The present invention relates to the field of electromechanical microsystems commonly referred to as micro electro mechanical systems (MEMS) type devices. More particularly, it relates to the anodic bonding between a wafer of which one surface is made from silicon and a wafer of which one surface is made from glass. These two elements constitute the basic components of most MEMS type devices, a microsystem comprising one or more mechanical elements that are able to use electricity as an energy source if necessary in order to perform a function as a sensor and/or actuator with at least one structure having dimensions in the micrometric range, the function of the system being assured in part by the shape of said structure.
ALD Atomic Layer Deposition
CVD Chemical Vapour Deposition
LPCVD Low Pressure Chemical Vapour Deposition
MEMS Micro Electro Mechanical Systems
MIP Micro Implantable Pump
PECVD Plasma Enhanced Chemical Vapour Deposition
PVD Physical Vapour Deposition
a-Si Amorphous silicon
A microfluidic system such as a pump or flow regulator must be protected against chemical attack, particularly if it is intended to be implanted in a patient for many years, such as a system for releasing an active ingredient.
Generally, elements that are sensitive to such chemical attack, such as silicon or glass wafers, are covered with a protective layer. It is not always a simple matter to assemble these elements together. Such an assembly process was the object of a patent application relating to an implantable micro-fluidic system [R11].
For many years, several research groups have been conducting research (successfully) [R1, R4] into the possibility of bonding a surface of silicon coated in silicon nitride to a glass surface (generally Pyrex 7740).
In addition, other research groups have shown that it is possible to join two wafers of the same kind (made from silicon [R6, R7] or glass [R2, R5]) by anodic bonding using intermediate layers. But as is stated in the article by Knowles [R3], the objective in these studies was to enable bonding between two substrates that were impossible or difficult to join a priori, without recourse to one or more intermediate layers.
Another approach uses a direct bonding technique (without the aid of electrical voltage but using pressure and surface preparation) to join a silicon wafer coated with silicon nitride to a glass wafer [R8].
The present invention consists of a MEMS type device comprising a wafer such as is defined in the claims.
Said protection layers preferably serve to protect said wafers from attacks on the surface, which may be for example chemical, electrochemical, physical and/or mechanical in nature. In particular, such an attack may be associated with the pH of a contact solution or with a dissolution effect of the wafer cause by a solution.
Unlike the teaching of the prior art [R11], which simply presents the design of a fluidic resistance for an implantable pump in the form of a capillary network with a layer that offers better pH protection than that of glass or silicon, the problem addressed by our invention relates to the packaging of a MEMS by conventional anodic bonding of a wafer having one surface made of silicon with a wafer having one surface made of glass—a hard material or alloy most often made of silicon oxide (SiO2 silica, the principle component of sand) and fluxes, while protecting one another from chemical attacks of the surface. In this case, borosilicate such as Pyrex 7740 or an equivalent material such as those described in Table 1 (see below) will be used for preference, since a possible objective is to gain the benefit of the transparency of this material.
Table 1 Examples of commercially available glasses and glass-ceramic used for anodic bonding
To achieve this protection from attacks on the surface, silicon may be protected by a thin layer of type Si3N4 or TiN (already described in the literature), or in a more sophisticated manner by a combination of two layers: TiO2+Si3N4, or TiO2+a-Si. In this case, the layer of a-Si or Si3N4 that is deposited on the protection layer is not intended to protect the device against attacks on the surface, but merely to make the bond possible. This is also true for all the layer combinations described in Table 2.
Table 2 Examples of various materials used as interlayer material in conjunction with anodic bonding
The particular feature of Si3N4 is that it can function both as a protection layer and as an anodic bonding layer. However, it is difficult to make conformal deposits with Si3N4, particularly on structured surfaces. Yet surfaces of this kind are essential to the effectiveness of such layers as protection. In fact, the slightest defect can become the weak point in the system, which will be most vulnerable to the chemical attacks. It is therefore preferable to use TiO2 as a protective material, which is easy to deposit conformally on a structured surface as it is compatible with techniques such as ALD. Si2N4, which is not compatible with ALD type conformal depositing methods, may be deposited on top of the TiO2, on the bonding zone to make anodic bonding possible. It is known from the literature that it is not possible to achieve anodic bonding directly on titanium oxide deposited on silicon.
In the present document, a conformal deposit is defined as a layer deposited on a surface having a very high aspect ratio (such as depressions) that mould homogenously to said surface.
If the glass is chemically inert with respect to a solution of basic pH, the solubility of silicon oxide, an essential component of glass, increases significantly with the pH, as shown in
Whereas silicon nitride or titanium oxide lend themselves very well to being deposited on the glass as a protective layer, on the other hand it is not possible to effect direct anodic bonding between one of these protected wafers and a silicon surface which itself has a protective layer. We do not know of any protective layer that can be applied to a glass wafer and is also directly compatible with anodic bonding. In the case of glass, for example, silicon nitride or titanium oxide will be used as the protective layer, which can be combined with a thin layer of silicon oxide as the bonding layer.
This bonding layer must not only enable anodic bonding to take place, but also serve to preserve said bond over time despite being exposed to a basic pH solution. The bonding layer must be thin enough to allow the creation of capillary forces that are strong enough to create a valve-type capillary stop, preventing the basic solution from infiltrating the bonding zone and thus avoiding the risks of delamination. Since anodic bonding induces a chemical change in the material in the bonding zone by creating covalent bonds, the result of said chemical transformation may change the chemical/physical properties of the material and render it more resistant to basic solutions than was the native form thereof before anodic bonding.
Capillary valves or capillary stop valves serve to stop the flow of a solution inside a microfluidic device using a capillary pressure barrier when the geometry of the channel changes suddenly.
1. Borosilicate glass (for example, Pyrex 7740)
2. Functional surface layer
3. Protective layer (TiO2 for example)
4. Protective layer (SiO2 for example)
5. Monocrystalline silicon
6. Protective layer (TiO2 for example)
7. Protective layer (Si3N4 for example)
Despite the presence of intermediate layers, it is still possible to use conventional anodic bonding parameters.
In order to reduce the risk of local defects (pinholes), it is possible to we can use a conformal depositing technique called Atomic Layer Deposition (ALD), which is considered not to create pinholes or, if depositing by Chemical Vapour Deposition (CVD), to carry out the deposit in multiple steps.
When a process to obtain conformal deposit is used, it is usually impossible to carry out bonding between the two wafers. However, the present invention makes it possible to bond two wafers, of which at least one is furnished with a conformal deposit.
Moreover, the device of the present invention is obtained by applying a layer for protection from an attack on the surface over at least one zone made of silicon and a layer for protection from an attack on the surface over at least a zone made of glass. The wafers of the device may be structured before or after said protective layers are applied. After the application of these protective layers, a material that enables the anodic bonding to take place is added in a thin layer between the two protective layers.
The unit that makes up a device is able to comprise at least one fluid path. Said fluid path enables a solution to circulate not only between the protective layers but also to pass through all or part of said wafers. It may consist of channels, a valve, a sensor, pumping means, and so on.
Besides enabling said protective layers to be bonded to one another, due to its thickness, said bonding layer prevents said solution from infiltrating the bonding zone that defines the lateral extremities of said fluid path, through which said solution passes.
These layers may be applied conformal using various techniques: by deposition (ADL, LPCVD, and so on) or by growths (dry and wet oxidations).
The wafers structured and protected in this way are assembled with each other in order to create a fluid path.
While using an anodic bonding technique with standard parameters (350-400° C., 500-1000 V) it is possible to bond a silicon wafer to a wafer of glass (Pyrex 7740) despite the presence of intermediate layers that serve as protection from chemical attack.
Silicon can be protected by a thin (<50 nm) layer of TiN or any form of silicon nitride (deposited by ALD, PECVD, LPCVD) with variable stoichiometry. By using two layers it is also possible to protect it using a combination of TiO2+Si3N4 or TiO2+a-Si. With thicknesses of up to 250 nm for the TiO2, up to 500 nm for the additional layer of Si3N4 (this thickness may be as much as <1 μm for silicon nitride alone) or <500 nm for the additional layer of amorphous silicon.
The Pyrex may be protected by two layers: TiO2 followed by SiO2. Both layers may be deposited by ALD, reactive sputtering, PECVD (SiO2), or LPCVD (SiO2). The range of usable thicknesses is:
The use of ALD (Atomic Layer Deposition) as the deposition technique is very useful in our case since the number of topical defects (pinholes) is significantly lower than with the other deposition techniques mentioned [R9].
The use of ALD also makes it possible to conceive of protecting structures with extremely complex shapes because the technique is almost perfectly conformal (aspect ratio 1:1000 demonstrated [R10]).
In the case where the protection layers are deposited by CVD (Chemical Vapour Deposition), it is useful to proceed in several distinct stages. By shutting off the vacuum, this makes it possible to significantly reduce the risk of having two defects (pinholes) superimposed.
It should also be noted that this technique of anodic bonding does not require any pretreatment of the surfaces to prepare the bond. Unlike many other bonding techniques (polymer-bonding, plasma-activated bonding, and so on), as long as the wafers are free from particles larger than 0.5 μm it is easy to obtain a reliable and very tight bond.
Pressure tests on the different bonding configurations did not show any differences in the strength of the bond. It therefore seems that whatever the protective layers present on the Pyrex or silicon, anodic bonding is just as strong as in the case of a simple bond without a protective layer.
I. Compatible Bond
Various experiments have demonstrated the difficulty of joining silicon and glass by anodic bonding in which intermediate layers are added. The nature of the materials, the thickness of layers, the order of deposition and the positions of the layers relative to the wafers are just a few of the key parameters that must be mastered to ensure reliable anodic bonding. In addition, the thickness of the bonding layer is a critical factor for achieving this function. For example, a thickness of more than 500 nm SiO2 does not enable a bond to be made between the intermediate layers.
The following two examples illustrate three-layer bonding:
Bonding tests were performed on a silicon—Pyrex assembly. A 100 nm layer of silicon nitride was deposited on the silicon. On the Pyrex side, a thin layer of TiO2 (50 nm) covers the substrate. 100 nm SiO2 was deposited on top of this assembly. The assembly was bonded at 380° C. with 750 V. Scalpel tests showed excellent adhesion.
A silicon wafer was covered with a 100 nm layer of TiO2 followed by a 200 nm layer of SiO2 and then a further 100 nm layer of SiO2. As before, the bond was completed at 380° C. and with 750 V was performed. The results of bonding also showed excellent adhesion between these two wafers.
Several phenomena are cited in the literature to explain anodic bonding. Below we compare our experimental results with these phenomena.
Firstly, oxidation at the interface is possible with oxygen from the Pyrex (particularly the NaOH dissociated by the electrical field). In our case, we found that this theory can possibly explain some of the results:
The second phenomenon proposed by Veenstra R12 relates to the electrostatic force applied to the interface. Associated with the oxidation of the layers at the interface, the electrostatic force is a key to understanding: in our case, the titanium deposited on the Pyrex reduces the electrostatic force at the interface substantially.
A third phenomenon is the distance between the two wafers. This is why an electric field is applied to obtain an electrostatic force large enough to bring the wafers to be bonded into close contact with one another. In our case, the surface roughness, which is one of the aspects of proximity, might be significant: the difference in roughness between ALD deposits and sputtering is known, but does not seem to play an important part in our case.
II. Fluid Resistance
In order to show the quality of the protection and the bond under high pH conditions, a test vehicle representing a fluid resistance was used (
The test vehicle was exposed to a pH 12 solution, which represents an accelerated study form compared with a less basic pH in the context of chemical attack on silicon. In addition, regarding glass,
The channel in question may comprise 4 different layers (a), (b), (c) and (d), as shown in
In the case in which the silicon is covered with a layer (d) that cannot be bonded, layer (a) may be deposited on protective layer (d) and be used as the bonding layer.
Depending on the type of materials used for the bonding layer, said layer may also be exposed to attack of the surface thereof by a solution passing through the fluid path. Moreover, a thickness of 200 nm ensures good anodic bonding of the two wafers, but with such a thickness the bond quickly begins to show weak points. Thus, a 200 nm layer of SiO2 only partly prevents the basic solution from infiltrating the bond zone, which entails a considerable risk of delamination over time. In order to provide a liquid-tight joint between the two wafers, the applied layers of SiO2 may have a thickness from 50 nm to 100 nm.
As shown in
R1. S. Weichel, R. Reus S. Bouaidat, P. A. Rasmussen, O. Hansen, K. Birkelund, H. Dirac, Low-temperature anodic bonding to silicon nitride, in: Sensors and Actuators A, 82 (2000) 249-253
R2 A. Berthold, L. Nicola, P. M. Sarro, M. J. Vellekoop, Glass-to-glass anodic bonding with standard IC technology thin films as intermediate layers, in: Sensors and Actuators A, 82 (2000) 224-228
R3 K. M. Knowles, A. T. J. van Helvoort, Anodic bonding, in: International Materials Reviews, 51-5 (2006) 273-310
R4 T. N. H. Lee, D. H. Y. Lee, C. Y. N. Liaw, A. I. K. Lao, I. M. Hsing, Detailed characterization of anodic bonding process between glass and thin film-coated silicon substrates, in: Sensors and Actuators A, 86 (2000) 103-107
R5 D. J. Lee, Y. H. Lee, J. Jang, B. K. Ju, Glass-to-glass electrostatic bonding with intermediate amorphous silicon movie for vacuum packaging of microelectronics and its application, in: Sensors and Actuators A, 89 (2001) 43-48
R6 R. Legtenberg, S. Bouwstra, M. Elwenspoek, Low-temperature sensors for glass bonding applications using boron oxide thin films, in: J. Micromech. Microeng., 1(1991) 157-160
R7 A. Hanneborg, M. Nese, H. Jakobsen, R. Holm, Review: Silicon-to-thin film anodic bonding, in: J. Micromech. Microeng., 2(1992) 117-121
R8 M. Wiegand, M. Reiche, U. Gösele, K. Gutjahr, D. Stolze, R. Longwitz, E. Hiller, Wafer bonding of silicon wafers covered with various layers area, in: Sensors and Actuators A, 86 (2000) 91-95
R9 X. Du, K. Zhang, K. Holland, T. Tombler, M. Moskovits, Chemical corrosion protection of optical components using atomic layer deposition, in: Applied Optics, 48-33 (2009) 6470-6477
R10 J. W. Elam, D. Routkevitch, P. P. Mardilovich, S. M. George, Conformal coating on ultrahigh-aspect ratio nanopores of anodic alumina by atomic layer deposition, in: Chem. Mater., 15 (2003) 3507-3517
R11. T. Bork, F. Bianchi, Capillary fluidic chip for regulating drug flow rates of infusion pumps, European Patent EP2138198
R12. T. T. Veenstra et al., “Use of selective anodic bonding to create micropump chambers with virtually no dead volume”, J. Electrochem. Soc., 2000, 148 (2) p. G68-G72
Number | Date | Country | Kind |
---|---|---|---|
11169070.7 | Jun 2011 | EP | regional |
Filing Document | Filing Date | Country | Kind | 371c Date |
---|---|---|---|---|
PCT/IB2012/052868 | 6/7/2012 | WO | 00 | 12/9/2013 |