EP3495894A1 - Method for manufacturing a clock component - Google Patents
Method for manufacturing a clock component Download PDFInfo
- Publication number
- EP3495894A1 EP3495894A1 EP17205320.9A EP17205320A EP3495894A1 EP 3495894 A1 EP3495894 A1 EP 3495894A1 EP 17205320 A EP17205320 A EP 17205320A EP 3495894 A1 EP3495894 A1 EP 3495894A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- wafer
- component
- manufacturing
- watch
- watch component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims description 26
- 239000000463 material Substances 0.000 claims abstract description 63
- 238000005530 etching Methods 0.000 claims abstract description 25
- 239000010703 silicon Substances 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 11
- 238000000576 coating method Methods 0.000 claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000010453 quartz Substances 0.000 claims abstract description 6
- 239000000919 ceramic Substances 0.000 claims abstract description 5
- 239000010432 diamond Substances 0.000 claims abstract description 5
- 229910003460 diamond Inorganic materials 0.000 claims abstract description 5
- 229910052594 sapphire Inorganic materials 0.000 claims abstract description 3
- 239000010980 sapphire Substances 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 238000005240 physical vapour deposition Methods 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000005229 chemical vapour deposition Methods 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000005238 degreasing Methods 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 238000009832 plasma treatment Methods 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 238000012423 maintenance Methods 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- 229920006254 polymer film Polymers 0.000 claims 1
- 235000012431 wafers Nutrition 0.000 description 85
- 239000011347 resin Substances 0.000 description 15
- 229920005989 resin Polymers 0.000 description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 238000004090 dissolution Methods 0.000 description 6
- 238000000708 deep reactive-ion etching Methods 0.000 description 5
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- 230000009975 flexible effect Effects 0.000 description 3
- 238000005459 micromachining Methods 0.000 description 3
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010849 ion bombardment Methods 0.000 description 2
- 229920000052 poly(p-xylylene) Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 241000897276 Termes Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- 239000012212 insulator Substances 0.000 description 1
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- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- OANVFVBYPNXRLD-UHFFFAOYSA-M propyromazine bromide Chemical compound [Br-].C12=CC=CC=C2SC2=CC=CC=C2N1C(=O)C(C)[N+]1(C)CCCC1 OANVFVBYPNXRLD-UHFFFAOYSA-M 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- G—PHYSICS
- G04—HOROLOGY
- G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
- G04B19/00—Indicating the time by visual means
- G04B19/04—Hands; Discs with a single mark or the like
- G04B19/042—Construction and manufacture of the hands; arrangements for increasing reading accuracy
-
- G—PHYSICS
- G04—HOROLOGY
- G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
- G04B13/00—Gearwork
- G04B13/02—Wheels; Pinions; Spindles; Pivots
-
- G—PHYSICS
- G04—HOROLOGY
- G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
- G04B15/00—Escapements
- G04B15/14—Component parts or constructional details, e.g. construction of the lever or the escape wheel
-
- G—PHYSICS
- G04—HOROLOGY
- G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
- G04B17/00—Mechanisms for stabilising frequency
- G04B17/04—Oscillators acting by spring tension
- G04B17/06—Oscillators with hairsprings, e.g. balance
- G04B17/066—Manufacture of the spiral spring
Definitions
- the present invention relates to a method for manufacturing a watch component made from a micro-machinable material.
- Such a method of manufacturing the state of the art comprises a first step E1 ( figure 1a ) consisting in providing a plate 1 which is called by its English name "wafer", consisting of a first wafer 2 of micro-machinable material, for example silicon, whose thickness corresponds to that of the final component, of the order of 10 to 200 microns, and intended to be worked to form the component.
- This first wafer 2 is connected to a second wafer 4, with a thickness of the order of 0.5 mm, intended to serve as a support and is for example similarly made of silicon, via an intermediate layer 3 of silicon oxide.
- Such a wafer 1 is generally referred to as "wafer SOI" for "wafer silicon on insulator”.
- the second plate 4 and the intermediate layer 3 thus form a support, which allows the stiffening of the entire wafer 1, its safe handling, and easy handling during the manufacture of the watch component.
- the manufacturing method then comprises a step of adding a mask on the apparent face of the wafer 1, via the deposit (step E2, figure 1b ) of a resin layer 5, in which free zones 6 are formed (step E3, Figure 1 (c) by partially removing the resin by photolithography techniques.
- a wafer a wafer or an assembly of wafers, and / or optionally comprising additional layers, used in a manufacturing method comprising at least one etching, from a masking step corresponding to step E2.
- This wafer has two faces: the apparent face, which we will call also superior surface by convention, which will be engraved, and the lower face.
- the mask formed in the preceding step then allows the formation of at least one watch component, by etching (step E4, figure 1d ) of the first plate 2 of the wafer 1 in the free zones 6 of resin.
- the component (s) is / are thus formed (s) according to a geometry determined by the previously formed mask.
- step E5 the at least one watch component 9, illustrated by the figure 1f is obtained by separating the first wafer 2 from the second wafer 4 by means of a release step E6.
- This release step therefore has the effect of separating the watch component or components, etched in the first wafer 2, the intermediate layer 3, but also the micro-machinable material whose second wafer 4 is formed.
- This release step E6 is a complex step. It can be achieved by a complete dissolution of the material of the intermediate layer 3 from the upper face of the wafer 1, more precisely from the engravings 7 made in the first plate 2 of the wafer 1, which has the disadvantage of a very long stage time.
- An object of the present invention is to provide a method of manufacturing a watch component which improves the method of the state of the art.
- the object of the present invention is to provide a simplified method of manufacturing a watch component.
- the step of providing a wafer may include a step of providing a wafer thickness substantially equal to the maximum thickness of the watch component to be manufactured.
- the method may comprise a step of etching the material of the component throughout the thickness of the entire material of the component present in the wafer and / or throughout the thickness of the single wafer component comprising the wafer component material.
- the method of manufacturing a watch component is improved in that it greatly simplifies the end of the method of the state of the art, by simplifying or even eliminating the step of E6 release described above.
- the adjective superior to designate a surface on the side of the face of a wafer which will undergo the first engraving
- the adjective inferior for a surface of an opposite side we will use the adjective superior to designate a surface on the side of the face of a wafer which will undergo the first engraving, and the adjective inferior for a surface of an opposite side.
- the figure 2 represents a method of manufacturing a watch component according to a first embodiment of the invention.
- such a manufacturing method comprises a first step E11 ( figure 2a ) consisting in providing a wafer 11 of micro-machinable material, for example silicon.
- a wafer comprises a single wafer 12 intended to be worked to form the watch component.
- This single wafer 12 preferably has a thickness greater than or equal to 100 microns, or even greater than or equal to 120 microns. This thickness may especially be between 100 or 120 microns and 300 microns, or even up to 500 microns.
- the manufacturing method then comprises a step of adding a mask on the upper surface of the wafer 11, via the deposit (step E12, figure 2b ) of a resin layer 15, in which free zones 16 are formed (step E13, Figure 2c ) by partially removing the resin by photolithography techniques.
- the mask formed in the preceding step then allows the formation of at least one watch component, by etching (step E14, figure 2d ) of the wafer 11 through the free zones 16 of the resin mask.
- the component (s) is / are thus formed (s) according to a geometry determined by the previously formed mask.
- fasteners are provided to maintain the component (s) attached to the wafer 11.
- step E15, figure 2f the remaining resin is removed by dissolution, in a revelation step (step E15, figure 2f ) which makes it possible to obtain directly the wafer 12 machined including the component (s) clock (s) 19.
- the steps E12 to E15 substantially correspond to the steps E2 to E5 of the solution of the state of the art, and are therefore not described in detail.
- the etching is carried out conventionally, by photolithography and DRIE.
- the great advantage of this first embodiment of the invention is to have removed the second wafer support plate, which makes it possible to eliminate the tedious step of E6 release of the state of the art by dissolving the layer intermediate 3.
- the wafer 11 made of micro-machinable material could be in several superimposed layers, and / or in several materials.
- the important feature of the embodiment is that the wafer does not include any layer whose function is limited to forming a support and is engraved throughout its thickness.
- the clock component obtained has a maximum final thickness substantially equal to the thickness of the wafer 11 used, that is to say to the thickness of the wafer 12.
- the embodiment described above makes it possible to greatly simplify the method of manufacturing a watch component. It is mainly based on the removal of any support in a wafer 11 micro-machinable material, and the unexpected finding that it is possible to manufacture a watch component from a wafer not comprising a support.
- the figure 3 represents a method of manufacturing a watch component according to a second embodiment of the invention.
- Such a manufacturing method comprises a first step E21 ( figure 3a ) of providing a wafer 21 comprising a micro-machinable material, for example silicon.
- a wafer 21 comprises a wafer 22 made of micro-machinable material, which corresponds to the material of the watch component, with a thickness greater than or equal to 100 microns, or even greater than or equal to 120 microns, intended for be worked to form the watch component.
- the wafer 21 further comprises a lower layer 24, preferably metal.
- this second embodiment comprises a prior step not shown, consisting of depositing or assembling a metal lower layer 24 to a wafer 21 of micro-machinable material, to form the wafer 21.
- this prior step consists in coating a surface of a micro-machinable material wafer with a layer of metal deposited by a physical vapor deposition technique, also called by its acronym PVD (for "Physical Vapor Deposition").
- PVD Physical Vapor Deposition
- such a lower metal layer may be a pure aluminum layer of 2 microns.
- such a lower layer may have any other thickness, preferably between 0.5 and 5 microns inclusive.
- any deposition technique of a pure metal and / or an alloy may be used to coat the lower surface of the wafer made of micro-machinable material with a metal layer.
- the deposited metal is aluminum, gold or platinum.
- a tie layer on the wafer of micro-machinable material, for example titanium or chromium, to improve the adhesion of the lower metal layer.
- any other technique for deposition or assembly of a metallic lower layer forming a coating on the surface of the micro-machinable material board may be used (eg electrolytic growth, chemical vapor deposition, bonding of a leaf ).
- the manufacturing method then comprises a step of adding a mask on the upper surface of the wafer 21, via the deposit (step E22, figure 3b ) of a resin layer 25, in which free zones 26 are formed (step E23, figure 3c ) by partially removing the resin by photolithography techniques.
- the mask formed in the preceding step then allows the formation of at least one watch component, by etching (step E24, figure 3d ) of the wafer 21 through the free zones 26 of the resin mask.
- the component (s) is / are thus formed (s) according to a geometry determined by the previously formed mask.
- Step E22 to E25 substantially correspond to steps E2 to E5 and E12 to E15.
- the method according to this second embodiment then comprises a release step E26 ( figure 3f ), which consists in removing the lower metal layer 24.
- This E26 release step is very simple and rapid: it is carried out by dissolving the metal, for example in an aluminum etching acid bath (mixture HNO3, H3PO4, CH3COOH, H2O).
- the composition of the bath must be adapted to the metal constituting the lower layer to allow dissolution, in a manner known to those skilled in the art.
- the material of the lower layer is completely dissolved.
- the second lower silicon wafer 4 then separates from the upper wafer carrying the components.
- this second embodiment is likewise very simple, since the final separation of the watch component 29, by the elimination of the manufacturing residues such as the resin and the lower layer, which is in the form of a metallic support layer according to a method of embodiment, comprises a step of E26 greatly simplified release compared to the method of the state of the art that uses a support consisting of two parts, one of which corresponds to the material of the component, and therefore can not be dissolved chemically without first protecting the components etched in the first wafer by an additional layer.
- the second embodiment described above makes it possible to greatly simplify the method of manufacturing a watch component. It relies on the use of a metal support for a wafer made of a micro-machinable material, and on the unexpected finding that it is possible to manufacture a watch component from a wafer comprising a single wafer of material micro-machinable and a thin metal bottom layer, much more fine that the support of the state of the art also made of micro-machinable material.
- the skilled person would have had a negative bias on such a solution, considering in particular that the metal would diffuse within the micro-machinable material by modifying its properties. Those skilled in the art would also have a negative bias on the feasibility of this manufacturing process, because the processing equipment is generally designed for wafers of a certain rigidity to ensure accuracy and robustness.
- This second embodiment has been described on the basis of a lower layer of metal.
- a silicon oxide SiO 2 or polymer layer for example a poly-p-xylylene polymer film better known as parylene, on the lower face of the insert of micro-machinable material, which in particular fulfills the same function of stiffening as a metal layer.
- the release step E26 will consist simply of a dissolution of the SiO 2 or polymer layer by means of acids such as mixtures based on hydrofluoric acid or by oxygen plasma treatment.
- the concept implemented in the two embodiments of the invention described above consists in proposing a method of manufacturing a watch component that is free from the step of releasing a support made of micro-machinable material. complex and time-consuming, avoiding the use of a micro-machinable material as a support.
- the entire thickness of the micro-machinable material present in the wafer is used to form the watch component without a support function. It therefore does not include a micro-machinable material wafer used for the sole support function: the single micro-machinable material wafer present within the wafer 11, 21 is intended for the formation of at least one watch component per engraving.
- the method does not include etching of micro-machinable material by the underside of the wafer to facilitate the release step E6, but only an etching by the upper face.
- the clock component obtained preferably has a maximum thickness substantially corresponding to the thickness of the entire micro-machinable material (corresponding to the sum of the thickness of all the layers of micro-machinable material in the case of a wafer multilayer) initially present in the wafer used for its manufacture.
- the method of manufacturing a watch component may also comprise additional processing steps, performed before or after release of the component of the resin and / or the metal support, such as a thinning of the wafer of micro-material. Machinable or component, mechanical or laser beam recovery, coating deposition, oxidation thermal treatment, cleaning / degreasing, etc.
- the method of the invention applies to the manufacture of a multitude of watch components.
- the watch component may be an entity ready to be mounted in a movement (for example a lever, a spring, etc.) or a part intended to be assembled to one or more other parts of the movement (for example a spiral to the axis of balance, a wheel board to its axis, an anchor to the rod (or axis) of anchor, a pendulum to the balance shaft, etc.).
- the watch component can be a dressing component, such as a needle. This method is particularly suitable for the manufacture of simple 2.5D (two-and-a-half) clock components with a thickness greater than or equal to 100 ⁇ m.
- the second embodiment will be preferred for the most fragile components, having fine structures, likely to be damaged, or the most flexible, likely to deform during the etching step, such as spiral springs or even more. thin, especially of thickness less than 100 microns.
- the first embodiment will be preferred for less fragile components, especially more massive, such as wheels and for components of thickness strictly greater than 100 microns.
- the two embodiments remain suitable for the manufacture of all these watch components.
- the deposited layer which serves as a mask for etching is made of a photoresist.
- This layer of photosensitive resin may be substituted by any other layer that can serve as a mask against a DRIE type attack, for example a layer of silicon oxide, silicon nitride, metal, etc. The skilled person will choose the appropriate layer to suit his needs.
- micro-machinable material any material suitable for micromachining, including in particular any material that can be etched directionally through a mask.
- micro-machining all the techniques that make it possible to make structures of micrometric size in a material through a mask, such as, for example, chemical etching or photolithography.
- the micro-machinable material used in the embodiments described above is silicon, but can be substituted by doped silicon, porous silicon, etc. micro-machinable materials could obviously be used, such as diamond, quartz, sapphire and ceramics. It can also be a hybrid material.
- the micro-machinable material can also be any microstructurable material, sufficiently rigid to be manipulated.
- the invention is more generally suitable for the manufacture of a watch component consisting of or comprising a material called "component material” that can be cut through a mask.
- component material will be worked from a wafer thickness greater than or equal to 100 microns, arranged within a wafer, as explained in the embodiments described, or more generally in a wafer comprising a layer. comprising one or more material (s) of the component whose entire thickness, preferably greater than or equal to 100 microns, will be etched to form the component.
- such a wafer may optionally comprise a support in another material, in particular a metal or a metal alloy, said support material, different from the material of the component and compatible with it, that is to say not being assigned during the etching of the material of the component, as implemented in the etching steps E14, E24 described above.
- the thickness of the possible support is very small, less than or equal to 10 microns, even less than or equal to 5 microns, or even less than or equal to 3 microns.
- this thickness is preferably greater than or equal to 0.5 microns. This thickness is therefore considered negligible relative to the thickness of the wafer made of component material, wafer, and manufactured watch component.
Abstract
Procédé de fabrication d'un composant horloger (19 ; 29), caractérisé en ce qu'il comprend les étapes suivantes :• se munir (E11 ; E21) d'un wafer (11 ; 21) comprenant une seule plaquette (12 ; 22) comprenant un matériau du composant, notamment du silicium, du diamant, du quartz, du saphir ou de la céramique,• optionnellement revêtir au préalable la surface inférieure de ladite plaquette (22) par une couche inférieure (24),• graver (E12 à E14 ; E22 à E24) ladite plaquette (12 ; 22) du wafer (11 ; 21) à partir de sa surface supérieure pour former au moins un composant horloger,• révéler (E15 ; E25) au moins un composant horloger (19 ; 29), en retirant une couche ayant servi de masque pour la gravure (E15 ; E25),• et optionnellement libérer (E26) ladite plaquette et le au moins un composant horloger gravé par enlèvement de la couche inférieure (24).A method of manufacturing a watch component (19; 29), characterized in that it comprises the following steps: • equipping (E11; E21) a wafer (11; 21) comprising a single wafer (12; ) comprising a material of the component, in particular silicon, diamond, quartz, sapphire or ceramic, • optionally first coating the lower surface of said wafer (22) with a lower layer (24), • etching (E12 at E14; E22 to E24) said plate (12; 22) of the wafer (11; 21) from its upper surface to form at least one watch component; • revealing (E15; E25) at least one watch component (19; 29), by removing a layer having served as a mask for etching (E15; E25), and optionally (E26) releasing said wafer and the at least one engraved watch component by removing the lower layer (24).
Description
La présente invention concerne un procédé de fabrication d'un composant horloger réalisé à partir d'un matériau micro-usinable.The present invention relates to a method for manufacturing a watch component made from a micro-machinable material.
Il est connu de fabriquer des composants horlogers à partir d'un matériau micro-usinable tel que le silicium et par des techniques de micro-usinage, notamment par gravure sèche, par exemple par gravure ionique réactive profonde (en anglais Deep Reactive Ion Etching DRIE) ou par gravure chimique humide (en anglais chemical wet etching).It is known to manufacture watch components from a micro-machinable material such as silicon and by micromachining techniques, in particular by dry etching, for example by deep reactive ion etching (in English Deep Reactive Ion Etching DRIE ) or wet chemical etching (in English chemical wet etching ).
Un tel procédé de fabrication de l'état de la technique, représenté par la
Le procédé de fabrication comprend ensuite une étape consistant à ajouter un masque sur la face apparente du wafer 1, par l'intermédiaire du dépôt (étape E2,
Le masque formé à l'étape précédente permet ensuite la formation d'au moins un composant horloger, par gravure (étape E4,
Enfin, la résine restante est retirée (étape E5,
Un objet de la présente invention est de proposer un procédé de fabrication d'un composant horloger qui améliore le procédé de l'état de la technique.An object of the present invention is to provide a method of manufacturing a watch component which improves the method of the state of the art.
Plus particulièrement, l'objet de la présente invention est de proposer un procédé de fabrication simplifié d'un composant horloger.More particularly, the object of the present invention is to provide a simplified method of manufacturing a watch component.
A cet effet, l'invention repose sur un procédé de fabrication d'un composant horloger, caractérisé en ce qu'il comprend les étapes suivantes :
- se munir d'un wafer comprenant une plaquette comprenant un matériau du composant, notamment du silicium, du diamant, du quartz ou de la céramique,
- optionnellement revêtir au préalable la surface inférieure de ladite plaquette par une couche inférieure,
- graver ladite plaquette du wafer à partir de sa surface supérieure pour former au moins un composant horloger,
- révéler au moins un composant horloger, en retirant une couche ayant servi de masque pour la gravure,
- et optionnellement libérer ladite plaquette et le au moins un composant horloger gravé par enlèvement de la couche inférieure.
- providing a wafer comprising a wafer comprising a material of the component, in particular silicon, diamond, quartz or ceramic,
- optionally, beforehand, coating the lower surface of said wafer with a lower layer,
- etching said wafer plate from its upper surface to form at least one watch component,
- reveal at least one watch component, by removing a layer that has served as a mask for etching,
- and optionally releasing said wafer and the at least one engraved watch component by removing the lower layer.
L'étape consistant à se munir d'un wafer peut comprendre une étape consistant à se munir d'un wafer d'épaisseur sensiblement égale à l'épaisseur maximale du composant horloger à fabriquer.The step of providing a wafer may include a step of providing a wafer thickness substantially equal to the maximum thickness of the watch component to be manufactured.
Le procédé peut comprendre une étape de gravure du matériau du composant dans toute l'épaisseur de l'ensemble du matériau du composant présent dans le wafer et/ou dans toute l'épaisseur de l'unique plaquette comprenant le matériau du composant du wafer.The method may comprise a step of etching the material of the component throughout the thickness of the entire material of the component present in the wafer and / or throughout the thickness of the single wafer component comprising the wafer component material.
L'invention est plus précisément définie par les revendications.The invention is more precisely defined by the claims.
Ces objets, caractéristiques et avantages de la présente invention seront exposés en détail dans la description suivante de modes de réalisation particuliers faits à titre non-limitatif en relation avec les figures jointes parmi lesquelles :
- La
figure 1 représente schématiquement les étapes de fabrication d'un composant horloger selon l'état de la technique. - Chaque
figure 1a à 1f représente plus précisément une étape de la fabrication selon l'état de la technique. - La
figure 2 représente schématiquement les étapes de fabrication d'un composant horloger selon un premier mode de réalisation de l'invention. - Chaque
figure 2a à 2d et 2f représente plus précisément une étape de la fabrication selon le premier mode de réalisation de l'invention. - La
figure 3 représente schématiquement les étapes de fabrication d'un composant horloger selon un deuxième mode de réalisation de l'invention. - Chaque
figure 3a à 3f représente plus précisément une étape de la fabrication selon le deuxième mode de réalisation de l'invention.
- The
figure 1 schematically represents the manufacturing steps of a watch component according to the state of the art. - Each
figure 1a to 1f represents more precisely a stage of manufacture according to the state of the art. - The
figure 2 schematically represents the manufacturing steps of a watch component according to a first embodiment of the invention. - Each
Figure 2a to 2d and 2f represents more precisely a manufacturing step according to the first embodiment of the invention. - The
figure 3 schematically represents the manufacturing steps of a watch component according to a second embodiment of the invention. - Each
figure 3a to 3f more precisely represents a manufacturing step according to the second embodiment of the invention.
Selon les modes de réalisation de l'invention, le procédé de fabrication d'un composant horloger est amélioré en ce qu'il simplifie fortement la fin du procédé de l'état de la technique, en simplifiant, voire en supprimant l'étape de libération E6 décrite précédemment. Par convention, comme mentionné précédemment, nous utiliserons l'adjectif supérieur pour désigner une surface du côté de la face d'un wafer qui va subir la première gravure, et l'adjectif inférieur pour une surface d'un côté opposé.According to the embodiments of the invention, the method of manufacturing a watch component is improved in that it greatly simplifies the end of the method of the state of the art, by simplifying or even eliminating the step of E6 release described above. By convention, as mentioned before, we will use the adjective superior to designate a surface on the side of the face of a wafer which will undergo the first engraving, and the adjective inferior for a surface of an opposite side.
La
A l'instar du procédé de l'état de l'art décrit plus haut, un tel procédé de fabrication comprend une première étape E11 (
Le procédé de fabrication comprend ensuite une étape consistant à ajouter un masque sur la surface supérieure du wafer 11, par l'intermédiaire du dépôt (étape E12,
Le masque formé à l'étape précédente permet ensuite la formation d'au moins un composant horloger, par gravure (étape E14,
Enfin, la résine restante est supprimée par dissolution, dans une étape de révélation (étape E15,
Les étapes E12 à E15 correspondent sensiblement aux étapes E2 à E5 de la solution de l'état de la technique, et ne sont donc pas décrites en détail. Notamment, la gravure est réalisée de manière conventionnelle, par photolithographie et DRIE. Le grand avantage de ce premier mode de réalisation de l'invention est d'avoir supprimé la deuxième plaquette de support du wafer, ce qui permet de supprimer l'étape fastidieuse de libération E6 de l'état de la technique par dissolution de la couche intermédiaire 3.The steps E12 to E15 substantially correspond to the steps E2 to E5 of the solution of the state of the art, and are therefore not described in detail. In particular, the etching is carried out conventionally, by photolithography and DRIE. The great advantage of this first embodiment of the invention is to have removed the second wafer support plate, which makes it possible to eliminate the tedious step of E6 release of the state of the art by dissolving the
En variante, le wafer 11 en matériau micro-usinable pourrait se présenter en plusieurs couches superposées, et/ou en plusieurs matériaux. La caractéristique importante du mode de réalisation est que le wafer ne comprend aucune couche dont la fonction se limite à former un support et qu'il est gravé dans toute son épaisseur. Autrement dit, le composant horloger obtenu présente une épaisseur finale maximale sensiblement égale à l'épaisseur du wafer 11 utilisé, c'est-à-dire à l'épaisseur de la plaquette 12.As a variant, the
Ainsi, le mode de réalisation décrit ci-dessus permet bien de simplifier fortement le procédé de fabrication d'un composant horloger. Il repose principalement sur la suppression de tout support dans un wafer 11 en matériau micro-usinable, et sur la constatation inattendue qu'il est possible de fabriquer un composant horloger à partir d'une plaquette ne comprenant pas de support.Thus, the embodiment described above makes it possible to greatly simplify the method of manufacturing a watch component. It is mainly based on the removal of any support in a
La
Un tel procédé de fabrication comprend une première étape E21 (
Ainsi, ce deuxième mode de réalisation comprend une étape préalable non représentée, consistant à déposer ou assembler une couche inférieure 24 métallique à une plaquette 22 en matériau micro-usinable, pour former le wafer 21. Selon un premier mode de réalisation, cette étape préalable consiste à revêtir une surface d'une plaquette en matériau micro-usinable d'une couche de métal déposé par une technique de dépôt physique en phase vapeur, aussi dénommée par son sigle PVD (pour « Physical Vapor Déposition »). A titre d'exemple, une telle couche inférieure métallique peut être une couche d'aluminium pur de 2 microns. En variante, une telle couche inférieure peut présenter toute autre épaisseur, de préférence comprise entre 0.5 et 5 microns inclus. Alternativement, toute technique de déposition d'un métal pur et/ou d'un alliage peut être utilisée pour revêtir la surface inférieure de la plaquette en matériau micro-usinable par une couche métallique. Préférentiellement, le métal déposé est de l'aluminium, de l'or ou du platine. En complément, il est possible de déposer préalablement une couche d'accroche sur la plaquette en matériau micro-usinable, par exemple en titane ou en chrome, pour améliorer l'adhésion de la couche inférieure métallique. En variante, toute autre technique de déposition ou d'assemblage d'une couche inférieure métallique formant un revêtement sur la surface de la plaquette en matériau micro-usinable peut être utilisée (p.ex. croissance électrolytique, déposition chimique en phase vapeur, collage d'une feuille ...).Thus, this second embodiment comprises a prior step not shown, consisting of depositing or assembling a metal
Le procédé de fabrication comprend ensuite une étape consistant à ajouter un masque sur la surface supérieure du wafer 21, par l'intermédiaire du dépôt (étape E22,
Le masque formé à l'étape précédente permet ensuite la formation d'au moins un composant horloger, par gravure (étape E24,
Enfin, la résine restante est supprimée par dissolution, dans une étape de révélation (étape E25,
Le procédé selon ce deuxième mode de réalisation comprend ensuite une étape de libération E26 (
Ainsi, ce deuxième mode de réalisation reste de même très simple, puisque la séparation finale du composant horloger 29, par la suppression des résidus de fabrication comme la résine et la couche inférieure, qui se présente comme une couche métallique de support selon un mode de réalisation, comprend une étape de libération E26 grandement simplifiée par rapport au procédé de l'état de la technique qui utilise un support constitué de deux parties dont l'une correspond au matériau du composant, et qui ne peut de ce fait pas être dissoute chimiquement sans avoir préalablement protégé les composants gravés dans la première plaquette par une couche additionnelle.Thus, this second embodiment is likewise very simple, since the final separation of the
Ainsi, le deuxième mode de réalisation décrit ci-dessus permet bien de simplifier fortement le procédé de fabrication d'un composant horloger. Il repose sur l'utilisation d'un support métallique pour une plaquette constituée d'un matériau micro-usinable, et sur la constatation inattendue qu'il est possible de fabriquer un composant horloger à partir d'un wafer comprenant une seule plaquette de matériau micro-usinable et une fine couche inférieure métallique, beaucoup plus fine que le support de l'état de la technique réalisé également en matériau micro-usinable. L'homme du métier aurait eu un préjugé négatif sur une telle solution, considérant notamment que le métal allait diffuser au sein du matériau micro-usinable en modifiant ses propriétés. L'homme du métier aurait également un préjugé négatif sur la faisabilité de ce procédé de fabrication, car les équipements de traitement sont en général conçus pour des wafers d'une certaine rigidité pour assurer la précision et la robustesse.Thus, the second embodiment described above makes it possible to greatly simplify the method of manufacturing a watch component. It relies on the use of a metal support for a wafer made of a micro-machinable material, and on the unexpected finding that it is possible to manufacture a watch component from a wafer comprising a single wafer of material micro-machinable and a thin metal bottom layer, much more fine that the support of the state of the art also made of micro-machinable material. The skilled person would have had a negative bias on such a solution, considering in particular that the metal would diffuse within the micro-machinable material by modifying its properties. Those skilled in the art would also have a negative bias on the feasibility of this manufacturing process, because the processing equipment is generally designed for wafers of a certain rigidity to ensure accuracy and robustness.
En remarque et par rapport au premier mode de réalisation, la couche inférieure métallique utilisée dans ce deuxième mode de réalisation présente en outre les autres avantages suivants :
- elle sert de couche d'arrêt lors de l'étape de gravure E24, elle permet de protéger le porte-plaquette en évitant qu'il ne soit exposé au bombardement ionique en fin de gravure ;
- elle évacue la chaleur produite dans les structures lors de la gravure (réaction chimique exothermique + bombardement ionique) ;
- elle permet aussi d'éviter les défauts qui peuvent apparaître dans certains cas en fond de gravure, souvent dénommés par leur terme anglais de « notching » ;
- elle protège la face inférieure de la couche en matériau micro-usinable, c'est-à-dire la plaquette, et maintient les composants gravés sur toute leur surface, évitant que les structures flexibles ne se déforment lors du gravage.
- it serves as a stop layer during the etching step E24, it protects the wafer holder by preventing it from being exposed to ion bombardment at the end of etching;
- it evacuates the heat produced in the structures during etching (exothermic chemical reaction + ion bombardment);
- it also makes it possible to avoid the defects that can appear in some cases in the background of engraving, often called by their English term of "notching";
- it protects the lower face of the layer of micro-machinable material, that is to say the wafer, and keeps the etched components on their entire surface, preventing the flexible structures from deforming during etching.
Ce deuxième mode de réalisation a été décrit sur la base d'une couche inférieure en métal. En variante, il est également possible de déposer ou faire croître une couche d'oxyde de silicium SiO2 ou de polymère, par exemple un film polymère de poly-p-xylylène mieux connu sous le nom de parylène, sur la face inférieure de la plaquette en matériau micro-usinable, qui remplit notamment la même fonction de rigidification qu'une couche métallique. L'étape de libération E26 consistera simplement en une dissolution de la couche de SiO2 ou de polymère au moyen d'acides tels que des mélanges à base d'acide flurohydrique ou par traitement plasma oxygène.This second embodiment has been described on the basis of a lower layer of metal. Alternatively, it is also possible to deposit or grow a silicon oxide SiO 2 or polymer layer, for example a poly-p-xylylene polymer film better known as parylene, on the lower face of the insert of micro-machinable material, which in particular fulfills the same function of stiffening as a metal layer. The release step E26 will consist simply of a dissolution of the SiO 2 or polymer layer by means of acids such as mixtures based on hydrofluoric acid or by oxygen plasma treatment.
Finalement, le concept mis en oeuvre dans les deux modes de réalisation de l'invention décrits précédemment consiste à proposer un procédé de fabrication d'un composant horloger qui s'affranchit de l'étape de libération d'un support en matériau micro-usinable complexe et chronophage, en évitant d'utiliser un matériau micro-usinable comme support. Autrement dit, la totalité de l'épaisseur du matériau micro-usinable présent dans le wafer est utilisé pour former le composant horloger, sans fonction de support. Il ne comprend donc pas de plaquette de matériau micro-usinable utilisée pour la seule fonction de support : l'unique plaquette de matériau micro-usinable présente au sein du wafer 11, 21 est destinée à la formation d'au moins un composant horloger par gravure. Ainsi, dans les modes de réalisation précédents, le procédé ne comprend pas de gravure de matériau micro-usinable par la face inférieure du wafer pour faciliter l'étape de libération E6, mais uniquement une gravure par la face supérieure. Le composant horloger obtenu présente de préférence une épaisseur maximale correspondant sensiblement à l'épaisseur de l'ensemble du matériau micro-usinable (correspondant à la somme de l'épaisseur de toutes les couches en matériau micro-usinable dans le cas d'une plaquette multicouches) présent initialement dans le wafer servant à sa fabrication.Finally, the concept implemented in the two embodiments of the invention described above consists in proposing a method of manufacturing a watch component that is free from the step of releasing a support made of micro-machinable material. complex and time-consuming, avoiding the use of a micro-machinable material as a support. In other words, the entire thickness of the micro-machinable material present in the wafer is used to form the watch component without a support function. It therefore does not include a micro-machinable material wafer used for the sole support function: the single micro-machinable material wafer present within the
En variante, le procédé de fabrication d'un composant horloger peut également comprendre des étapes supplémentaires de traitement, réalisées avant ou après libération du composant de la résine et/ou du support métallique, telles qu'un amincissement de la plaquette de matériau micro-usinable ou du composant, une reprise mécanique ou par faisceau laser, un dépôt de revêtement, un traitement thermique d'oxydation, un nettoyage/dégraissage, etc.Alternatively, the method of manufacturing a watch component may also comprise additional processing steps, performed before or after release of the component of the resin and / or the metal support, such as a thinning of the wafer of micro-material. Machinable or component, mechanical or laser beam recovery, coating deposition, oxidation thermal treatment, cleaning / degreasing, etc.
Bien évidemment, le procédé de l'invention s'applique à la fabrication d'une multitude de composants horlogers. Le composant horloger peut être une entité prête à être montée dans un mouvement (par exemple un levier, un ressort, etc.) ou une pièce destinée à être assemblée à une ou plusieurs autres pièces du mouvement (par exemple un spiral à l'axe de balancier, une planche de roue à son axe, une ancre à la tige (ou axe) d'ancre, un balancier à l'axe de balancier, etc). Alternativement, le composant horloger peut être un composant d'habillage, comme une aiguille. Ce procédé est particulièrement adapté à la fabrication de composants horlogers 2.5D (deux dimensions et demi) simples, d'épaisseur supérieure ou égale à 100 µm. Le deuxième mode de réalisation sera préféré pour les composants les plus fragiles, présentant des structures fines, risquant d'être abimés, ou les plus souples, risquant de se déformer lors de l'étape de gravure, comme les ressorts spiraux ou encore les plus fines, notamment d'épaisseur inférieure à 100 microns. Le premier mode de réalisation sera préféré pour les composants moins fragiles, notamment plus massifs, comme les roues ainsi que pour des composants d'épaisseur strictement supérieure à 100 µm. Toutefois, les deux modes de réalisation restent adaptés pour la fabrication de tous ces composants horlogers.Of course, the method of the invention applies to the manufacture of a multitude of watch components. The watch component may be an entity ready to be mounted in a movement (for example a lever, a spring, etc.) or a part intended to be assembled to one or more other parts of the movement (for example a spiral to the axis of balance, a wheel board to its axis, an anchor to the rod (or axis) of anchor, a pendulum to the balance shaft, etc.). Alternatively, the watch component can be a dressing component, such as a needle. This method is particularly suitable for the manufacture of simple 2.5D (two-and-a-half) clock components with a thickness greater than or equal to 100 μm. The second embodiment will be preferred for the most fragile components, having fine structures, likely to be damaged, or the most flexible, likely to deform during the etching step, such as spiral springs or even more. thin, especially of thickness less than 100 microns. The first embodiment will be preferred for less fragile components, especially more massive, such as wheels and for components of thickness strictly greater than 100 microns. However, the two embodiments remain suitable for the manufacture of all these watch components.
Dans les exemples de réalisation décrits ci-dessus, la couche déposée qui sert comme masque pour la gravure est réalisée en une résine photosensible. Cette couche en résine photosensible peut être substituée par toute autre couche qui peut servir comme masque contre une attaque de type DRIE, par exemple une couche en oxyde de silicium, nitrure de silicium, métallique, etc. L'homme du métier choisira la couche adaptée pour convenir à ses besoins.In the embodiments described above, the deposited layer which serves as a mask for etching is made of a photoresist. This layer of photosensitive resin may be substituted by any other layer that can serve as a mask against a DRIE type attack, for example a layer of silicon oxide, silicon nitride, metal, etc. The skilled person will choose the appropriate layer to suit his needs.
Dans les modes de réalisation de l'invention décrits précédemment, nous entendons par matériau micro-usinable tout matériau adapté pour le micro-usinage, incluant notamment tout matériau qui peut être gravé de manière directionnelle au travers d'un masque. Nous entendons de plus par micro-usinage l'ensemble des techniques permettant de venir réaliser des structures de taille micrométrique dans un matériau au travers d'un masque, comme par exemple les attaques chimiques ou la photolithographie. Le matériau micro-usinable utilisé dans les exemples de réalisation décrits ci-dessus est le silicium, mais peut être substitué par le silicium dopé, le silicium poreux, etc.... D'autres matériaux micro-usinables pourraient évidemment être utilisés, comme par exemple le diamant, le quartz, le saphir et la céramique. Il peut aussi s'agir d'un matériau hybride. Le matériau micro-usinable peut aussi être tout matériau microstructurable, suffisamment rigide pour pouvoir être manipulé. Ainsi, l'invention convient plus généralement à la fabrication d'un composant horloger constitué de ou comprenant un matériau dit « matériau du composant » qu'on peut découper au travers d'un masque. Avantageusement, ce matériau du composant sera travaillé à partir d'une plaquette d'épaisseur supérieure ou égale à 100 µm, agencée au sein d'un wafer, comme explicité dans les modes de réalisation décrits, ou plus généralement dans un wafer comprenant une couche comprenant un ou plusieurs matériau(x) du composant dont la totalité de l'épaisseur, de préférence supérieure ou égale à 100 µm, sera gravée pour former le composant. De plus, un tel wafer pourra éventuellement comprendre un support dans un autre matériau, notamment un métal ou un alliage métallique, dit matériau du support, différent du matériau du composant et compatible avec lui, c'est-à-dire n'étant pas affecté lors de la gravure du matériau du composant, telle que mise en oeuvre dans les étapes de gravure E14, E24 décrites précédemment. Avantageusement, l'épaisseur de l'éventuel support est très faible, inférieure ou égale à 10 µm, voire inférieure ou égale à 5 µm, voire inférieure ou égale 3 µm. De plus, cette épaisseur est de préférence supérieure ou égale à 0,5 µm. Cette épaisseur est donc considérée comme négligeable relativement à l'épaisseur de la plaquette en matériau du composant, du wafer, et du composant horloger fabriqué.In the embodiments of the invention described above, we mean by micro-machinable material any material suitable for micromachining, including in particular any material that can be etched directionally through a mask. We also mean by micro-machining all the techniques that make it possible to make structures of micrometric size in a material through a mask, such as, for example, chemical etching or photolithography. The micro-machinable material used in the embodiments described above is silicon, but can be substituted by doped silicon, porous silicon, etc. micro-machinable materials could obviously be used, such as diamond, quartz, sapphire and ceramics. It can also be a hybrid material. The micro-machinable material can also be any microstructurable material, sufficiently rigid to be manipulated. Thus, the invention is more generally suitable for the manufacture of a watch component consisting of or comprising a material called "component material" that can be cut through a mask. Advantageously, this component material will be worked from a wafer thickness greater than or equal to 100 microns, arranged within a wafer, as explained in the embodiments described, or more generally in a wafer comprising a layer. comprising one or more material (s) of the component whose entire thickness, preferably greater than or equal to 100 microns, will be etched to form the component. In addition, such a wafer may optionally comprise a support in another material, in particular a metal or a metal alloy, said support material, different from the material of the component and compatible with it, that is to say not being assigned during the etching of the material of the component, as implemented in the etching steps E14, E24 described above. Advantageously, the thickness of the possible support is very small, less than or equal to 10 microns, even less than or equal to 5 microns, or even less than or equal to 3 microns. In addition, this thickness is preferably greater than or equal to 0.5 microns. This thickness is therefore considered negligible relative to the thickness of the wafer made of component material, wafer, and manufactured watch component.
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EP17205320.9A EP3495894B1 (en) | 2017-12-05 | 2017-12-05 | Method for manufacturing a clock component |
US16/202,284 US11429065B2 (en) | 2017-12-05 | 2018-11-28 | Method of manufacturing a clock or watch component |
JP2018224857A JP7393120B2 (en) | 2017-12-05 | 2018-11-30 | Manufacturing method for clocks or small watch parts |
CN201811474412.3A CN109870891B (en) | 2017-12-05 | 2018-12-04 | Method for manufacturing a part of a clock or watch |
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JP2016133494A (en) * | 2015-01-22 | 2016-07-25 | シチズンホールディングス株式会社 | Method of manufacturing timepiece component and timepiece component |
JP2016133495A (en) | 2015-01-22 | 2016-07-25 | シチズンホールディングス株式会社 | Method of manufacturing timepiece component and timepiece component |
EP3168696A1 (en) * | 2015-11-11 | 2017-05-17 | Nivarox-FAR S.A. | Method for manufacturing a silicon-based part with at least one optical illusion pattern |
JP6690973B2 (en) | 2016-03-18 | 2020-04-28 | セイコーインスツル株式会社 | Precision parts manufacturing method |
-
2017
- 2017-12-05 EP EP17205320.9A patent/EP3495894B1/en active Active
-
2018
- 2018-11-28 US US16/202,284 patent/US11429065B2/en active Active
- 2018-11-30 JP JP2018224857A patent/JP7393120B2/en active Active
- 2018-12-04 CN CN201811474412.3A patent/CN109870891B/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0732635A1 (en) * | 1995-03-17 | 1996-09-18 | C.S.E.M. Centre Suisse D'electronique Et De Microtechnique Sa | Micromechanical element and process for its manufacture |
WO2013087173A1 (en) * | 2011-12-12 | 2013-06-20 | The Swatch Group Research And Development Ltd | Shock-proof bearing for a timepiece |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP4022398B1 (en) * | 2019-08-29 | 2023-07-26 | ETA SA Manufacture Horlogère Suisse | Method for gluing clock components |
Also Published As
Publication number | Publication date |
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CN109870891A (en) | 2019-06-11 |
CN109870891B (en) | 2023-05-30 |
JP7393120B2 (en) | 2023-12-06 |
EP3495894B1 (en) | 2023-01-04 |
US20190171164A1 (en) | 2019-06-06 |
JP2019132827A (en) | 2019-08-08 |
US11429065B2 (en) | 2022-08-30 |
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