the intermediate layer of the trap-rich type for accomplishing epitaxy, it may be advantageous to introduce an additional layer between the receiver substrate and the intermediate layer of the trap-rich type, to prevent its recrystallization during a heat treatment.
(21) According to a first implementation, the method includes a transfer of the seed layer of a donor substrate on to a support substrate, followed by the above-mentioned step of epitaxy. In this case, the material of the seed layer is advantageously a material of composition ABO.sub.3, where A consists of at least one element from among: Li, Na, K, H, and B consists of at least one element from among: Nb, Ta, Sb, V. According to one implementation, both A and B consist of a single element. For example, the formula of ABO.sub.3 can be Li.sub.x1K.sub.1-x1Nb.sub.y1Ta.sub.1-y1O.sub.3, where x1=0 or 1 and y1=0 or 1. Two very widely used representatives of this family of materials are LiNbO.sub.3 and LiTaO.sub.3. To a lesser extent, substrates KNbO.sub.3 and KTaO.sub.3 are also available. In the present text, such a composition is called a binary composition. Such a binary material is generally manufactured by drawing in the form of an ingot. In this case, the composition of the epitaxial layer is advantageously different from the composition of the seed layer, of the A′B′O.sub.3 type, where A′ consists of one or more of the following elements: Li, Na, K, H; B′ consists of one or more of the following elements: Nb, Ta, Sb, V; A′ is different from A or B′ is different from B. To continue the previous example, the formula of A′B′O.sub.3 can be Li.sub.x2K.sub.1-x2Nb.sub.y2Ta.sub.1-y2O.sub.3, where 0≤x2≤1 and 0≤y2≤1 and where x2 is different from x1 or y2 is different from y1.
(22) In the present text, if the total number of elements comprising A and B is equal to 3, such a composition is called ternary; if the total number of elements comprising A′ and B′ is equal to 4, such a composition is called quaternary. Unlike with binary materials, such ternary or quaternary materials are not, in the vast majority of cases, obtained by drawing an ingot, but must be obtained by epitaxy on a suitable support in order to be of sufficient quality for the desired dimensions.
(23) In the first implementation, a material of binary composition ABO.sub.3 and a material of ternary (or higher order) composition A′B′O.sub.3 will be preferred. More specifically, preference will be given to the preceding ABO.sub.3 and A′B′O.sub.3 compositions in which A′ includes at least one element in common with A, and/or B′ includes at least one element in common with B, where this element in common is advantageously the predominant one in the composition of A or B. In an even more preferred manner, the preceding ABO.sub.3 and A′B′O.sub.3 compositions will be chosen in which A′ is identical to A when B′ is different from B, and B′ is identical to B when A′ is different from A. A′ may possibly be appreciably identical to A, or B′ appreciably identical to B, when the content of a majority element of A or B varies slightly (for example, when A is Li and A′ is Li.sub.0.9Na.sub.0.1, or alternatively when B is Ta.sub.0.5Nb.sub.0.5 and B′ is Ta.sub.0.6Nb.sub.0.4).
(24) According to a second implementation, the step of epitaxy is accomplished before the transfer step. In this case, the donor substrate material serving as the seed for the epitaxy is a material of composition A′B′O.sub.3, where A′ consists of one or more of the following elements: Li, Na, K, H; B′ consists of one or more of the following elements: Nb, Ta, Sb, V. In this case, the composition of the epitaxial layer is of the A″B″O.sub.3 type, where A″ consists of one or more of the following elements: Li, Na, K, H; B″ consists of one or more of the following elements: Nb, Ta, Sb, V. For example, the composition of the seed layer is Li.sub.x1K.sub.1-x1Nb.sub.y1Ta.sub.1-y1O.sub.3, where 0≤x1≤1 and 0≤y1≤1 and the composition of the epitaxial layer is Li.sub.x2K.sub.1-x2Nb.sub.y2Ta.sub.1-y2O.sub.3, where 0≤x2≤1 and 0≤y2≤1. The material of the epitaxial layer can be identical to that of the seed layer (in other words, A′ is identical to A″ and B′ is identical to B″, i.e., in the above-mentioned example, x1=x2 and y1=y2). Alternatively, the material of the epitaxial layer is different from that of the seed layer (in other words, A′ is different from A″ or B′ is different from B″; i.e., in the above-mentioned example, x1 is different from x2 or y1 is different from y2).
(25) In the second implementation, a material of binary composition A′B′O.sub.3 and a material of ternary (or higher order) composition A″B″O.sub.3 will be preferred. More specifically, preference will be given to the preceding A′B′O.sub.3 and A″B″O.sub.3 compositions in which A″ includes at least one element in common with A′, and/or B″ includes at least one element in common with B′, where this element in common is advantageously the predominant one in the composition of A or B. In an even more preferred manner, the preceding A′B′O.sub.3 and A″B″O.sub.3 compositions will be chosen in which A″ is identical to A′ when B″ is different from B′, and B″ is identical to B′ when A″ is different from A′. A′ may possibly be appreciably identical to A, or B′ appreciably identical to B, when the content of a majority element of A or B varies slightly (for example, when A is Li and A′ is Li.sub.0.9Na.sub.0.1 or, alternatively, when B is Ta.sub.0.5Nb.sub.0.5 and B′ is Ta.sub.0.6Nb.sub.0.4).
(26) According to a variant of the second implementation, the method also includes, after the transfer step, the resumption of epitaxy on the transferred layer, so as to form a monocrystalline layer of composition A′″B′″O.sub.3, where A′″ consists of one or more of the following elements: Li, Na, K, H; B′″ consists of one or more of the following elements: Nb, Ta, Sb, V. For example, the composition of the additional epitaxial layer can be of the Li.sub.x3K.sub.1-x3Nb.sub.y3Ta.sub.1-y3O.sub.3 type, where 0≤x3≤1 and 0≤y3≤1. x3 is preferably different from x2 or y3 is different from y2 (in other words, more generally, A′″ is different from A″ or B′″ is different from B″).
(27) The disclosure thus enables, in particular, a thin layer of a compound A′B′O.sub.3, A″B″O.sub.3, or A′″B′″O.sub.3, to be formed of excellent crystalline quality, and at least equal to that of the homogeneous substrates of the binary materials of this family, with a controlled thickness in a very wide range of thicknesses and, in particular, for a thickness of less than 20 μm, and a large variety of properties that can be adjusted through the composition of the material.
(28) The epitaxy can be accomplished by any appropriate technique, in particular, by chemical vapor deposition (CVD), liquid phase epitaxy (LPE) or pulsed laser deposition (PLD), etc. With respect to the materials considered here, reference may be made, for example, to the publications referenced at [2], [3], [4], [5], and [6].
(29) Those skilled in the art will be able to determine the reagents and the operating conditions according to the material that must be grown, and the chosen technique.
(30) The composition of the materials of the different layers is adjusted, through the choice of the elements constituting A, A′, A″ and/or A′″ and B, B′, B″ and/or B′″ and their stoichiometry in regard to the desired properties (for example, depending on the application: piezoelectric coupling factor, refraction index, etc.), but also taking into account the need to achieve consistency of the crystal lattice constants of the materials of the epitaxiated layers and their epitaxy support. The adaptation of lattice constants in the field of epitaxy is known to those skilled in the art.
(31) It is understood that in addition to the various epitaxial layers described, additional epitaxial layers may be added, in particular, buffer layers, intended to control the changes of the lattice constants, or of the stored stresses or, alternatively, layers intended to provide selective etching stop layers.
(32) The transfer of the seed layer (or, respectively, of the epitaxial layer) typically implies a step of bonding of the donor substrate and of the receiver substrate, as the seed layer (respectively, epitaxial layer) is located at the bonding interface, followed by a step of thinning of the receiver substrate so as to expose the seed layer (respectively, epitaxial layer).
(33) In a particularly advantageous manner, the transfer is performed using the SMART CUT® method, which is well known for the transfer of thin semiconducting layers, particularly when made of silicon.
(34) To this end, according to the first implementation, with reference to
(35) With reference to
(36) With reference to
(37) With reference to
(38) With reference to
(39) As can be seen in
(40) Layer 10 includes: a first portion 102 at the interface with receiver substrate 110, corresponding to the seed layer, a second portion 103 extending from first portion 102, corresponding to the epitaxial layer, made of a material of composition A′B′O.sub.3, where the material can be at least ternary.
(41) This substrate is advantageously used to manufacture a surface acoustic wave device as illustrated in
(42) The seed layer is typically less than 2 μm thick, and preferably less than 1 μm thick.
(43) The thickness of the epitaxial layer depends on the specifications of the device intended to incorporate the monocrystalline layer. In this regard, the thickness of the epitaxial layer is not limited either in terms of minimum value or of maximum value. Purely for information, the table below gives combinations of thicknesses of the seed layer and of the epitaxial layer:
(44) TABLE-US-00001 Seed layer 0.5 μm 0.05 μm 0.1 μm 0.03 μm Epitaxial layer 2.5 μm 0.95 μm 5 μm 0.15 μm
(45)
(46) With reference to
(47) An embrittlement area is then formed in an embrittlement area in donor substrate 100 or in epitaxial layer 103 of composition A″B″O.sub.3, so as to delimit a layer that is to be transferred. The embrittlement area can be formed by implantation of ionic species (shown diagrammatically by the arrows in
(48) In the example illustrated in
(49) According to another implementation (not illustrated), the embrittlement area is formed in layer 103. The layer that is to be transferred, in this case, consists of the portion extending between the free surface of layer 103 and embrittlement area 101.
(50) With reference to
(51) With reference to
(52) With reference to
(53) Layer 103 obtained in this manner can then be used to manufacture a surface acoustic wave or bulk acoustic wave device.
(54) According to a variant of this second implementation, an additional step is performed, illustrated in
(55) The thickness of layer 103 and, if applicable, of layer 104, is chosen according to the specifications of the radiofrequency device intended to incorporate the layer. The thickness of layer 103 is typically between 0.05 and 2 μm. The thickness of layer 104 is typically between 0.5 and 20 μm.
(56) Whichever implementation is utilized, as an alternative (not illustrated) to the SMART CUT® method, the transfer can be performed, after bonding of the donor substrate and the receiver substrate, through the removal of material, for example, by mechanical polishing and/or chemical etching of the donor substrate until the seed layer is exposed. This variant is less advantageous as it involves consumption of the donor substrate, whereas the SMART CUT® method allows possible recycling of the donor substrate. Conversely, this variant requires no implantation within the donor substrate.
(57) As can be seen in
(58) This substrate is advantageously used to manufacture a surface acoustic wave device as illustrated in
(59) In certain cases, it is possible for the receiver substrate on which the epitaxial growth occurs not to be optimal for the final application. Since the receiver substrate will be subjected to the operating conditions of epitaxy, there is, in fact, a limited choice of suitable materials. In particular, the receiver substrate cannot contain layers or elements that may be damaged by the epitaxy temperature. It can then be advantageous to transfer layer 10 onto a final substrate 111, the properties of which are chosen according to the desired application, by bonding it onto final substrate 111 through the surface of epitaxial layer 103 (cf.
(60) If it is desired to manufacture a surface acoustic wave device, metal electrodes 12, 13 in the form of two interdigitated combs are deposited on the surface of layer 10 opposite receiver substrate 110 or, if applicable, the final substrate (whether this concerns receiver substrate 110 or final substrate 111, the substrate forms the support substrate 11 noted in
(61) If it is desired to manufacture a bulk acoustic wave device, the method described above must be adapted accordingly. First, before the step of bonding illustrated in
(62) Whichever implementation is chosen, the method according to the disclosure enables a monocrystalline layer to be formed, which is not only binary but also ternary or quaternary, and thus allows a larger choice of properties for the layer than materials traditionally used for surface acoustic wave or bulk acoustic wave devices. By this means, a satisfactory compromise between the coupling coefficient and the electromechanical efficiency of the piezoelectric material can be obtained more easily.
(63) Another field of application where the development of such solutions of piezoelectric materials is of particular interest is that of micro-sensors and micro-actuators. In the case of micro-sensors, the purpose will, in general, be to measure a deformation caused by an external stress. In the case of micro-actuators, conversely, it will be sought to cause deformation of an element or motion of a moving part by application of an electric field, whether continuous or variable. Use of the piezoelectric material enables mechanical deformation and an electric signal to be linked. In the field of acoustics, for example, the external stress is a pressure wave that deforms a membrane. It can be within the audible spectrum, and objects that may typically be of interest are microphones (in sensor mode) and loudspeakers (in actuator mode). It can go beyond audible frequencies, for example, for the production of Piezo Micromachined Ultrasonic Transducers (PMUT). It may also concern static pressure sensors or, alternatively, inertial sensors (acceleration sensors, gyroscopes, etc.), for which the motion of a moving mass that moves under the effect of acceleration is measured by means of the piezoelectric material. The piezoelectric material comprises the entire deformed element (membrane, beam, cantilever, etc.), or advantageously only a portion of it, by stacking it with other materials such as silicon, for example, in order to ensure improved mechanical properties of the deformable portion. In the actuators category, piezoelectric materials can control a very precise movement and can be used, for example, to expel the ink from printer cartridges, or from micro-fluid systems, or, alternatively, to adjust a focal distance of an optical microsystem.
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