Sound transducer structure and method for manufacturing a sound transducer structure
11115755 · 2021-09-07
Assignee
Inventors
Cpc classification
H04R31/00
ELECTRICITY
International classification
H04R31/00
ELECTRICITY
Abstract
For manufacturing a sound transducer structure, membrane support material is applied on a first main surface of a membrane carrier material and membrane material is applied in a sound transducing region and an edge region on a surface of the membrane support material. In addition, counter electrode support material is applied on a surface of the membrane material and recesses are formed in the sound transducing region of the membrane material. Counter electrode material is applied to the counter electrode support material and membrane carrier material and membrane support material are removed in the sound transducing region to the membrane material.
Claims
1. A sound transducer structure comprising: a membrane; and a counter electrode spaced apart from the membrane, the counter electrode including: a plurality of openings disposed in a two-dimensional arrangement; and a plurality of elevations directed toward the membrane, the elevations disposed in a two-dimensional arrangement, the plurality of elevations being intermingled with the plurality of openings, wherein three or more of the plurality of elevations are each disposed on the counter electrode inside a respective triangle including vertices defined by centers of three openings of the plurality of openings that are closer to the respective elevation than any other opening of the plurality of openings.
2. The sound transducer structure of claim 1, wherein the two-dimensional arrangement of the plurality of openings includes a plurality of rows and a plurality of columns such that each row of the plurality of rows is staggered in relation to an adjacent row and each column of the plurality of columns is staggered in relation of an adjacent column, and wherein the two-dimensional arrangement of the plurality of openings includes a plurality of diagonals such that each diagonal of the plurality of diagonals is staggered in relation to an adjacent diagonal.
3. The sound transducer structure of claim 1, wherein each opening of the plurality of openings includes a circular shape.
4. The sound transducer structure of claim 1, wherein the plurality of elevations comprises a plurality of bumps.
5. The sound transducer structure of claim 1, wherein the counter electrode is positioned opposite the membrane.
6. The sound transducer structure of claim 1, wherein the counter electrode overlies the membrane.
7. The sound transducer structure of claim 1, wherein the plurality of elevations are disposed within a sound transducing region of the sound transducer structure.
8. The sound transducer structure of claim 1, wherein at least one of the membrane or the counter electrode includes a polysilicon material.
9. The sound transducer structure of claim 1, further comprising a stability improvement material arranged on a side of the counter electrode facing the membrane, wherein the counter electrode comprises a counter electrode material, the stability improvement material having a greater mechanical rigidity than the counter electrode material.
10. The sound transducer structure of claim 1, wherein the counter electrode includes a plurality of outwardly protruding connective elements.
11. The sound transducer structure of claim 10, wherein each outwardly protruding connective element of the plurality of outwardly protruding connective elements comprises at least one opening of the plurality of openings.
12. A sound transducer structure comprising: a membrane; and a counter electrode spaced apart from the membrane, the counter electrode including: a plurality of openings disposed in a two-dimensional arrangement on the counter electrode, wherein the two-dimensional arrangement of the plurality of openings includes a plurality of rows and a plurality of columns such that each row of the plurality of rows is staggered in relation to an adjacent row and each column of the plurality of columns is staggered in relation of an adjacent column, further wherein the two-dimensional arrangement of the plurality of openings includes a plurality of diagonals such that each diagonal of the plurality of diagonals is staggered in relation to an adjacent diagonal; a plurality of elevations directed toward the membrane, the elevations disposed in a two-dimensional arrangement, the plurality of elevations being intermingled with the plurality of openings, wherein three or more of the plurality of elevations are each disposed on the counter electrode inside a respective triangle including vertices defined by centers of three openings of the plurality of openings that are closer to the respective elevation than any other opening of the plurality of openings; and a plurality of outwardly protruding connective elements.
13. The sound transducer structure of claim 12, wherein each outwardly protruding connective elements of the plurality of outwardly protruding connective elements comprises at least one opening of the plurality of openings.
14. The sound transducer structure of claim 12, wherein the counter electrode is opposite the membrane.
15. The sound transducer structure of claim 12, wherein the counter electrode overlies the membrane.
16. A sound transducer structure comprising: a membrane; and a counter electrode spaced apart from the membrane, the counter electrode including: a plurality of openings disposed in a two-dimensional arrangement; and a plurality of elevations directed toward the membrane, the elevations disposed in a two-dimensional arrangement, each of the elevations being disposed central to three triangularly arranged openings of the plurality of openings that are each adjacent to the elevation.
17. The sound transducer structure of claim 16, wherein the counter electrode is positioned opposite the membrane.
18. The sound transducer structure of claim 16, wherein the counter electrode overlies the membrane.
19. The sound transducer structure of claim 16, wherein the plurality of elevations are disposed within a sound transducing region of the sound transducer structure.
20. The sound transducer structure of claim 16, wherein each opening of the plurality of openings includes a circular shape.
21. The sound transducer structure of claim 16, wherein the two-dimensional arrangement of the plurality of openings includes a plurality of rows and a plurality of columns such that each row of the plurality of rows is staggered in relation to an adjacent row and each column of the plurality of columns is staggered in relation of an adjacent column, and wherein the two-dimensional arrangement of the plurality of openings includes a plurality of diagonals such that each diagonal of the plurality of diagonals is staggered in relation to an adjacent diagonal.
22. The sound transducer structure of claim 12, wherein each outwardly protruding connective elements of the plurality of outwardly protruding connective elements comprises at least one elevation of the plurality of elevations.
23. A sound transducer structure comprising: a membrane; and a counter electrode spaced apart from the membrane, the counter electrode including: a plurality of openings disposed in a two-dimensional arrangement; a plurality of bumps directed toward the membrane; and a plurality of outwardly protruding connective elements, wherein the plurality of bumps are disposed within a sound transducing region of the sound transducer structure, wherein each outwardly protruding connective element of the plurality of outwardly protruding connective elements comprises at least one opening of the plurality of openings and at least one bump of the plurality of bumps, and wherein each bump of the plurality of bumps is disposed on the counter electrode central to three triangularly arranged openings of the plurality of openings that are each adjacent to the bump.
Description
BRIEF DESCRIPTION OF THE FIGURES
(1) Embodiments of the present invention will be detailed subsequently referring to the appended drawings.
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DETAILED DESCRIPTION
(17) Different embodiments of the present invention will be discussed subsequently referring to
(18) The same applies to the embodiments of inventive methods for manufacturing a sound transducer structure described referring to
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(24) As has already been described above, sound transducing in the inventive embodiment of a silicon microphone is based on a membrane 6 being deflected relative to a fixed counter electrode 4 and the resulting change in capacity between the membrane 6 and the counter electrode 4 being detected as a measured quantity. A number of requirements are made to the membrane 6, the counter electrode 4 and contacting thereof, which will be described shortly below and in greater detail referring to
(25) In general, the membrane 6 has to be arranged to be movable relative to the counter electrode 4, requiring it to be arranged above a free volume which in this sectional view cannot be seen for reasons of perspective, but is arranged below the membrane 6. In the sectional views of further embodiments of the present invention shown in
(26) The least requirement to wiring the embodiment of the present invention of
(27) In general, it is a goal when constructing a microphone to achieve the highest signal-to-noise ratio (SNR) possible. Among other things, this can be achieved when the change in capacity to be measured is as great as possible compared to the static capacity of the assembly to which no pressure is applied. This may, among other things, be achieved by forming the membrane to be as thin as possible so that it will deform significantly with slight changes in pressure (small sound pressure levels). In this context, the edge regions 16 are important in which unavoidably a static capacity forms between the membrane 6 and the counter electrode 4 which cannot be changed since the distance from the counter electrode 4 to the membrane 6 is fixed. The greater this static portion of the capacity relative to the overall capacity, the smaller the SNR
(28) Thus, for optimizing purposes, the counter electrode 4 in the inventive embodiment is not connected to the carrier substrate along its entire circumference but only to connective elements 19 arranged in an equidistant manner which are exemplarily enlarged in
(29) As can be seen clearly in
(30) A piston-like movement of the membrane 6 would be desirable for an idealized measurement free of disturbances. If the membrane as a whole moved relative to the counter electrode 4 without deforming, a linear connection would result between an (infinitesimal) change in deflection and the capacity measured, in analogy to a plate capacitor.
(31) Due to the highly integrated assembly of the inventive embodiment of a silicon microphone, this requirement can only be fulfilled approximately. To increase mechanical sensitivity, i.e. the ability of reacting to slight sound pressure changes, the thickness of the membrane may, for example, be reduced. At the same time, the inventive embodiment of the microphone may be operated by different operating voltages, i.e. different voltages may be applied between the counter electrode 4 and the membrane 6. Due to the electrostatic attraction resulting between the counter electrode 4 and the membrane 6, the sensitivity of the membrane or the entire arrangement may also be varied. However, a problem might result in that with too high a voltage the counter electrode 4 may also be deformed under the influence of the electrostatic force, which as far as reproducibility of the measurements is concerned is not desirable.
(32) The reduction in the membrane's thickness is limited on the one hand by the stability of the membrane itself (destruction with too high a sound pressure or too high a voltage). On the other hand, with too strongly bending a membrane there is the danger that it is deflected to the counter electrode and sticks thereto due to adhesion forces. Another parameter which may be varied when designing embodiments of an inventive microphone and have considerable influence on the measuring results, is the membrane's diameter. When producing a plurality of microphones, it is ideally to be kept to exactly to ensure reproducibility of a measurement of several inventive microphones. This will be of particular relevance if several inventive microphones are to be operated in an array.
(33) As has been described above, there are a number of geometrical boundary conditions which are to be considered when designing a microphone or sound transducer structure and have to be kept to with high precision. Ways of complying with individual boundary conditions or providing a microphone optimized for the intended purpose of usage by means of suitable design measures will be indicated in the embodiments of the present invention described below.
(34) Thus, at least one embodiment of the present invention offers the great advantage that all the design options can be realized in a single manufacturing process since it has complete modularity. At least one embodiment of the present invention allows a unique way of implementing individual ones of the options described subsequently without preventing realizing an option by omitting another option. Embodiments of the inventive manufacturing process or inventive manufacturing method described below are such that all the microphone variations can be manufactured by the smallest possible number of steps. Depending on the demands, sub-modules may be implemented or omitted.
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(37) In addition,
(38) In this context, it is to be pointed out that in order to unambiguously refer to the relevant surfaces of the three-dimensional material layers mentioned in connection with this embodiment of the invention, the term main surface will subsequently refer to those surfaces the area normal of which is parallel or anti-parallel to the setup direction 24 indicated in
(39) In particular, the term first main surface subsequently means that surface the area normal of which is in the direction of the setup direction 24. The setup direction 24 here indicates that direction in which individual subsequent layers of the sound transducer structure are applied on the surface of the carrier substrate 2 during manufacturing. In analogy, the term second main surface refers to those surfaces the area normal of which is opposite to the setup direction 24.
(40) A second oxide layer 26 on which the counter electrode 4 is arranged and which mechanically supports the same is arranged on the first main surface of the membrane 6, in the edge region. Since the second oxide layer 26 serves supporting the counter electrode 4 and, among other things, the thickness thereof determines the spacing between the counter electrode 4 and the membrane 6, the term second oxide layer will subsequently be used as a synonym to the term counter electrode support material to emphasize the function of the second oxide layer. According to an embodiment of the present invention, the thickness of the counter electrode support material 26 exemplarily is between 1000 nm and 3000 nm or between 500 nm and 3000 nm to achieve the desired functionality of an embodiment of an inventive microphone.
(41) In another embodiment of the present invention, the thickness of the membrane 6 or the membrane material is 100 nm to 500 nm or 100 nm to 1000 nm. In another embodiment of the present invention, the thickness of the membrane support material is between 100 nm and 1000 nm to achieve the desired membrane support.
(42) In another embodiment of the present invention, the thickness of the counter electrode material is 600 nm to 1800 nm or 500 nm to 2500 nm to achieve the required stability of the counter electrode 4.
(43) In order to protect the embodiment of the inventive sound transducer assembly of
(44) As has been described above, the membrane 6 is fixed or connected to the carrier substrate 2 in the edge region 16 via the membrane support material 22 so that under sound pressure the membrane 6 can move or deform only in the sound transducer region 30 delineated in
(45) In the embodiment of the present invention shown in
(46) Sticking of the membrane 6 to the counter electrode 4 can be prevented by the bumps 32 even if it is deflected to such an extent that it mechanically contacts the counter electrode 4.
(47) Compared to the possibility of arranging bumps on the surface of the membrane 6 itself, the inventive embodiment of
(48) Thus, in the embodiment of the present invention shown in
(49) In an embodiment of the present invention, amorphous silicon which is doped with phosphorus is used as the membrane material. After doping, crystallization is performed which allows polycrystalline, doped silicon to form by annealing. Thus, the doping and annealing determine the stress in the material.
(50) In another embodiment of the present invention, the counter electrode is made of a metal layer which may additionally be reinforced with silicon nitride.
(51) The following embodiments of the present invention illustrated in
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(53) A corrugation groove is a structure of the membrane 6 forming a closed contour in the membrane material. In the embodiment of
(54) The fact that the corrugation grooves 34 and bumps 32 are not both arranged on the membrane 6 has the great advantage that all options are left open in the manufacturing method to be described below, i.e. corrugation grooves 34, bumps 32 or both structures can be produced, wherein omitting one component does not influence the production process negatively.
(55) In addition, the embodiment of the invention of
(56) In another embodiment of the present invention, the corrugation grooves are raised from the surface of the membrane by 300 nm to 2000 nm or 300 nm to 3000 nm.
(57) In the embodiment of the present invention shown in
(58) In the inventive embodiment, the counter electrode 4 also becomes more rigid with the thickness of the stability improvement material 40, the possible increase in thickness here only being limited by the resulting topology. Different materials may be used here for precisely dimensioning the improvement in rigidity, wherein two different effects may be utilized here. On the one hand, materials may be used which themselves have a considerably higher layer stress than, for example, silicon which may be used for forming the counter electrode 4 (polysilicon), which has a layer stress of <100 MPa. If, for example, silicon nitride (Si.sub.3N.sub.4) is used for increasing the rigidity, a thin layer will already be sufficient to achieve a significant increase in the bending rigidity of the counter electrode 4 since a thin silicon nitride layer has a typical layer stress of 0.5 to 1 GPa.
(59) In another embodiment of the present invention, silicon oxy nitride Si.sub.xO.sub.yN.sub.z having a low oxygen content is used as a stability improvement material 40. In another embodiment of the present invention, silicides, such as, for example, WSi, are used as a stability improvement material.
(60) In a modular manufacturing method, applying the additional layer of stability improvement material 40 is simply possible by applying, before applying the counter electrode material 4, a thin layer of stability improvement material 40 which in one embodiment of the present invention consists of silicon nitride which additionally has high an etching selectivity and can thus at the same time serve as an etch stop when removing the counter electrode support material 26 between the membrane 6 and the counter electrode 4.
(61) The high flexibility of embodiment of the inventive method and embodiments of the inventive overall concept also allows providing most different materials as stability improvement materials 40, wherein polycrystalline materials may, for example, be selected, also due to their lattice constants, to form a stability-improving layer of stability improvement material 40. If materials having slightly different lattice constants are used, even warping of the counter electrode in the setup direction 24 may be produced by deposition at the interface between the stability improvement material 40 and the counter electrode support material 4.
(62) In another embodiment of the present invention, the thickness of the stability improvement material is between 10 nm and 300 nm or between 10 nm and 1000 nm.
(63) In another embodiment of the present invention, a ratio of the thickness of stability improvement material and the counter electrode material is between 0.005 and 0.5.
(64) In another embodiment of the present invention, any other semiconductor nitrides and semiconductor oxides, such as, for example, GaN, are used as a stability improvement material.
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(66) In a general case, the lateral walls of the carrier substrate 2 having formed by etching and limiting a free volume below the membrane 6 will have an, within certain limits, erratic shape. If the membrane carrier material 42 which is etching-resistive is missing, the unsupported membrane diameter of a membrane 6 will be determined by the etch process and thus be little precise.
(67) As is the case in the embodiment of the invention shown in
(68) To begin with, it should be noted that in the case shown in
(69) If the membrane diameter in
(70) If the movability of the membrane, when reducing the membrane diameter, is, for example, compensated by using thinner a membrane and if the same polarization voltage is used, the signal will also be maximized. Again, the ratio of the acoustic rigidity of the membrane and the rigidity of the cavity volume will improve.
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(72) Thus, the embodiment of the present invention shown in
(73) The combination of several characteristics of the embodiments of
(74) High modularity or flexibility of the embodiments of the inventive methods for manufacturing a sound transducer structure (MEMS process) is decisive which allows manufacturing sound transducer structures, such as, for example, microphones, for different applications by one and the same technology. Thus, microphones can, for example, be produced having high or low sensitivities, wherein they can at the same time be produced in a highly precise and cheap manner. Aspects which may optionally be implemented are:
(75) robust membrane electrode including corrugation
(76) robust membrane electrode without corrugation
(77) counter electrode stabilized using stability improvement material
(78) additional bottom membrane carrier layer (such as, for example, polysilicon) for making the membrane diameter more precise or for optimizing the ratio of membrane diameter and cavity volume
(79) Before examples of embodiments of inventive methods for manufacturing sound transducer structures will be discussed in greater detail using flow charts and schematic illustrations, the procedure when manufacturing inventive sound transducer structures will be discussed briefly referring to
(80) The sound transducer structure is set up successively in a setup direction 24 on the carrier substrate, wherein a layer sequence as may, for example, occur during production of the embodiment shown in
(81) An embodiment of a method for manufacturing a sound transducer structure is illustrated in the flow chart of
(82) The process starts from a carrier substrate 2 or wafer exemplarily illustrated in
(83) In a first step 60, membrane support material 22 (MSM) is applied to a first main surface of a membrane carrier material (MCM). As will be explained in greater detail below referring to
(84) In a second step 62, membrane material (MM) is applied in a sound transducing region 16 and edge region 30 on a first main surface of the membrane support material 22 opposite the first main surface of the membrane carrier material.
(85) In a third step 64, counter electrode support material 26 (CESM) is applied to a first main surface of the membrane material 6 opposite the first main surface of the membrane support material 22.
(86) In a fourth step 66, the counter electrode support material 26 is patterned by producing a plurality of recesses in a first main surface of the counter electrode support material 26 opposite the first main surface of the membrane material 6 in the sound transducing region.
(87) In a fifth step 68, counter electrode material 4 (CEM) is applied to the first main surface of the counter electrode support material 26.
(88) In a sixth step 70, membrane carrier material 2 and membrane support material 22 are removed in the sound transducing region 30 to a second main surface of the membrane material 6 abutting on the first main surface of the membrane support material 22.
(89) As has already been mentioned, it is a great advantage of the embodiments of inventive methods for manufacturing a sound transducer structure that these have great modularity. Thus, many individual steps may be combined with one another freely without unavoidably excluding of another optional step or another optional module when adding an individual step or module.
(90) This will be explained in greater detail below referring to
(91) Method steps being identical to the example shown in
(92) In
(93) The first options already result before the first step 60, i.e. before applying the membrane support material when the feature shown in the embodiments of
(94) Another option also results before applying the membrane support material, in case producing corrugation grooves 34 in the membrane is desired. In this case, in a third optional step 84, a closed contour of a predetermined height of additional membrane support material can be arranged on the first main surface of the membrane carrier material in the sound transducing region, as is described referring to
(95) The situation after applying the membrane material 6 in the second step is shown in the right illustration of
(96) Since, as has already been mentioned, the rounded shape of the corrugation grooves is not absolutely necessary, it is also possible to perform the third optional step 84 only after the first step 60, as is indicated in
(97) Further options or applying further optional modules in the embodiment shown in
(98) In the next step along the path A, the counter electrode material 4 is applied so that the result is a configuration 90a in which the recesses 88 are filled directly with counter electrode material. In the section enlargement shown it can be recognized that the recess 88 is completely filled with counter electrode material 4 so that the result is the configuration shown in the enlargement wherein the structure preventing the membrane 6 from sticking to the counter electrode 4 has a planar surface in the direction of the membrane 4.
(99) If path B is taken, additional counter electrode support material 92 is applied between the counter electrode support material 26 and the counter electrode material 4 in a fourth optional step 86 so that the result is a configuration 90b. Thus, the geometrical dimensions of the recesses 88 may be adjusted in a controlled manner or edges of the recesses 88 may be rounded, roughly in analogy to manufacturing the corrugation grooves.
(100) The section enlargement shown for path B thus shows another embodiment of the present invention in which, by suitably dimensioning the width b of the recess 88 and the thickness t of the additional counter electrode support material 92, the additional advantage can be achieved that the structure in the counter electrode material 4 preventing sticking to form a tip. With such a tip, sticking is prevented even more efficiently since in this case the membrane 6 and the counter electrode 4 can contact only in minimal areas.
(101) In an embodiment of the present invention, the thickness t of the additional membrane support material 92 exemplarily is about double the width b of the recess 88 (b≲2t). The result is the configuration shown in the section enlargement having tip structures on the surface of the counter electrode 4 which can efficiently prevent membrane 6 sticking.
(102) In order to obtain an embodiment of the present invention shown in
(103) Thus, the starting position in
(104) Similarly to the section enlargements already shown in
(105) It is to be mentioned here that final steps may be performed after the sixth step for completing production of a functional sound transducer, which may, for example, include patterning the counter electrode material 4 to provide pressure compensation holes in the counter electrode material 4 so that the membrane 6 can directly contact the surrounding gas mixture. Further completing steps may be opening and producing contact holes for contacting, applying pads to be contacted electrically and etching the cavity from the backside or removing by etching counter electrode support material 26 and membrane support material 22 to obtain a freely movable membrane 6. Even dicing individual microphone chips from a wafer belongs to the measures mentioned here.
(106) In summary, in an inventive embodiment of a sound transducer structure, the setup basically consists of up to three patterned polysilicon layers separated from one another by oxide layers. The membrane region on the carrier material (such as, for example, an Si wafer) is released from support by means of a dry etch method from the backside. In a last step, the membrane and the counter electrode are released from support by means of wet-chemical sacrificial layer etching of the oxide.
(107) Conductive tracks, pads and passivations may serve electrical coupling to an ASIC for processing data and supplying a voltage, or contacting other evaluating or measuring units.
(108) As is shown referring to
(109) Thus, the modules described again roughly below can be combined to one another to achieve an embodiment of an inventive sound transducer structure. As regards the terminology of the terms of the layers in the individual modules, reference is made to
(110) wafer
(111) module 1: poly1—precise membrane diameter (“substructure”) depositing an oxide layer 1 for the etch stop of etching the cavity (300 nm TEOS) depositing the poly1 layer (300 nm) implantation (phosphorus) crystallization patterning the poly1
(112) module 2: corrugation grooves depositing an oxide layer 2 (600 nm) patterning the oxide layer to form corrugation grooves
(113) module 3: poly2—membrane depositing an oxide layer 3 as an etch stop and intermediate layer to poly1 and, if necessary, for rounding the bumps (300 nm) depositing the membrane poly (300 nm) implantation (phosphorus) crystallization patterning the poly2 to form the membrane and, if applicable, guard ring
(114) module 4: sacrificial layer-gap distance-bumps depositing an oxide 4 (2000 nm) patterning holes as a pre-form of the bumps (diameter 1 μm, depth 0.7 μm-1 μm) depositing another 600 nm of oxide 4 for adjusting the sacrificial layer thickness and the gap distance, at the same time the shape for the pointed bump is defined
(115) module 5: back plate depositing an SiN layer for the case of a considerably stiffened counter electrode depositing the counter electrode poly3 (800-1600 nm) implantation (phosphorus) crystallization patterning the poly3 to form the counter electrode and perforation subsequent patterning of the oxide stack of the gap distance
(116) module 6: metallization/passivation depositing an intermediate oxide and, if applicable, flowing or CMP for leveling the topology or rounding edges patterning and opening contact holes on the substrate,
(117) poly1, poly2 and 3 depositing and patterning a metallization for conductive tracks and pads depositing the passivation opening the passivation via pads and membrane region
(118) module 7: MEMS etching the cavity on the backside of the wafer definition of a resist layer on the front side having an opening above the membrane region sacrificial layer etching of the oxide and the etch stop layer in an etching mixture containing hydrofluoric acid, rinsing, resist removing and drying
Dicing the wafer into individual microphone chips
(119) The inventive concept or the inventive method is not limited in its application to the manufacturing of microphones alone although it has been illustrated before predominantly using silicon microphone.
(120) The inventive concept may be applied to any other fields where measuring a pressure difference is important. Thus, in particular absolute or relative pressure sensors or pressure sensors for liquids including the inventive concept may also be configured or produced flexibly.
(121) Also, inventive sound or pressure transducers may be used for generating sound, i.e., for example, as loudspeakers, or for producing a pressure in a liquid.
(122) While this invention has been described in terms of several preferred embodiments, there are alterations, permutations, and equivalents which fall within the scope of this invention. It should also be noted that there are many alternative ways of implementing the methods and compositions of the present invention. It is therefore intended that the following appended claims be interpreted as including all such alterations, permutations, and equivalents as fall within the true spirit and scope of the present invention.