WO2004016384A1 - Method of bonding a piezoelectric material and a substrate - Google Patents

Method of bonding a piezoelectric material and a substrate Download PDF

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Publication number
WO2004016384A1
WO2004016384A1 PCT/GB2003/003531 GB0303531W WO2004016384A1 WO 2004016384 A1 WO2004016384 A1 WO 2004016384A1 GB 0303531 W GB0303531 W GB 0303531W WO 2004016384 A1 WO2004016384 A1 WO 2004016384A1
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WIPO (PCT)
Prior art keywords
bonding
materials
piezoelectric material
substrate
melting point
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PCT/GB2003/003531
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French (fr)
Inventor
Yury Nikolaevich Korkishko
Vyachesloav Alexandrovich Fedorov
Viktor Borisovich Yakovlev
Sergei Alexandrovich Gavrilov
Dmitry Gennadievich Gromov
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New Transducers Limited
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Priority claimed from RU2002122364/28A external-priority patent/RU2002122364A/en
Application filed by New Transducers Limited filed Critical New Transducers Limited
Priority to AU2003264717A priority Critical patent/AU2003264717A1/en
Publication of WO2004016384A1 publication Critical patent/WO2004016384A1/en

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    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00Piezoelectric or electrostrictive devices
    • H10N30/01Manufacture or treatment
    • H10N30/07Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base
    • H10N30/072Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by laminating or bonding of piezoelectric or electrostrictive bodies
    • H10N30/073Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by laminating or bonding of piezoelectric or electrostrictive bodies by fusion of metals or by adhesives

Definitions

  • the present invention relates to a method of bonding, in particular, to a method of bonding a piezoelectric material and a substrate by liquid phase diffusion bonding .
  • Solid phase bonding usually occurs by means of applying high pressure and/or high temperature to bonding articles or to additional bonding layer (s) to facilitate and/or accelerate diffusion between two or more materials which all are in solid state.
  • additional bonding layer s
  • the second type of bonding method i.e. liquid phase bonding, involves formation of a liquid phase made of one or more bonding materials or an additional bonding layer (s) between them and subsequent cooling of the resulting structure to transform said liquid phase into solid state. Namely, these are welding, soldering, fusion bonding and the like.
  • the present invention may be regarded as a new kind of fusion bonding method.
  • silicon fusion bonding at 1000°C and anodic bonding at 450°C are known from A . R . Mirza et al . , Silicon wafer bonding: key to MEMS high-volume manufacturing, Sensors 15 (12) (1998) 24 -33 .
  • the process temperature is relatively high in this case.
  • the anodic bonding can be performed at 180°C by using high alkaline content glass [see S . Shoji et al . , Low- temperature anodic bonding using li thium aluminosilicate - quartz glass ceramic, Sens . Actuators, A 64 (1998) 95- 100] , nevertheless, it is not a commercially available process.
  • the combination of the materials of the first and second coatings is preferably Au/Au, Au/Al, Zn/Cu, or Sn/Cu.
  • the method further includes the step of bringing the first and second coatings into close contact with each other and heating them under pressure to form a metallic bond or intermetallic compound between the first and second coatings, thereby bonding the piezoelectric element and the electrode.
  • the method disclosed in the US 09/822,636 (see claim 1) relates to the solid phase diffusion bonding type. Though there is no reference on this fact in claim 1, but according to paragraphs 0040 and 0044 of the specification "...the temperature of the laminate was about 200°C" and "...the bonding portion between the base electrode 24 and the piezoelectric element 28a was heated to 200°C without heating the head 56" .
  • the temperature of 200°C is lower than the lowest liquidus temperature in the preferable Au/Au, Au/Al, Zn/Cu, or Sn/Cu systems. Thus, there is no liquid phase occurred during the bonding process.
  • the method has several disadvantages.
  • the method discloses the bonding between piezoelectric element and electrode, while the electrode is usually made of metal or metal alloys. Thus, there is no reference to the bonding between piezoelectric material and substrate made of materials different from metal or metal alloys.
  • the method discloses heating under pressure, i.e. requires applying additional pressure to form a bond.
  • the method does not disclose the formation of bond having a melting point which is higher than bonding temperature, what makes it impossible to assemble a structure wherein previous bonding layer between structure elements should be in solid state during the subsequent bonding of other structure elements.
  • two preferable systems include Au component which is very expensive, and other components are pure metal which are relatively expensive too.
  • the method disclosed in claim 7 of the US 09/822,636 relates to conventional soldering methods and, consequently, has all corresponding disadvantages thereof.
  • a method of bonding a piezoelectric material and a substrate having a melting point T SUB comprising the steps of: a) depositing a layer of a first metallic material (Ml) having a melting point i on a bonding surface of the piezoelectric material; b) depositing a layer of the material Ml or a layer of a second metallic material (M2) having a melting point T 2 which is lower than T x , on a bonding surface of said substrate, wherein the material M2 being melted is capable to interact by diffusion with the material Ml to form a metallic bond having a melting point T1 2 which is higher than T 2 ; c) depositing at least one layer of the material M2 on the bonding surface of said piezoelectric material and/or substrate; d) bringing said bonding surfaces of the piezoelectric material and the substrate into close contact ; and e) heating a place of said contact to a temperature which is higher than T
  • a method of bonding a piezoelectric material and a substrate having a melting point SUB/ the method comprising the steps of: a) depositing a layer of a first metallic material (Ml) having a melting point T x on a bonding surface of the piezoelectric material; b) depositing a layer of the material Ml or a layer of a second metallic material (M2) having a melting point T 2 which is lower than Ti, on a bonding surface of said substrate, wherein the material M2 being melted is capable to interact by diffusion with the material Ml to form a metallic bond which comprises an alloy and/or intermetallic compound and/or solid solution; c) depositing at least one layer of the material M2 on the bonding surface of said piezoelectric material and/or said substrate; d) bringing said bonding surfaces of the piezoelectric material and the substrate into close contact ; and e) heating a place of said contact to a temperature which is higher than T
  • a method of articles bonding comprising the steps of: a) depositing a layer of a first material (Ml) having a melting point T x on a bonding surface of a first article having a melting point T AR1 ; b) depositing a layer of a second material (M2) having a melting point T 2 which is lower than Ti on a bonding surface of a second article having a melting point T AR2 , wherein the material M2 being melted is capable to interact by diffusion with the material Ml to form a bond having a melting point T 12 which is higher than T 2 ; c) bringing said bonding surfaces of the first and second articles into close contact; d) heating a place of said contact to a temperature which is higher than T 2 but lower than any of the temperatures T 12 , T_ , T ARX and AR2 to form said bond.
  • the main idea of bonding method according to the present invention is in formation of at least two layers of metallic materials (i.e. metal or metallic alloy) consisted of one or more components on bonding surfaces of the piezoelectric material and the substrate to be bonded, wherein one of said materials has a low melting point . Diffusion mixing of the metallic materials after melting the material with low melting point results in formation of intermetallic compounds or solid solutions with required melting temperatures.
  • the materials Ml or M2 are chosen so that they can be well adhered to the bonding surfaces of the piezoelectric material and the substrate.
  • the substrate may be of any material to which the materials Ml and M2 may be adhered, preferable, of plastic materials (for example, polycarbonates) , dielectrics (for example, glasses and ceramics) , semiconductors (for example, Si wafers) , metals (steel, stainless steel, nickel, brass) and the like.
  • plastic materials for example, polycarbonates
  • dielectrics for example, glasses and ceramics
  • semiconductors for example, Si wafers
  • metals for example, stainless steel, nickel, brass
  • a piezoelectric material may be also used as the substrate, and the piezoelectric materials which forms both bonding articles may be the same material with different polarization directions.
  • the invention is not limited by bonding the piezoelectric material and the substrate and is adapted for bonding any articles made of the materials to which the materials Ml and M2 may be adhered.
  • the Ml and M2 layers may be deposited on the piezoelectric material and the substrate, respectively; or the Ml and M2 layers may be sequentially deposited on the piezoelectric material while the M2 layer is deposited on the substrate; or the Ml and M2 layers may be sequentially deposited on the substrate while the Ml layer is deposited on the piezoelectric material; preferably, both Ml and M2 layers are sequentially deposited both on the piezoelectric material and the substrate.
  • the Ml and M2 layers deposited on the piezoelectric material may have different compositions comparing the Ml and M2 layers deposited on the substrate.
  • the step of heating comprises two substeps, wherein the first substep is carried out to form a liquid phase of the material M2 , and the heating temperature on the second substep is increased to activate mutual diffusion of the materials Ml and M2 and to facilitate/accelerate formation of the metallic bond.
  • the metallic bond comprises at least one intermetallic compound or at least one solid solution based on said intermetallic compound.
  • the metallic bond may comprise a solid solution based on the materials Ml and M2.
  • the piezoelectric material is a Pb(Zr x Ti ⁇ - X )0 3 based material (PZT) .
  • the piezoelectric material may have other chemical composition as well as may be a composite.
  • Two types of low- temperature bonding may be used for formation of bi- and multi- morph structures comprising the piezoelectric material .
  • the first type has a bonding temperature lower than temperature of depolarization (a Curie temperature Tc) .
  • Second one has a higher temperature than temperature of depolarization.
  • the polarization process for piezoelectric material is usually carried out by applying high voltage (for example, 1-5 kV per one cm of piezoelectric material thickness) .
  • the piezoelectric material is previously poled before bonding and has a Curie temperature T c which is higher than T 2 , and the heating temperature is lower than T c .
  • the depolarization process for piezoelectric material occurs when the temperature of piezoelectric material approaches or overcomes the Curie temperature T c , and the rate of depolarization process is increased with rising the temperature.
  • the piezoelectric material is the Pb (Zr x Ti ⁇ _ ⁇ )0 3 based material (the Curie temperature T c is about 200 - 250°C)
  • maximum temperature is preferably lower than 400°C to prevent Pb loses from PZT.
  • the preferable materials Ml and M2 are Ni or Ni-based alloy and In or In-based alloy, respectively; most preferably, the materials Ml and M2 are Ni 70 wt . % - Cu 30 w . % alloy and In, respectively, and the heating temperature on the is between about 160°C and about 200°C because the experimental data show that heating treatment of the piezoelectric material in the temperature range from 2/3 T c to T c leads to partial depolarization and respective decreasing piezoelectric coefficients of the piezoelectric material .
  • additional layers of other materials are deposited on the bonding surfaces of the piezoelectric material and the substrate before depositing of said Ml or M2 layers.
  • the material M2 is deposited in a such amount comparing to an amount of the material Ml, and the step of heating is carried out during a such period of time so that the material M2 is completely spent on formation of the metallic bond.
  • the method is adapted for assembling a structure, wherein every previous bonding of structure elements should be in solid state during the subsequent bonding of structure elements.
  • FIGS la) - c) are schematic diagrams illustrating contacting, compressing and temperature-raising stages of the present invention respectively, magnified detail of the interface between the contacting layers being shown within the magnifying glass symbol .
  • FIGS. 2 to 7 shows a phase diagram of Ni-In, Ni-Sn, Cu-Sn, Bi-Cu, Bi-Zn, Al-Bi binary systems, respectively.
  • the layer Ml and the layer M2 are sequentially formed on each of two PZT wafers 10,20.
  • Material of the layer M2 is a metal (for example, In, Sn, Bi, Pb, Ga) or an alloy based on said metal (for example, In-Sn, Sn-Pb) having low melting temperature (lower 400°C) .
  • Material of the layer Ml is metal (for example, Ni, Co, Cu, Zn, Al , Ti, Zr, Au, Ag, Pt) having more high melting temperature (over 600°C) , than material of layer M2.
  • the selection of Ml and M2 materials is determined by the formation of solid solutions or compounds between them.
  • the bonding of wafers is performed by an axial loading of more 0.5 kg/cm 2 and a sequential annealing at the temperature higher than the melting point of the layer M2. After that the temperature may be raised up to 300-400°C to dissolve liquid phase and to form solid compound (s) or solid solution.
  • the system where the material of layer Ml is Ti, and the material of layer M2 is Al, can not be used for the bonding, nevertheless the significant difference between the melting temperature of these materials.
  • the active interaction between Al and Ti thin films occurs at 400- 450°C and compounds Ti 3 Al and TiAl 3 are formed (the melting temperature of Al is 660°C) .
  • the appearance of the Al liquid phase is not practically possible for the comparable amounts of Al and Ti, since the all Al will be consumed for the Ti x Al y compound formation.
  • the indium the melting temperature of which is 156°C only, may be used as material of the layer M2.
  • the nickel the melting temperature of which is 1453 °C, may be used as material of the layer Ml.
  • the Ni-In phase diagram see Fig. 2
  • the formation of few compounds Ni x In y is possible in Ni-In system. These compounds have the significantly higher melting temperature, than the pure indium.
  • the liquid phase is formed between two PZT plates, and the successful wafer bonding take place. Such procedure can be applied for bonding of previously poled PZT plates.
  • the two-step heat treatment may be performed.
  • the In is melting, and at the second stage the temperature is increased up to 300-400°C to activate diffusion of In and to form the Ni x In y compound.
  • the formed compound has melting point higher than both the melting point of In and Curie point of PZT. Duration of the second stage is defined by full consumption of In melt .
  • Ni-Sn pair (Fig. 3) .
  • This pair of metals can be used for bonding of non-polarized PZT plates.
  • Low melting temperature of Sn (232 °C) and high melting temperature of Ni (1453°C) allows to provide vacuum annealing.
  • the Sn becomes liquid, and then during Ni-Sn interdiffusion, the melting point of Ni x Sn y compounds rises extremely from 232°C up to 1200°C with Sn content from 100 to 40 atom.%.
  • the poling procedure could be performed after bonding.
  • Cu-Sn pair (Fig. 4) .
  • This pair of metals can be used for bonding of non-polarized PZT plates.
  • Low melting temperature of Sn (232 °C) and high melting temperature of Cu (1085°C) allows to provide vacuum annealing.
  • the Sn becomes liquid, and then during Cu-Sn interdiffusion, the melting point of several phases forming in this system (for example, ⁇ -, ⁇ -, ⁇ -, ⁇ -, ⁇ -phases) rises extremely from 232 °C up to 750°C with Sn content from 100 to 30 atom.%.
  • the poling procedure could be performed after bonding.
  • Cu-Bi pair (Fig. 5) .
  • This pair of metals can be used for bonding of non-polarized PZT plates.
  • Low melting temperature of Bi (271°C) and high melting temperature of Cu (1085°C) allows to provide vacuum annealing.
  • the Bi becomes liquid and then during Cu-Bi interdiffusion, the melting point of CU x Bi ⁇ .- x solid solution rises extremely from 271°C up to 800 °C with Bi content from 100 to 20 wt . % .
  • the poling procedure could be performed after bonding.
  • Zn-Bi pair (Fig. 6) .
  • This system may be used for bonding of unpoled PZT plates .
  • Low melting temperature of Bi (271°C) and relatively high melting temperature of Zn (419, 5°C) allows to provide vacuum annealing.
  • the Bi becomes liquid and then during Zn-Bi interdiffusion, the melting point of Zn x Bi ⁇ _ x solid solution rises from 271°C up to 400°C.
  • the poling procedure could be performed after bonding.
  • Al-Bi pair (Fig. 7) reveals similar behavior as the Bi-Zn pair.
  • This system may be used for bonding of unpoled PZT plates.
  • Low melting temperature of Bi (271°C) and relatively high melting temperature of Al (660°C) allows to provide vacuum annealing.
  • the Bi becomes liquid and then during Al-Bi interdiffusion, the melting point of Al x Bi ⁇ - x solid solution rises from 271°C up to 660°C.
  • the poling procedure could be performed after bonding.
  • the following are examples of binary systems which are not suitable for bonding in accordance with the present invention.
  • Sn-Pb system is not suitable for PZT bonding because of melting points of both components are higher than the Curie temperature of PZT, and eutectic temperature is lower than temperature required for the subsequent poling.
  • Bi-Sn system is not suitable for PZT bonding because of melting points both of components is higher than the Curie temperature, and eutectic temperature is lower than temperature required for the poling.
  • Both Ni and In films may be formed by vacuum deposition or by electrochemical deposition.
  • PZT surface is extremely rough always. In this reason application of thick (more than 5 ⁇ m) metal films is required. Electrochemical metal deposition from aqueous solutions is an attractive technique for this purpose. Compared with vacuum deposition, an electrochemical technique requires a cheaper equipment and shorter time of processing.
  • In (indium) electrodeposition was used at Ni electrode, which was previously formed at PZT surface by vacuum deposition. Electrochemical deposition was performed in water solution of In 2 S04 (50 g/1) under 10 mA/cm 2 current density during 30 or higher minutes. Indium deposition rate was about 0.1 ⁇ m/min. Before electrodeposition the PZT plate was cleaned in boiling propanol during 5 min to dissolve organic contaminations on the surface.
  • Electrolyte compositions are follows:

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Abstract

A method of bonding a piezoelectric material and a substrate having a melting point TSUB comprises the steps of: a) depositing a layer of a first metallic material (M1) having a melting point T1 on a bonding surface of the piezoelectric material; b) depositing a layer of the first metallic material (M1) or a layer of a second metallic material (M2) having a melting point T2 which is lower than T1, on a bonding surface of said substrate, wherein the second metallic material (M2) being melted is capable to interact by diffusion with the material (Ml) to form a metallic bond having a melting point T12 which is higher than T2; c) depositing at least one layer of the second metallic material (M2) on the bonding surface of said piezoelectric material and/or substrate; d) bringing said bonding surfaces of the piezoelectric material and the substrate into close contact; and e) heating a place of said contact to a temperature which is higher than T2 but lower than any of the temperatures T12, T1 and TSUB to form the metallic bond.

Description

METHOD OF BONDING A PIEZOELECTRIC MATERIAL AND A SUBSTRATE
TECHNICAL FIELD
The present invention relates to a method of bonding, in particular, to a method of bonding a piezoelectric material and a substrate by liquid phase diffusion bonding .
BACKGROUND ART
Two types of bonding method are most widely used: 1) solid phase bonding and 2) liquid phase bonding. Solid phase bonding usually occurs by means of applying high pressure and/or high temperature to bonding articles or to additional bonding layer (s) to facilitate and/or accelerate diffusion between two or more materials which all are in solid state. Several approaches have been proposed, namely, high pressure bonding, bonding with heating of bonding materials or additional layers to a temperature near the melting point (s) thereof, explosive bonding and the like. The second type of bonding method, i.e. liquid phase bonding, involves formation of a liquid phase made of one or more bonding materials or an additional bonding layer (s) between them and subsequent cooling of the resulting structure to transform said liquid phase into solid state. Namely, these are welding, soldering, fusion bonding and the like. In accordance with this classification the present invention may be regarded as a new kind of fusion bonding method.
Many methods of article or wafer bonding or article- to-substrate bonding which allow the formation of all-in- one microstructures such as pressure sensors, accelerometer, microsensors and the like have been developed in recent decades. In most cases, hermetic sealing, high interface bonding strength and low bonding temperature are of major concern. In addition, a rigidity of bonding layer (s) is essential where a piezoelectric material and a substrate are bonded to facilitate vibration transfer from the piezoelectric material to the substrate. However, the general trend in the technology of lowering the bonding temperature often results in a lowering of the rigidity of the bonding layer (s). Furthermore, it is well known that materials with low melting points generally have a low rigidity due to softening affect which occurs when the temperature approaches the melting point. Thus, it is desirable to combine low bonding temperature and improved rigidity of the bonding layer (s) between the piezoelectric material and the substrate .
In addition, there are many cases which need bonding materials with a melting point which is higher than the bonding temperature, for example, to assemble a structure wherein previous bonding layer between structure elements should be in solid state during the subsequent bonding of other structure elements. The present invention provides an improved bonding method which meets both of said requirements .
Several technologies utilizing fusion bonding are known in art. Namely, silicon fusion bonding at 1000°C and anodic bonding at 450°C are known from A . R . Mirza et al . , Silicon wafer bonding: key to MEMS high-volume manufacturing, Sensors 15 (12) (1998) 24 -33 . However, the process temperature is relatively high in this case. The anodic bonding can be performed at 180°C by using high alkaline content glass [see S . Shoji et al . , Low- temperature anodic bonding using li thium aluminosilicate - quartz glass ceramic, Sens . Actuators, A 64 (1998) 95- 100] , nevertheless, it is not a commercially available process. The intermediate bonding by using Au-Si eutectic bonding material with eutectic temperature of 363 °C has been proposed in R. F. Wolffenbuttel , Low- temperature intermediate Au-Si wafer bonding; eutectic or silicide bond, Sens . Actuators, A 62 (1997) 680-686. Au/Sn to Ni/Au solder bonding, and Sn/Pb to Ni/Au solder bonding were used for making a sealed cavity of capacitive pressure sensor, while the respective treatment temperatures were 300°C, and 250°C for fluxless soldering in a vacuum oven with infrared light [see B . Rogge et al . , Solder-bonded micromachined capaci tive pressure sensors, Proc. SPIE 3514
(1998) 307-315] . A low-temperature wafer bonding process based on using In-Sn alloy as the intermediate layer for bonding was described in C. Lee et al . , Wafer bonding by low- temperature soldering, Sensors and Actuators 85 (2000) 330-334.
Actually, all materials that provide enough bonding force to the adhesive can be used at the bonding inter ace. Epoxy and thermoplastic polymers have been applied to the wafer level packaging with heat treatment temperatures of 150°C and 280°C, respectively [see G. Klink et al . , Wafer bonding wi th an adhesive coating, Proc . SPIE 3514 (1998) 50-61] . The following Patent documents may be regarded as being relevant: US 6,419,147; 6,404,063; 6,173,886; 6,059,175; 6,024,276; 5,994,666; 5,686,318; 5,655,000; 5,318,217; 5,242,102; 4,988,035.
The nearest prior art is disclosed in the JP Patent application 2000-335867 filed 02.11.2000 and relating US Patent application No 09/822,636 filed 30.03.2001 in the name of FUJITSU LIMITED and published 20.06.2002 under No 2002/0074902, IPC7 H01L 41/04. Namely, the last document discloses a method of bonding a piezoelectric element and an electrode, including the steps of forming a first coating of a material selected from the group consisting of Au, Al, Zn, Cu, and Sn on a bonding surface of the piezoelectric element, and forming a second coating of a material selected from the group consisting of Au, Al, Zn, Cu, and Sn on a bonding surface of the electrode. The combination of the materials of the first and second coatings is preferably Au/Au, Au/Al, Zn/Cu, or Sn/Cu. The method further includes the step of bringing the first and second coatings into close contact with each other and heating them under pressure to form a metallic bond or intermetallic compound between the first and second coatings, thereby bonding the piezoelectric element and the electrode.
The method disclosed in the US 09/822,636 (see claim 1) relates to the solid phase diffusion bonding type. Though there is no reference on this fact in claim 1, but according to paragraphs 0040 and 0044 of the specification "...the temperature of the laminate was about 200°C" and "...the bonding portion between the base electrode 24 and the piezoelectric element 28a was heated to 200°C without heating the head 56" . The temperature of 200°C is lower than the lowest liquidus temperature in the preferable Au/Au, Au/Al, Zn/Cu, or Sn/Cu systems. Thus, there is no liquid phase occurred during the bonding process.
In addition, the method has several disadvantages. For the first, the method discloses the bonding between piezoelectric element and electrode, while the electrode is usually made of metal or metal alloys. Thus, there is no reference to the bonding between piezoelectric material and substrate made of materials different from metal or metal alloys. For the second, the method discloses heating under pressure, i.e. requires applying additional pressure to form a bond. For the third, the method does not disclose the formation of bond having a melting point which is higher than bonding temperature, what makes it impossible to assemble a structure wherein previous bonding layer between structure elements should be in solid state during the subsequent bonding of other structure elements. For the fourth, two preferable systems include Au component which is very expensive, and other components are pure metal which are relatively expensive too. The method disclosed in claim 7 of the US 09/822,636 relates to conventional soldering methods and, consequently, has all corresponding disadvantages thereof.
DISCLOSURE OF INVENTION
It is therefore an object of the present invention to provide a method of bonding a piezoelectric material and a substrate, which makes it possible to assemble a structure wherein previous bonding layer between structure elements should be in solid state during the subsequent bonding of other structure elements.
It is another object of the present invention to provide a method of bonding a piezoelectric material and a substrate, wherein a resulting bonding layer has relatively high rigidity to facilitate vibrations transfer from the piezoelectric material to the substrate.
It is still another object of the present invention to provide a method of bonding a piezoelectric material and a substrate, which is relatively easy and not expensive.
It is still another object of the present invention to provide a method of bonding articles made of any materials, which makes it possible to assemble a structure wherein previous bonding layer between structure elements should be in solid state during the subsequent bonding of other structure elements.
In accordance with an aspect of the present invention, there is provided a method of bonding a piezoelectric material and a substrate having a melting point TSUB the method comprising the steps of: a) depositing a layer of a first metallic material (Ml) having a melting point i on a bonding surface of the piezoelectric material; b) depositing a layer of the material Ml or a layer of a second metallic material (M2) having a melting point T2 which is lower than Tx, on a bonding surface of said substrate, wherein the material M2 being melted is capable to interact by diffusion with the material Ml to form a metallic bond having a melting point T12 which is higher than T2; c) depositing at least one layer of the material M2 on the bonding surface of said piezoelectric material and/or substrate; d) bringing said bonding surfaces of the piezoelectric material and the substrate into close contact ; and e) heating a place of said contact to a temperature which is higher than T2 but lower than any of the temperatures T12 , Ti and TSUB to form the metallic bond.
In accordance with another aspect of the present invention, there is provided a method of bonding a piezoelectric material and a substrate having a melting point SUB/ the method comprising the steps of: a) depositing a layer of a first metallic material (Ml) having a melting point Tx on a bonding surface of the piezoelectric material; b) depositing a layer of the material Ml or a layer of a second metallic material (M2) having a melting point T2 which is lower than Ti, on a bonding surface of said substrate, wherein the material M2 being melted is capable to interact by diffusion with the material Ml to form a metallic bond which comprises an alloy and/or intermetallic compound and/or solid solution; c) depositing at least one layer of the material M2 on the bonding surface of said piezoelectric material and/or said substrate; d) bringing said bonding surfaces of the piezoelectric material and the substrate into close contact ; and e) heating a place of said contact to a temperature which is higher than T2 but lower than any of the temperatures Tx and TSUB to form the metallic bond. In accordance with a further aspect of the present invention, there is provided a method of articles bonding, the method comprising the steps of: a) depositing a layer of a first material (Ml) having a melting point Tx on a bonding surface of a first article having a melting point TAR1; b) depositing a layer of a second material (M2) having a melting point T2 which is lower than Ti on a bonding surface of a second article having a melting point TAR2, wherein the material M2 being melted is capable to interact by diffusion with the material Ml to form a bond having a melting point T12 which is higher than T2; c) bringing said bonding surfaces of the first and second articles into close contact; d) heating a place of said contact to a temperature which is higher than T2 but lower than any of the temperatures T12, T_ , TARX and AR2 to form said bond. The main idea of bonding method according to the present invention is in formation of at least two layers of metallic materials (i.e. metal or metallic alloy) consisted of one or more components on bonding surfaces of the piezoelectric material and the substrate to be bonded, wherein one of said materials has a low melting point . Diffusion mixing of the metallic materials after melting the material with low melting point results in formation of intermetallic compounds or solid solutions with required melting temperatures. According to one of the preferred embodiments of the present invention the materials Ml or M2 are chosen so that they can be well adhered to the bonding surfaces of the piezoelectric material and the substrate.
The substrate (or bonding surface thereof) may be of any material to which the materials Ml and M2 may be adhered, preferable, of plastic materials (for example, polycarbonates) , dielectrics (for example, glasses and ceramics) , semiconductors (for example, Si wafers) , metals (steel, stainless steel, nickel, brass) and the like. A piezoelectric material may be also used as the substrate, and the piezoelectric materials which forms both bonding articles may be the same material with different polarization directions.
However, the invention is not limited by bonding the piezoelectric material and the substrate and is adapted for bonding any articles made of the materials to which the materials Ml and M2 may be adhered. The Ml and M2 layers may be deposited on the piezoelectric material and the substrate, respectively; or the Ml and M2 layers may be sequentially deposited on the piezoelectric material while the M2 layer is deposited on the substrate; or the Ml and M2 layers may be sequentially deposited on the substrate while the Ml layer is deposited on the piezoelectric material; preferably, both Ml and M2 layers are sequentially deposited both on the piezoelectric material and the substrate. According to preferred embodiment of the present invention, the Ml and M2 layers deposited on the piezoelectric material may have different compositions comparing the Ml and M2 layers deposited on the substrate.
According to another preferred embodiment of the present invention the step of heating comprises two substeps, wherein the first substep is carried out to form a liquid phase of the material M2 , and the heating temperature on the second substep is increased to activate mutual diffusion of the materials Ml and M2 and to facilitate/accelerate formation of the metallic bond. According to another preferred embodiment of the present invention, in case the materials Ml and M2 are the following metals or alloys based on the following metals: Ni and In, Ni and Sn or Cu and Sn, respectively, the metallic bond comprises at least one intermetallic compound or at least one solid solution based on said intermetallic compound. In case the materials Ml and M2 are the following metals or alloys based on the following metals: Cu and Bi, Zn and Bi, Al and Bi, respectively, the metallic bond may comprise a solid solution based on the materials Ml and M2.
According to still another preferred embodiment of the present invention, the piezoelectric material is a Pb(ZrxTiι-X)03 based material (PZT) . However, the piezoelectric material may have other chemical composition as well as may be a composite. Two types of low- temperature bonding may be used for formation of bi- and multi- morph structures comprising the piezoelectric material . The first type has a bonding temperature lower than temperature of depolarization (a Curie temperature Tc) . Second one has a higher temperature than temperature of depolarization. The polarization process for piezoelectric material is usually carried out by applying high voltage (for example, 1-5 kV per one cm of piezoelectric material thickness) . Preferably, the piezoelectric material is previously poled before bonding and has a Curie temperature Tc which is higher than T2, and the heating temperature is lower than Tc. The depolarization process for piezoelectric material occurs when the temperature of piezoelectric material approaches or overcomes the Curie temperature Tc, and the rate of depolarization process is increased with rising the temperature. When the piezoelectric material is the Pb (ZrxTiι_χ)03 based material (the Curie temperature Tc is about 200 - 250°C) , in both cases maximum temperature is preferably lower than 400°C to prevent Pb loses from PZT. If the piezoelectric material is the previously poled PZT, the preferable materials Ml and M2 are Ni or Ni-based alloy and In or In-based alloy, respectively; most preferably, the materials Ml and M2 are Ni 70 wt . % - Cu 30 w . % alloy and In, respectively, and the heating temperature on the is between about 160°C and about 200°C because the experimental data show that heating treatment of the piezoelectric material in the temperature range from 2/3 Tc to Tc leads to partial depolarization and respective decreasing piezoelectric coefficients of the piezoelectric material .
According to still another preferred embodiment of the present invention, additional layers of other materials are deposited on the bonding surfaces of the piezoelectric material and the substrate before depositing of said Ml or M2 layers.
According to still another preferred embodiment of the present invention, the material M2 is deposited in a such amount comparing to an amount of the material Ml, and the step of heating is carried out during a such period of time so that the material M2 is completely spent on formation of the metallic bond. In this case the method is adapted for assembling a structure, wherein every previous bonding of structure elements should be in solid state during the subsequent bonding of structure elements. The above and other objects, features and advantages of the present invention and the manner of realizing them will become more apparent, and the invention itself will best be understood from a study of the following description and appended claims with reference to the attached drawings showing some preferred embodiments of the invention. BRIEF DESCRIPTION OF DRAWINGS
FIGS la) - c) are schematic diagrams illustrating contacting, compressing and temperature-raising stages of the present invention respectively, magnified detail of the interface between the contacting layers being shown within the magnifying glass symbol .
FIGS. 2 to 7 shows a phase diagram of Ni-In, Ni-Sn, Cu-Sn, Bi-Cu, Bi-Zn, Al-Bi binary systems, respectively.
BEST MODE FOR CARRYING OUT THE INVENTION Some preferred embodiments of the present invention for the case of PZT piezoelectric material will now be described in detail with reference to the drawings.
The layer Ml and the layer M2 are sequentially formed on each of two PZT wafers 10,20. Material of the layer M2 is a metal (for example, In, Sn, Bi, Pb, Ga) or an alloy based on said metal (for example, In-Sn, Sn-Pb) having low melting temperature (lower 400°C) . Material of the layer Ml is metal (for example, Ni, Co, Cu, Zn, Al , Ti, Zr, Au, Ag, Pt) having more high melting temperature (over 600°C) , than material of layer M2. The selection of Ml and M2 materials is determined by the formation of solid solutions or compounds between them. The bonding of wafers is performed by an axial loading of more 0.5 kg/cm2 and a sequential annealing at the temperature higher than the melting point of the layer M2. After that the temperature may be raised up to 300-400°C to dissolve liquid phase and to form solid compound (s) or solid solution.
High roughness of PZT surface results in formation of many voids at the mechanical-connected layers M2 (Fig. la) . At the same time the interface between the layer Ml and the layer M2 is much more uniform. As the result of this, the interaction between the layer Ml and the layer M2 is preferable compared to interaction between the layers M2. This problem may be solved partially by compressing (if material of the layer M2 has high plasticity (Fig. lb) . The complete solution of this problem is in transformation of the contacting layers M2 in liquid phase that guarantees uniform wetting of surfaces, filling of voids and, finally, mutual dissolving of two layers M2 and the creation of an intermetallic compound or solid solution M3 (Fig. lc) . The appearance of liquid phase results in increasing both the diffusion mobility and chemical activity of atoms of the layer M2. Therefore, the general requirement to the material of layer M2 is the low melting temperature, at which interaction between layer M2 and layer Ml occurs. Let's consider two different cases.
The system, where the material of layer Ml is Ti, and the material of layer M2 is Al, can not be used for the bonding, nevertheless the significant difference between the melting temperature of these materials. The active interaction between Al and Ti thin films occurs at 400- 450°C and compounds Ti3Al and TiAl3 are formed (the melting temperature of Al is 660°C) . Thus, the appearance of the Al liquid phase is not practically possible for the comparable amounts of Al and Ti, since the all Al will be consumed for the TixAly compound formation.
The indium, the melting temperature of which is 156°C only, may be used as material of the layer M2. The nickel, the melting temperature of which is 1453 °C, may be used as material of the layer Ml. As can be seen from the Ni-In phase diagram (see Fig. 2) , the formation of few compounds NixIny is possible in Ni-In system. These compounds have the significantly higher melting temperature, than the pure indium. At temperatures below Curie point of PZT (about 200-250°C) the liquid phase is formed between two PZT plates, and the successful wafer bonding take place. Such procedure can be applied for bonding of previously poled PZT plates.
If the PZT wafers are not previously poled or the piezoelectric material has higher Curie temperature, the two-step heat treatment may be performed. At the first stage the In is melting, and at the second stage the temperature is increased up to 300-400°C to activate diffusion of In and to form the NixIny compound. The formed compound has melting point higher than both the melting point of In and Curie point of PZT. Duration of the second stage is defined by full consumption of In melt .
Below several possible pairs of metals which can be used for bonding are given.
Ni-Sn pair (Fig. 3) . This pair of metals can be used for bonding of non-polarized PZT plates. Low melting temperature of Sn (232 °C) and high melting temperature of Ni (1453°C) allows to provide vacuum annealing. At first stage of heat treatment the Sn becomes liquid, and then during Ni-Sn interdiffusion, the melting point of NixSny compounds rises extremely from 232°C up to 1200°C with Sn content from 100 to 40 atom.%. The poling procedure could be performed after bonding.
Cu-Sn pair (Fig. 4) . This pair of metals can be used for bonding of non-polarized PZT plates. Low melting temperature of Sn (232 °C) and high melting temperature of Cu (1085°C) allows to provide vacuum annealing. At first stage of heat treatment the Sn becomes liquid, and then during Cu-Sn interdiffusion, the melting point of several phases forming in this system (for example, η-, ε-, ζ- , δ-, γ-, β-phases) rises extremely from 232 °C up to 750°C with Sn content from 100 to 30 atom.%. The poling procedure could be performed after bonding.
Cu-Bi pair (Fig. 5) . This pair of metals can be used for bonding of non-polarized PZT plates. Low melting temperature of Bi (271°C) and high melting temperature of Cu (1085°C) allows to provide vacuum annealing. At first stage of heat treatment the Bi becomes liquid and then during Cu-Bi interdiffusion, the melting point of CUxBiπ.-x solid solution rises extremely from 271°C up to 800 °C with Bi content from 100 to 20 wt . % . The poling procedure could be performed after bonding.
Zn-Bi pair (Fig. 6) . This system may be used for bonding of unpoled PZT plates . Low melting temperature of Bi (271°C) and relatively high melting temperature of Zn (419, 5°C) allows to provide vacuum annealing. At first stage of heat treatment the Bi becomes liquid and then during Zn-Bi interdiffusion, the melting point of ZnxBiι_x solid solution rises from 271°C up to 400°C. The poling procedure could be performed after bonding.
Al-Bi pair (Fig. 7) reveals similar behavior as the Bi-Zn pair. This system may be used for bonding of unpoled PZT plates. Low melting temperature of Bi (271°C) and relatively high melting temperature of Al (660°C) allows to provide vacuum annealing. At first stage of heat treatment the Bi becomes liquid and then during Al-Bi interdiffusion, the melting point of AlxBiι-x solid solution rises from 271°C up to 660°C. The poling procedure could be performed after bonding. The following are examples of binary systems which are not suitable for bonding in accordance with the present invention. Sn-Pb system is not suitable for PZT bonding because of melting points of both components are higher than the Curie temperature of PZT, and eutectic temperature is lower than temperature required for the subsequent poling. Bi-Sn system is not suitable for PZT bonding because of melting points both of components is higher than the Curie temperature, and eutectic temperature is lower than temperature required for the poling.
EXAMPLE 1
Both Ni and In films may be formed by vacuum deposition or by electrochemical deposition.
PZT surface is extremely rough always. In this reason application of thick (more than 5 μm) metal films is required. Electrochemical metal deposition from aqueous solutions is an attractive technique for this purpose. Compared with vacuum deposition, an electrochemical technique requires a cheaper equipment and shorter time of processing.
In our case In (indium) electrodeposition was used at Ni electrode, which was previously formed at PZT surface by vacuum deposition. Electrochemical deposition was performed in water solution of In2S04 (50 g/1) under 10 mA/cm2 current density during 30 or higher minutes. Indium deposition rate was about 0.1 μm/min. Before electrodeposition the PZT plate was cleaned in boiling propanol during 5 min to dissolve organic contaminations on the surface.
After In deposition, two PZT plates were mechanically bonded and annealed in vacuum (lxl0 Tor) at 200°C during time from 30 to 60 min.
It was found that during annealing of Ni-In system, the indium dissolves in nickel film or nickel dissolves in indium. Melting point of the formed peritectic NixIny alloy is higher than melting point of pure In and is higher than temperature of annealing (200°C) . It was ensured that piezo properties of PZT didn't change after bonding procedure. Measurements have shown, that the coefficient d3ι was not less than 255xl0~12 Kl/N. The total thickness of the bimorph structure consisted of two PZT plates bonded was 0,34-0,35 mm.
Electrolyte compositions for deposition of the metals mentioned above
Applied for thickness increasing of vacuum evaporated Ni film. An additional Ni thickness is required for dissolving of low-temperature melted metal (In, Bi, Sn) . Electrolyte compositions are follows:
Table 1 . Conditions of Ni deposition .
Figure imgf000019_0001
Table 2. Conditions of Bi deposition.
Figure imgf000020_0001
Table 3 Conditions of In deposition.
Figure imgf000020_0002
Table 4. Conditions of Cu deposition
Figure imgf000021_0001
Table 5. Conditions of Sn deposition
Figure imgf000021_0002
Table 6. Conditions of Pb deposition
Figure imgf000021_0003
The foregoing specification was described in the various embodiments of present invention which has a number of advantages over the prior art . Various modifications and variations can be made without departing from the scope of the present invention, as set forth in the accompanying claims .

Claims

1. A method of bonding a piezoelectric material and a substrate having a melting point TSUB, the method comprising the steps of: a) depositing a layer of a first metallic material (Ml) having a melting point i on a bonding surface of the piezoelectric material; b) depositing a layer of the material Ml or a layer of a second metallic material (M2) having a melting point T2 which is lower than Ti, on a bonding surface of said substrate, wherein the material M2 being melted is capable to interact by diffusion with the material Ml to form a metallic bond having a melting point Tι2 which is higher than T2; c) depositing at least one layer of the material M2 on the bonding surface of said piezoelectric material and/or substrate; d) bringing said bonding surfaces of the piezoelectric material and the substrate into close contact; and e) heating a place of said contact to a temperature which is higher than T2 but lower than any of the temperatures Tι2, T_ and TSUB to form the metallic bond.
2. A method according to claim 1 characterized in that said bonding surfaces of the piezoelectric material and the substrate are of materials to which the materials Ml or M2 may be adhered.
3. A method according to claim 1 characterized in that the step e) comprises two substeps, wherein the first substep is carried out to form a liquid phase of the material M2 , and the heating temperature on the second substep is increased to activate mutual diffusion of the materials Ml and M2 and to facilitate/accelerate formation of the metallic bond.
4. A method according to claim 1 characterized in that said piezoelectric material is previously poled and has a
Curie temperature T which is higher than T2, and in that the heating temperature on the step e) is lower than Tc.
5. A method according to claim 1 characterized in that said metallic bond comprises at least one intermetallic compound or a solid solution based on said intermetallic compound.
6. A method according to claim 1 characterized in that said metallic bond comprises a solid solution based on the materials Ml and M2.
7. A method according to claim 1 characterized in that said piezoelectric material is a Pb (ZrxTi!-x) 03 based material .
8. A method according to claim 1 characterized in that the materials Ml and M2 are the following metals or alloys based on the following metals, respectively: Ni and In, Ni and Sn, Cu and Bi, Cu and Sn, Zn and Bi, Al and Bi .
9. A method according to claim 7 characterized in that the heating temperature on the step e) is lower than about 400°C to prevent Pb loss from the Pb (ZrxTiι_x) 03 based material .
10. A method according to claim 4 characterized in that said previously poled piezoelectric material is a Pb (ZrxTiι-X) 03 based material, and said materials Ml and M2 are Ni or Ni-based alloy and In or In-based alloy, respectively.
11. A method according to claim 10 characterized in that said materials Ml and M2 are Ni 70 wt . % - Cu 30 wt . % alloy and In, respectively.
12. A method according to claim 10 or claim 11 characterized in that the heating temperature on the step e) is between about 160°C and about 200°C.
13. A method according to claim 1 characterized in that additional layers of other materials are deposited on the bonding surfaces of the piezoelectric material and the substrate before depositing of said Ml or M2 layers.
14. A method according to claim 1 characterized in that the material M2 is deposited in a such amount comparing to an amount of the material Ml, and the step e) is carried out during a such period of time so that the material M2 is completely spent on formation of the metallic bond.
15. A method according to claim 14 characterized in that it is adapted for assembling a structure, wherein every previous bonding of structure elements should be in solid state during the subsequent bonding of structure elements.
16. A method according to claim 1 characterized in that a piezoelectric material is used as the substrate.
17. A method according to claim 16 characterized in that the piezoelectric materials are the same material with different polarization directions.
18. A method according to claim 1 characterized in that said Ml and M2 layers are sequentially deposited both on the piezoelectric material and the substrate.
19. A method according to claim 18 characterized in that the Ml and M2 layers deposited on the piezoelectric material have different compositions comparing the Ml and M2 layers deposited on the substrate.
20. A method of bonding a piezoelectric material and a substrate having a melting point TSUB, the method comprising the steps of: a) depositing a layer of a first metallic material (Ml) having a melting point Ti on a bonding surface of the piezoelectric material; b) depositing a layer of the material Ml or a layer of a second metallic material (M2) having a melting point T2 which is lower than Ti, on a bonding surface of said substrate, wherein the material M2 being melted is capable to interact by diffusion with the material Ml to form a metallic bond which comprises an alloy and/or intermetallic compound and/or solid solution; c) depositing at least one layer of the material M2 on the bonding surface of said piezoelectric material and/or said substrate; d) bringing said bonding surfaces of the piezoelectric material and the substrate into close contact; and e) heating a place of said contact to a temperature which is higher than T2 but lower than any of the temperatures Tx and TSUB to form the metallic bond.
21. A method according to claim 20 characterized in that said bonding surfaces of the piezoelectric material and the substrate are of materials to which the materials Ml or M2 may be adhered.
22. A method according to claim 20 characterized in that the step e) is carried out to form a liquid phase of the material M2.
23. A method according to claim 20 characterized in that the step e) is carried out to form a liquid phase resulting from the interaction between the materials Ml and M2.
24. A method according to claim 20 characterized in that the step e) comprises two substeps, wherein the first substep is carried out to form a liquid phase of the material M2, and the heating temperature on the second substep is increased to form the intermetallic compound and/or solid solution.
25. A method according to claim 20 characterized in that the step e) comprises two substeps, wherein first substep is carried out to form a liquid phase resulting from the interaction between the materials Ml and M2, and the heating temperature on second substep is increased to form the intermetallic compound and/or solid solution.
26. A method according to claim 20 characterized in that said piezoelectric material is previously poled and has a Curie temperature Tc which is higher than T2, and in that the heating temperature on the step e) is lower than Tc-
27. A method according to claim 20 characterized in that said piezoelectric material is a Pb (ZrxTiι_x) 03 based material .
28. A method according to claim 20 characterized in that the materials Ml and M2 are the following metals or alloys based on the following metals, respectively: Ni and In, Ni and Sn, Cu and Bi, Cu and Sn, Zn and Bi, Al and Bi .
29. A method according to claim 27 characterized in that the heating temperature on the step e) is lower than about 400°C to prevent Pb loss from the Pb (ZrxTi1_x) 03 based material .
30. A method according to claim 26 characterized in that said previously poled piezoelectric material is a Pb(ZrxTiι-.x) 03 based material, and said materials Ml and M2 are Ni or Ni-based alloy and In or In-based alloy, respectively.
31. A method according to claim 30 characterized in that said materials Ml and M2 are Ni 70 wt . % - Cu 30 wt . % alloy and In, respectively.
32. A method according to claim 30 or claim 31 characterized in that the heating temperature on the step e) is between about 160°C and about 200°C.
33. A method according to claim 20 characterized in that additional layers of other materials are deposited on the bonding surfaces of the piezoelectric material and the substrate before depositing of said Ml and/or M2 layers.
34. A method according to claim 20 characterized in that the material M2 is deposited in a such amount comparing to an amount of the material Ml, and the step e) is carried out during a such period of time so that the material M2 is completely spent on formation of the metallic bond.
35. A method according to claim 34 characterized in that it is adapted for assembling a structure, wherein every previous bonding of structure elements should be in solid state during the subsequent bonding of structure elements.
36. A method according to claim 20 characterized in that a piezoelectric material is used as the substrate.
37. A method according to claim 36 characterized in that the piezoelectric materials are the same material having different polarization directions.
38. A method according to claim 20 characterized in that said Ml and M2 layers are sequentially deposited both on the piezoelectric material and the substrate.
39. A method according to claim 38 characterized in that the Ml and M2 layers deposited on the piezoelectric material have different compositions comparing the Ml and M2 layers deposited on the substrate.
40. A method of articles bonding, the method comprising the steps of : a) depositing a layer of a first material (Ml) having a melting point Ti on a bonding surface of a first article having a melting point TARI; b) depositing a layer of a second material (M2) having a melting point T2 which is lower than Ti on a bonding surface of a second article having a melting point .AR2, wherein the material M2 being melted is capable to interact by diffusion with the material Ml to form a bond having a melting point T12 which is higher than T2; c) bringing said bonding surfaces of the first and second articles into close contact; d) heating a place of said contact to a temperature which is higher than T2 but lower than any of the temperatures Tι2, Tx, TARI and TAR2 to form said bond.
41. A method according to claim 40 characterized in that said bonding surfaces of the articles are of materials to which the material Ml or M2 may be adhered.
42. A method according to claim 40 characterized in that the material M2 is deposited in a such amount comparing to an amount of the material Ml, and the step d) is carried out during a such period of time so that the material M2 is completely spent on formation of said bond.
43. A method according to claim 42 characterized in that the steps a) - d) are repeated for assembling a structure, wherein every previous bonding of structure elements should be in solid state during the subsequent bonding of structure elements.
44. A method according to claim 40 characterized in that said bond comprises at least one compound or a solid solution based on said compound.
45. A method according to claim 40 characterized in that said bond comprises a solid solution based on the materials Ml and M2.
46. A method according to claim 40 characterized in that at least one of the articles comprises a piezoelectric material .
47. A method according to claim 46 characterized in that both of the articles comprises the same piezoelectric material having different polarization directions.
48. A method according to claim 46 characterized in that said piezoelectric material is previously poled and has a
Curie temperature Tc which is higher than T2, and the heating temperature on the step d) is lower than Tc.
49. A method according to claim 46 characterized in that said piezoelectric material is a Pb (ZrxTiι_x) 03 based material.
50. A method according to claim 49 characterized in that the heating temperature on the step d) is lower than about 400°C to prevent Pb loss from the Pb (ZrxTiX-X) 03 based material .
51. A method according to claim 40 characterized in that the materials Ml and M2 are metallic materials.
52. A method according to claim 51 characterized in that the materials Ml and M2 are the following metals or alloys based on the following metals, respectively: Ni and In, Ni and Sn, Cu and Bi, Cu and Sn, Zn and Bi, Al and Bi .
53. A method according to claim 48 characterized in that said previously poled piezoelectric material is a Pb (ZrxTiι_x) 03 based material, and said materials Ml and M2 are Ni or Ni-based alloy and In or In-based alloy, respectively.
54. A method according to claim 40 characterized in that additional layers of other materials are deposited on the bonding surfaces of the articles before depositing of said Ml and/or M2 layers .
55. A method according to claim 40 characterized in that said Ml and M2 layers are sequentially deposited both on the first and second article.
56. A method according to claim 55 characterized in that the Ml and M2 layers deposited on the first article have different composition comparing the Ml and M2 layers deposited on the second article.
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