Method for manufacturing timepiece hairsprings

Technical field of the invention

0001The present invention relates to the field of watchmaking. More specifically, it relates to a process for manufacturing watch hairsprings, which may in particular be watch hairsprings with thermocompensation.

State of the art

0002In a clockwork movement, an oscillator has the function of providing a reference frequency, from which the measurement of the passage of time is carried out. This oscillator is often called the regulating organ of the watch movement. It can be mechanical in particular when it is provided for a mechanical clock movement.

0003A mechanical oscillator conventionally used in watchmaking results from the combination of a watchmaker's hairspring and a balance wheel, which is pivotally mounted and which plays the role of a flywheel, while the watchmaker's hairspring is a spring designed to produce a restoring torque on this pendulum.

0004A few years ago, we began to use new materials for the manufacture of watch balance springs, resulting in new manufacturing techniques such as deep reactive ion etching (also called DRIE etching, which is the acronym for Deep Reaction Ionic Etching) may have been used.

0005In the document<patcit id="pcit0001" dnum="EP1422436A"><text>EP 1 422 436</text></patcit>, it is proposed to manufacture a watchmaker's hairspring which comprises a silicon core and which has thermal compensation thanks to a coating made of silicon dioxide. In the document<patcit id="pcit0002" dnum="EP3412625A1"><text>EP 3 412 625 A1</text></patcit>, a process for manufacturing hairsprings by anisotropic etching in a substrate is described. During a photolithography step, a protective mask made of a photosensitive resin is structured by means of selective radiation. Anisotropic etching makes it possible to etch the substrate at the level of the zones not protected by the protective mask.

0006Manufacturing several watch hairsprings in the same wafer, by engraving, makes it possible to reduce manufacturing costs. However, there is a geometric dispersion between watch hairsprings belonging to batches, each of which consists of watch hairsprings all cut according to the same pattern, by engraving, in the same wafer.

0007In this regard, the document<patcit id="pcit0003" dnum="EP3181938A1"><text>EP 3 181 938 A1</text></patcit> proposes a method for manufacturing a watch hairspring having a predetermined elastic torque. In this process, a watchmaker's balance-spring blank cut to dimensions greater than the intended final dimensions is adjusted after cutting by shrinking material over a thickness calculated from a measurement on the watchmaker's balance-spring blank. The solution proposed in this document<patcit id="pcit0004" dnum="EP3181938A"><text>EP 3 181 938</text></patcit> gives sufficiently precise results when it is applied individually, that is to say when a single watch spring is processed at a time, which is expensive and complicated to implement. When the solution proposed in<patcit id="pcit0005" dnum="EP3181938A"><text>EP 3 181 938</text></patcit> is applied collectively to a batch of watch hairsprings cut by engraving in the same plate, a large number of the watch hairsprings of this batch have an elastic torque so far removed from the predetermined elastic torque that they are unusable and constitute a quantitatively very large and little scrap. compatible, or even incompatible, with the profitability requirements of industrial production.

Brief description of the invention

0008The object of the invention is at least to enable a geometric dispersion between watch hairsprings to be reduced collectively over several watch hairsprings cut out by engraving in the same wafer.

0009According to the invention, this object is achieved by means of a process for manufacturing watch hairsprings in a wafer, comprising a step in which: b) between at least one source emitting radiation and a photosensitive resin carried by one face of the wafer, a reusable mask stops at least part of the radiation except at the level of zones comprising several windows which define the contours of the watch hairsprings and which comprise this reusable mask.

0010According to the invention, the reusable mask is a reusable mask corrected in that at least some of the windows are dimensionally different from each other so as to reduce an extent of dispersion of the elastic torques of at least some of the watch hairsprings made in the same wafer.

0011The manufacturing method defined above can incorporate one or more other advantageous characteristics, individually or in combination, in particular among those defined below.

0012Advantageously, the manufacturing process comprises steps which follow step b) and in which:<ul id="ul0001" list-style="none"><li>c) from the photosensitive resin, a sacrificial mask is produced on the wafer by removing from the wafer the photosensitive resin having been irradiated by the radiation in step b) or the photosensitive resin having been subtracted from the radiation in step b) by the corrected reusable mask,</li><li>d) in the wafer, the watch hairsprings are produced by engraving using the sacrificial mask.</li></ul>

0013Advantageously, the manufacturing process is a manufacturing process for a batch of watch hairsprings whose elastic torques have an average within a predetermined range. Advantageously, in step d), the watch hairsprings are produced with dimensions greater than the dimensions necessary to obtain the batch of watch hairsprings whose elastic torques have the average in the predetermined range. Advantageously, the manufacturing process comprises steps which follow step d) and in which:<ul id="ul0002" list-style="none"><li>e) the quantity of material to be removed from the watch hairsprings produced in step d) is determined to obtain the batch of watch hairsprings having the elastic torques whose average is in the predetermined range,</li><li>f) from several or all of the watch hairsprings made in step d), said quantity of material to be removed is removed.</li></ul>

0014Advantageously, step f) is performed collectively on the watchmakers' hairsprings still attached to the wafer.

0015Advantageously, in step e), the quantity of material to be removed is determined from a measurement carried out on a sacrificial sample taken from among the watch springs of the wafer and which is dissociated from the wafer.

0016Advantageously, in step e), the quantity of material to be removed is determined by means of a correspondence table indicating the thickness of material to be removed for each of several average elastic couples or for each of several quantities linked to such average elastic torques.

0017Advantageously, the quantity of material to be removed is a thickness of material to be removed from the watch springs made in step d).

0018Advantageously, the wafer is made of a silicon-based material, step f) comprising sub-steps in which:<ul id="ul0003" list-style="none"><li>f1) several or all of the watch hairsprings produced in step d) are subjected to oxidation so as to be transformed into watch hairsprings superficially oxidized over a thickness which is the thickness of material to be removed determined in step e),</li><li>f2) from the superficially oxidized watch hairsprings, the silicon-based material which was oxidized during sub-step f1) is removed.</li></ul>

0019Advantageously, step d) is carried out by deep reactive ion etching.

0020Advantageously, the manufacturing process comprises a step in which: g) on ​​each of several or all of the watch balance springs, a thermal compensation portion is formed modifying the sensitivity to temperature variations of the elastic torque of the corresponding watch balance spring.

0021Advantageously, the manufacturing process comprises a preparatory step which precedes step b) and in which:<ol id="ol0001" compact="compact"><li>a) the corrected reusable mask is developed.</li></ol>

0022Advantageously, the preparatory step comprises sub-steps in which:<ul id="ul0004" list-style="none"><li>a1) a mapping of degrees of correction to be applied at different positions on a wafer plane is produced to reduce spatial heterogeneity of an etching produced by an etching device,</li><li>a2) the corrected reusable mask is produced in such a way that the windows are sized according to the mapping produced in sub-step a1).</li></ul>

0023Advantageously, in sub-step a1), the following is carried out:<ul id="ul0005" list-style="none"><li>a11) between at least the source and a photoresist carried by one face of a test wafer, an uncorrected mask stops at least part of the radiation from the source except at the level of zones comprising several windows which define the contours of structures of test and which are distant from each other within the uncorrected mask,</li><li>a12) the photoresist having been irradiated by the radiation or the photoresist having been subtracted from the radiation by the uncorrected mask is removed from the test wafer,</li><li>a13) in the test wafer, the test structures are produced by etching in different positions,</li><li>a14) measurements are taken for correction on the test structures, degrees of correction are determined from these measurements for correction and, to these degrees of correction, locations are assigned on a wafer plane according to the positions of the structures of testing.</li></ul>

0024Advantageously, the test structures are test watch hairsprings.

0025Advantageously, the measurements for correction comprise measurements of the frequencies of oscillators each comprising a balance wheel with a predetermined inertia and one of the test watch hairsprings.

0026Advantageously, the windows of the uncorrected mask are dimensionally identical to each other.

0027Advantageously, in sub-step a2), the corrected reusable mask is produced in such a way that, in addition to being sized according to the mapping produced in sub-step a1), the windows are sized so that at the step d), the watch hairsprings are made according to dimensions greater than the dimensions necessary to obtain the batch of watch hairsprings whose elastic torques have the average in the predetermined range.

0028A second manufacturing method aims at least to improve the manufacturing precision of a batch of watch hairsprings whose elastic torques have an average within a predetermined range.

0029The second manufacturing process is a process for manufacturing a batch of watch hairsprings whose elastic torques have an average within a predetermined range.

0030The second manufacturing process includes steps in which:<ul id="ul0006" list-style="none"><li>d) in a wafer made of a silicon-based material, the watch hairsprings are produced with dimensions greater than the dimensions necessary to obtain the batch of watch hairsprings whose elastic torques have the average in the predetermined range,</li><li>w) several or all of the watch hairsprings are subjected to a first oxidation so as to be transformed into superficially oxidized watch hairsprings each in a zone where, from the silicon-based material, the first oxidation creates a thermal compensation portion (50 ) to modify the sensitivity to temperature variations of the elastic torque of the corresponding watch balance spring, then</li><li>e) from at least one measurement on at least part of the oxidized watch hairsprings, the quantity of silicon-based material to be removed from the oxidized watch hairsprings is determined, to obtain the batch of watch hairsprings having the elastic couples whose average is within the predetermined range,</li><li>x) from the thermal compensation portion of several or all of the watch hairsprings, a residual thickness is removed which corresponds to the quantity of silicon-based material to be removed, then</li><li>y) several or all of the oxidized watch springs are subjected to a second oxidation such that the thermal compensation portion is regenerated.</li></ul>

0031In the second manufacturing process, the measurement or measurements used in step e) to determine the quantity of silicon-based material to be removed are carried out on one or more watch hairsprings each already provided with a thermal compensation portion which is predefined. In this way, the elastic torques of the watch hairsprings at the end of the second manufacturing process have their average in the predetermined range, whereas these watch hairsprings are each already provided with the predefined thermal compensation portion.

0032In step x), the residual thickness removed from the thermal compensation portion corresponds to the quantity of silicon-based material to be removed and it may not be equal to the thickness of this quantity of silicon-based material to remove.

0033Indeed, the residual thickness removed in step x) is made of the material based on oxidized silicon, which constitutes the thermal compensation portion and which can be silicon dioxide in the case where the material based on silicon is silicon. In other words, the residual thickness removed from the thermal compensation portion in step x) is not made of the same material as the quantity of silicon-based material to be removed. The residual thickness removed from the thermal compensation portion in step x) is made of the material resulting from the oxidation of the silicon-based material to be removed.

0034In the case where the silicon-based material to be removed is silicon (doped or undoped), the residual thickness removed from the thermal compensation portion in step x) is made of silicon dioxide. In the case where the silicon-based material to be removed is silicon (doped or undoped), the residual thickness removed from the thermal compensation portion in step x) is equal to approximately 227% of the thickness of the amount of silicon-based material to be removed.

0035The residual thickness removed in stage x) is such that the quantity of silicon-based material consumed during a second oxidation regenerating the thermal compensation portion in stage y) is equal to the quantity of material to be silicon base to be removed in step x).

0036Advantageously, in step d), the watch hairsprings are produced by engraving.

0037Advantageously, step d) is carried out by deep reactive ion etching.

0038Advantageously, step w) is carried out collectively on the watchmakers' hairsprings still attached to the wafer.

0039Advantageously, step x) is carried out collectively on the watchmakers' hairsprings still attached to the wafer.

0040Advantageously, step y) is carried out collectively on the watchmakers' hairsprings still attached to the wafer.

0041Advantageously, in step e), the quantity of silicon-based material to be removed is determined from a measurement carried out on a sacrificial sample taken from among the watch springs of the wafer and which is dissociated from the wafer.

0042Advantageously, in step e), the quantity of silicon-based material to be removed is determined by means of a correspondence table indicating the thickness of silicon-based material to be removed for each of several average elastic couples or for each of several quantities related to such mean elastic torques.

0043Advantageously, the quantity of silicon-based material to be removed is a thickness of silicon-based material to be removed from the watch hairsprings produced in step d).

0044Advantageously, the silicon-based material is silicon, for example doped silicon.

0045Advantageously, the manufacturing process according to the invention is a manufacturing process for a batch of watch hairsprings, namely the second manufacturing process.

0046Advantageously, the manufacturing method according to the invention comprises a step which follows step b) and in which: c) from the photosensitive resin, a sacrificial mask is produced on the wafer by removing from the wafer the photosensitive resin having been irradiated by the radiation in step b) or the photosensitive resin having been subtracted from the radiation in step b) by the corrected reusable mask.

0047Advantageously, step d) is carried out using the sacrificial mask.

0048The manufacturing process according to the invention and the second manufacturing process can be combined. Despite this, the process according to the invention and the second process are independent of each other.

Brief description of the drawings

0049Other advantages and characteristics will emerge more clearly from the following description of particular embodiments of the invention given by way of non-limiting example and represented in the appended drawings, among which:<ul id="ul0007" list-style="dash"><li>there<figref idref="f0001">figure 1</figref> is a perspective view of one of several watch hairsprings produced in a wafer by implementing a manufacturing method according to a first embodiment of the invention,</li><li>there<figref idref="f0001">figure 2</figref> is a mechanical oscillator comprising the horological hairspring shown in<figref idref="f0001">figure 1</figref>,</li><li>there<figref idref="f0002">picture 3</figref> is a block diagram of a manufacturing process according to a first embodiment of the invention,</li><li>there<figref idref="f0003">figure 4</figref> is a schematic view, in perspective, illustrating a step in the manufacturing process of the<figref idref="f0002">picture 3</figref>,</li><li>there<figref idref="f0004">figure 5</figref> is a schematic and partial view, in section, and illustrates a step in the manufacturing process of the<figref idref="f0002">picture 3</figref>,</li><li>there<figref idref="f0005">figure 6</figref> is a schematic view, in perspective, illustrating an intermediate state between two stages of the manufacturing process of the<figref idref="f0002">picture 3</figref>,</li><li>there<figref idref="f0006">figure 7</figref> is a schematic view, in perspective, of a wafer and a set of watch hairsprings having been cut out at the same time by engraving, all of them in this wafer, during the implementation of the manufacturing process of the<figref idref="f0002">picture 3</figref>,</li><li>there<figref idref="f0007">figure 8</figref> is a schematic view of a map of degrees of dimensional correction to be applied at different locations on a wafer plane to reduce the heterogeneity of an engraving produced by an engraving device,</li><li>there<figref idref="f0007">figure 9</figref> is a double graph where a first curve is the graphical representation (distribution of elastic torques) of the number n of watch hairsprings as a function of the elastic torque M, among a set of watch hairsprings cut collectively by etching in the same wafer without implementing the invention, and where a second curve is the graphical representation (distribution of elastic torques) of the number n of watch hairsprings as a function of the elastic torque M, from a set of watch hairsprings collectively cut out by engraving in the same wafer using the manufacturing process of the<figref idref="f0002">picture 3</figref>,</li><li>there<figref idref="f0008">figure 10A</figref> is a schematic cross-section of an elastically flexible strand of a watch balance spring between two steps in the manufacturing process of the<figref idref="f0002">picture 3</figref>,</li><li>there<figref idref="f0008">figure 10B</figref> is a schematic cross-section of an elastically flexible strand of a watch balance spring between two steps in the manufacturing process of the<figref idref="f0002">picture 3</figref>,</li><li>there<figref idref="f0008">figure 10C</figref> is a schematic cross-section of an elastically flexible strand of a watch balance spring between two steps in the manufacturing process of the<figref idref="f0002">picture 3</figref>,</li><li>there<figref idref="f0009">figure 11A</figref> is a triple graph where each of the three curves is the graphic representation (distribution of elastic torques) of the number n of watch hairsprings as a function of the elastic torque M, among a set of watch hairsprings made collectively in the same wafer by incompletely implementing the manufacturing process of<figref idref="f0002">picture 3</figref>,</li><li>there<figref idref="f0009">figure 11B</figref> is a triple graph where each of the three curves is the graphical representation (the distribution of elastic torques) of the number n of watch hairsprings as a function of the elastic torque M, among a set of watch hairsprings produced collectively in the same plate by completely implementing the process of<figref idref="f0002">picture 3</figref>, including steps performing a correction by removal of material with respect to the measured watch hairsprings to establish the three distributions of elastic torque shown in<figref idref="f0009">figure 11A</figref>, And</li><li>there<figref idref="f0010">figure 12</figref> is a schematic cross-section of an elastically flexible strand of a completely finished watch balance spring, once all the steps of the manufacturing process of the<figref idref="f0002">picture 3</figref>,</li><li>there<figref idref="f0011">figure 13</figref> is a block diagram of a manufacturing process which is according to a second embodiment of the invention and which comprises the second manufacturing process,</li><li>there<figref idref="f0012">Figure 14A</figref> is a schematic cross-section of an elastically flexible strand of a watch balance spring between two steps in the manufacturing process of the<figref idref="f0011">figure 13</figref>,</li><li>there<figref idref="f0012">Figure 14B</figref> is a schematic cross-section of an elastically flexible strand of a watch balance spring between two steps in the manufacturing process of the<figref idref="f0011">figure 13</figref>,</li><li>there<figref idref="f0012">Fig. 14C</figref> is a schematic cross-section of an elastically flexible strand of a watch balance spring between two steps in the manufacturing process of the<figref idref="f0011">figure 13</figref>,</li><li>there<figref idref="f0012">figure 14D</figref> is a schematic cross-section of an elastically flexible strand of a completely finished watch balance spring, once all the steps of the manufacturing process of the<figref idref="f0011">figure 13</figref>.</li></ul>

Description of preferred embodiments of the inventions

0050On the<figref idref="f0001">figure 1</figref> a watchmaker's hairspring 1 is shown, which comprises a ferrule 2 intended to be secured to a pivoting shaft. The watchmaker's hairspring 1 also comprises an elastically flexible strand 3 connecting at one end to the ferrule 2 and wound in a spiral so as to form several consecutive turns, the last of which is extended by an attachment segment 4 intended to be attached to a fixed balance bridge (not shown), for example via a peak (not shown).

0051On the<figref idref="f0001">figure 2</figref> there is shown a mechanical oscillator 6, which is of a type called a “balance-spring” and which comprises the horological balance-spring 1, a balance 8 and a shaft 9 carrying this balance 8 as well as the ferrule 2. In the mechanical oscillator 6 , watchmaker's hairspring 1 is coupled to balance wheel 8 by the fact that ferrule 2 and balance wheel 8 are both integral with shaft 9.

0052The watchmaker's hairspring 1 is part of a batch of watchmakers' hairsprings 1 which have been produced in the same wafer by implementing a manufacturing method 10 according to a first embodiment of the invention, which has numerous advantages. This manufacturing process 10 comprises several successive steps as shown in the<figref idref="f0002">picture 3</figref>.

0053In the manufacturing process 10, a corrected reusable mask 11 is used, visible at the<figref idref="f0003">figure 4</figref>. This corrected reusable mask 11 comprises several windows 12 which define the contours of watch hairsprings. In the manufacturing process 10, the windows 12 define the outer contours of watch hairsprings. As a variant, the windows 12 could define the internal contours of watch hairsprings (depending on the type of photosensitive resin used, see below).

0054In the example shown in<figref idref="f0003">figure 4</figref>, the windows 12 are 4 in number, whereby this<figref idref="f0003">figure 4</figref> is simplified and more details can be included. Of course, the number of windows 12 can be different from 4. The number of windows 12 in the corrected reusable mask 11 can be several tens. Preferably, the number of windows 12 in the corrected reusable mask 11 is greater than 100. Even more preferably, the number of windows 12 in the corrected reusable mask 11 is several hundred.

0055The corrected reusable mask 11 is used in a photolithography forming part of the manufacturing process 10. Except at the level of the windows 12, the corrected reusable mask 11 forms a screen capable of stopping at least part of a radiation intended to transform a photoresist . In other words, at least part of such radiation is stopped by the corrected reusable mask 11 except at the level of the windows 12.

0056In the first embodiment of the invention described here, the windows 12 are the only zones where the corrected reusable mask 11 does not form a screen capable of stopping at least part of a radiation intended to transform a photoresist. However, it could be otherwise without departing from the scope of the invention. For example, in addition to the windows 12, the corrected reusable mask could comprise one or more zones which define the outlines (internal and/or external) of characterization structures and where the screen capable of stopping at least part of the characterization is absent. radiation intended to transform a photoresist. Such characterization structures may be different from the watch hairsprings 1 and can be used to quantify an engraving by being measured and to determine a level of adjustment to be made by removing material from the watch hairsprings 1, in a manner which will be explained later. far.

0057The corrected reusable mask 11 may comprise a glass plate which is transparent so that the aforementioned radiation can pass through it and one of the two main faces of which bears a chromium-based coating except in certain areas including the windows 12. The coating with chromium base is able to stop all or part of the aforementioned radiation. Each window 12 is an area where this chrome-based coating is absent.

0058When the corrected reusable mask 11 is available, the first step of the manufacturing process 10 is step 100, which is that illustrated in<figref idref="f0003">figure 4</figref>.

0059On the<figref idref="f0003">figure 4</figref>, a wafer 15 has two main faces, one of which is covered with a photoresist 16. As will be explained below, the wafer 15 is a multilayer structure, which is not shown in<figref idref="f0003">figure 4</figref> for the sake of clarity. In the manufacturing process 10, the wafer 15 is a multilayer structure, but it could be otherwise. In particular, the wafer 15 could be monolayer and made up of the wafer which, further on, is referenced 22.

0060Always on the<figref idref="f0003">figure 4</figref>, the corrected reusable mask 11 is placed between a source emitting R radiation and the assembly formed by the photosensitive resin 16 and the wafer 15. The R radiation may in particular be radiation comprising UV, that is to say ultraviolet rays, or even be made up of UV rays.

0061At least part of the R radiation is able to transform the photosensitive resin 16 so as to make it soluble or insoluble in an appropriate chemical bath. In the manufacturing process 10, the photosensitive resin 16 is chosen so that its irradiation by radiation R makes this photosensitive resin 16 soluble in an appropriate chemical bath. In a variant, the photosensitive resin is chosen so that its irradiation by radiation analogous or identical to radiation R renders this photosensitive resin insoluble in an appropriate chemical bath, in which case the corrected reusable mask 11 is transformed accordingly.

0062In step 100, the corrected reusable mask 11 stops the radiation R except at the level of the windows 12. In this way, the photosensitive resin 16 is irradiated in the zones facing the windows 12. The reference 17 designates the photosensitive resin 16 which has been irradiated by the R radiation through the windows 12 and which has thus become soluble in an appropriate chemical bath.

0063As can be seen at the<figref idref="f0002">picture 3</figref>, a step 101 follows step 100. In step 101, the irradiated photoresist 17 is removed by dissolving it in an appropriate chemical bath, which is called development. The photosensitive resin 16 which has not been irradiated and transformed by the radiation R resists the chemical bath, thus remains in place on the wafer 15 and forms a sacrificial mask, which is referenced 18 at the<figref idref="f0004">figure 5</figref>. In other words, the sacrificial mask 18 is made in step 101.

0064The step referenced 102 in<figref idref="f0002">picture 3</figref> follows step 101. Step 102 is illustrated in<figref idref="f0004">figure 5</figref>, on which it can be seen that the multilayer structure of the wafer 15 comprises a support 20, a barrier layer 21 and a wafer 22. The wafer 22 is made of a material capable of being etched, for example of a silicon-based material. Preferably, wafer 22 is made of silicon. The silicon of wafer 22 can be polycrystalline. Preferably, wafer 22 is made of monocrystalline silicon. The silicon of wafer 22 may not be doped. Preferably, the wafer 22 is made of doped silicon, which is electrically conductive, more dimensionally stable and of better mechanical resistance. Preferably, wafer 22 is made of phosphorus-doped silicon. Preferably, wafer 22 is made of silicon which is {1,1,1} oriented and/or which is doped. Preferably, the wafer 22 is made of silicon which has an orientation <1,1,1> and/or which is doped so as to have a resistivity less than or equal to 0.1 Ω.cm^-1, for example a resistivity equal to 0.05 Ω.cm^-1.

0065Preferably, the wafer is of the silicon-silicon-silicon oxide type, that is to say of the type commonly designated by the acronym “SOI”. Such is the case in manufacturing process 10. In manufacturing process 10, support 20 is made of silicon, barrier layer 21 is made of silicon dioxide and wafer 22 is made of silicon.

0066In step 102, several horological hairsprings 1 are cut collectively, together and at the same time, all in the wafer 22, by means of an engraving 25, which is a directional engraving occurring where the wafer 22 is not protected by the sacrificial mask 18. In the manufacturing process 10, the etching 25 is a deep reactive ion etching, also called DRIE etching (acronym for “deep reaction ion etching”, which is the English designation for deep reactive ion etching) or etching according to the Bosch process. Behind the sacrificial mask 18, the wafer 22 is not engraved. Stop layer 21 is insensitive to etching 25 which therefore does not affect it. The stop layer 21 therefore has the function of stopping the etching 25.

0067The sacrificial mask 18 is sacrificial insofar as it is ephemeral and is destroyed once the etching 25 is completed.

0068There<figref idref="f0005">figure 6</figref> represents the state of wafer 15 once etching 25 is complete. On this<figref idref="f0005">figure 6</figref>, the wafer 22 and the watch springs 1 cut therein are still linked to the support 20 by the stop layer 21. The support 20 and the stop layer 21 can be removed locally. In the manufacturing process 10, the support 20 and the stop layer 21 are totally removed, for example by etching, so that the watchmakers' hairsprings 1 and the wafer 22 are released, after which the wafer 22 and the watchmakers' hairsprings 1 cut therein are as shown in<figref idref="f0006">figure 7</figref>.

0069On the<figref idref="f0006">figure 7</figref>, the watchmakers' hairsprings 1 cut out from the wafer 22 are still attached to this wafer 22, so that they can easily be moved together and treated collectively and at the same time.

0070The corrected reusable mask 11 is corrected in that at least some of the windows 12 are dimensionally different from each other so as to reduce an extent of a dispersion of the elastic couples of the watch hairsprings 1 cut out by engraving in the same wafer 12.

0071It has in fact been discovered that, if the reusable mask is not corrected, that is to say if all its windows similar to the windows 12 are dimensionally identical to each other, the elastic couples of the watch hairsprings cut from the same wafer 22 by DRIE etching using a sacrificial mask formed by means of this uncorrected reusable mask have highly dispersed values, and the extent of the dispersion of these elastic couples is significant. This is believed to be due to etching chamber imperfections (non-uniform distribution of plasmas/gases).

0072On the graph of<figref idref="f0007">figure 9</figref>, the elastic torque M is on the abscissa, while the numbers n of watch hairsprings among all the watch hairsprings made in the same wafer 22 are on the ordinate. Always on the graph of the<figref idref="f0007">figure 9</figref>, curves C1 and C2 are normally histograms but they have been smoothed for clarity. Still on the graph of the<figref idref="f0007">figure 9</figref>, increasing classes of elastic torque are also shown along the abscissa axis. In the example shown in the<figref idref="f0007">figure 9</figref>, the number of classes is equal to 80, but it could be different with another segmentation into classes. For example, the number of classes could be equal to 20 as was the practice in the past.

0073On the<figref idref="f0007">figure 9</figref>, the curve C1 is the graphic representation of the dispersion of the elastic couples of watch springs made in the same wafer 22 using an uncorrected reusable mask.

0074Always on the<figref idref="f0007">figure 9</figref>, the curve C2 is the graphic representation of the dispersion of the elastic couples of the watch hairsprings 1 made in the same wafer 22 by using the corrected reusable mask 11, during an implementation of the manufacturing method 10.

0075Stated in a simplified manner, the correction incorporated in the corrected reusable mask 11 makes it possible to pass from the curve C1 to the curve C2.

0076On the<figref idref="f0007">figure 9</figref>, we see that the standard deviation associated with the curve C1 is much higher than the standard deviation associated with the curve C2. In other words, the extent D1 of the dispersion of the elastic couples of the watch springs produced in the same wafer by means of an uncorrected reusable mask is large. The extent D2 of the dispersion of the elastic couples of the watch hairsprings 1 produced in the same wafer 22 by means of the corrected reusable mask 11 is markedly smaller than the extent D1.

0077In particular, the range D2 is small enough for all or practically all of the watchmakers' hairsprings 1 produced in the same wafer 22 by means of the corrected reusable mask 11 to be able to be classified in a reduced number of classes and paired with balance wheels distributed in a reduced number of classes.

0078A class of watch hairsprings is intended to receive all watch hairsprings having an elastic torque situated between two predefined limits. A class of pendulums is intended to receive all the pendulums having an inertia situated between two predefined limits. By pairing any horological hairspring and any balance wheel belonging to corresponding classes, a mechanical oscillator is obtained which is ready to be fitted in a horological movement insofar as the final adjustment of this mechanical oscillator can be carried out by means of of a rack or by playing on the inertia of the balance wheel, while the mechanical oscillator is in place in the watch movement.

0079The corrected reusable mask 11 is produced during a preparatory step 500. As the corrected reusable mask 11 is reusable and can be used a very large number of times, the preparatory step 500 can only be carried out once for all, after which the manufacturing process 10 can be carried out a very large number of times, starting directly with step 100, without redoing the preparatory step 500.

0080The corrected reusable mask 11 is suitable for a specific etching installation, namely the etching installation with and for which it was developed. This engraving installation may change over time. From the measurements carried out on the watchmakers' hairsprings 1 produced by means of the engraving installation, it is possible to detect an evolution requiring the design and production of a new corrected reusable mask 11.

0081The preparatory step 500 includes a sub-step 520, in which a mapping of degrees of correction to be applied at different positions on a wafer plane is produced to reduce spatial heterogeneity of an etching produced by the etching device. Such a map 30 is represented on the<figref idref="f0007">figure 8</figref>.

0082Sub-step 520 includes an operation 522, which is identical to step 100 except that the wafer 22 is replaced by a test wafer and except that an uncorrected mask is used in place of the corrected reusable mask 11. This uncorrected mask is used in photolithography. In this uncorrected mask, there are windows which, like windows 12, are areas where there is no screen capable of stopping at least part of the R radiation. The windows of the uncorrected mask define the contours (internal and/or external) of test watch hairsprings or the contours (internal and/or external) of other test structures. In the manufacturing process 10, the windows of the uncorrected mask are dimensionally identical to each other and define the contours of the test watch hairsprings.

0083During operation 522, the uncorrected mask is located between the source emitting the radiation R in the etching installation considered and a photoresist carried by one face of the test wafer. Still in operation 522, the corrected mask stops at least part of the radiation from the source except at the level of the windows, facing which the photoresist is irradiated and transformed. In the manufacturing process 10, the photosensitive resin is chosen so that its irradiation by radiation R renders this photosensitive resin soluble in an appropriate chemical bath. In a variant, the photosensitive resin is chosen so that its irradiation by radiation analogous or identical to R radiation renders this photosensitive resin insoluble in an appropriate chemical bath, in which case the uncorrected reusable mask is transformed accordingly.

0084Still in sub-step 520, an operation 524 follows operation 522. Operation 524 is identical to step 101 except that the photoresist that is then removed is that which was irradiated during operation 522 and what is on the test plate. In operation 524, a sacrificial mask is therefore formed from the photoresist.

0085In sub-step 520, an operation 526 follows operation 524. Operation 526 is identical to step 102 except that the cutting by engraving in this operation 526 is a cutting of test watch hairsprings and that it is carried out by means of the sacrificial mask produced during operation 524. In operation 526, test watch hairsprings are cut from the same test wafer, by DRIE engraving, in the engraving installation, at positions distributed over a plate plan.

0086In sub-step 520, an operation 528 follows operation 526. In operation 528, measurements are performed for correction on the test watch hairsprings made in the test wafer during operation 526. Preferably, these measurements for correction are measurements of the frequencies of oscillators each consisting of a predetermined inertia balance wheel and one of the test watch springs coupled to this predetermined inertia oscillator. Preferably, the test watch hairspring has been detached from the test wafer before being coupled to the predetermined inertia balance wheel and before the frequency measurement is performed. The frequency measurement can also be performed while the test watch hairspring is still attached to the test wafer. In this case, the frequency measurement can be carried out according to the teachings of the document<patcit id="pcit0006" dnum="EP2423764A"><text>EP 2 423 764</text></patcit>.

0087Still in operation 528, the degrees of correction are determined from the measurements for correction carried out on the test watch hairsprings produced in the same test wafer.

0088To do this, we use the relationship that establishes the elastic torque of a hairspring as a function in particular of its dimensions and which is as follows:<maths id="math0001" num=" (1)"><math display="block"><mi>M</mi><mo>=</mo><mfrac><mrow><mi>E</mi><mo>.</mo><mi>h</mi><mo>.</mo><msup><mi>I</mi><mn>3</mn></msup></mrow><mrow><mn>12</mn><mo>.</mo><mi>I</mi></mrow></mfrac></math><img file="EP3845770B1_D0001.tif" /></maths> where: - M is the elastic torque of the hairspring,<ul id="ul0008" list-style="dash" compact="compact"><li>E is the modulus of elasticity of the elastically flexible strand of the watch balance spring,</li><li>h is the height of the elastically flexible strand of the watch balance spring,</li><li><i>I</i> is the thickness of the elastically flexible strand of the watch balance spring, and</li><li>L is the length of the elastically flexible strand of the watch balance spring.</li></ul>

0089On the<figref idref="f0007">figure 8</figref>, a wafer plane 35 indicates the position of cells 36, each of which is a region in which to cut a single horological hairspring.

0090To each cell 36, the degree of correction deduced from the measurement for correction carried out on the test watch balance spring cut at the level of this cell 36 is attributed.

0091For example, to determine the degrees of correction from measurements for correction carried out on the test watch hairsprings made in the same test wafer, one can proceed as follows.

0092The relation (1) in a specific case allows to choose h₆, I₆ And<i>I</i>₆ to get the value M₆ intended, because:<maths id="math0002"><math display="block"><msub><mi>M</mi><mn>6</mn></msub><mo>=</mo><mfrac><mrow><mi>E</mi><mo>.</mo><msub><mi>h</mi><mn>6</mn></msub><mo>.</mo><msubsup><mi>I</mi><mn>6</mn><mn>3</mn></msubsup></mrow><mrow><mn>12</mn><mo>.</mo><msub><mi>I</mi><mn>6</mn></msub></mrow></mfrac></math><img file="EP3845770B1_D0002.tif" /></maths> Or :<ul id="ul0009" list-style="dash" compact="compact"><li>M₆ is the target elastic torque,</li><li>E is the modulus of elasticity of the elastically flexible strand of the watch balance spring,</li><li>h₆ is the target height of the elastically flexible strand of the watch balance spring,</li><li><i>I</i>₆ is the target thickness of the elastically flexible strand of the watch balance spring, and</li><li>I₆ is the target length of the elastically flexible strand of the watch balance spring.</li></ul>

0093The shape of a watch balance spring is such that the error (due to DRIE engraving) which affects the elastic modulus M much more than the other errors is the error on the width<i>I</i> of the watch balance spring. The error in the height h of the hairspring, as well as the error in the length L of the hairspring, can therefore be neglected.

0094From an elastic modulus M₇ obtained by measurement on a test watch hairspring in a cell 36, the correction Δ is determined<i>I</i> to be applied in this cell 36 by solving the following equation:<maths id="math0003"><math display="block"><msub><mi>M</mi><mn>7</mn></msub><mo>=</mo><mfrac><mrow><mi>E</mi><mo>.</mo><msub><mi>h</mi><mn>6</mn></msub><mo>.</mo><msup><mfenced><msub><mi>I</mi><mn>6</mn></msub><mo>+</mo><mi>Δ</mi><mspace width="1ex" /><mi>I</mi></mfenced><mn>3</mn></msup></mrow><mrow><mn>12</mn><mo>.</mo><msub><mi>I</mi><mn>6</mn></msub></mrow></mfrac></math><img file="EP3845770B1_D0003.tif" /></maths>

0095In case M₇ measured is greater than M₆ targeted, the width of the window 12 at the level of the corresponding elastically flexible strand 3, having to have substantially the width<i>I</i>₆, will be reduced by the magnitude Δ<i>I</i>.

0096In case M₇ measured is less than M₆ targeted, the width of the window 12 at the level of the corresponding elastically flexible strand 3, having to have substantially the width<i>I</i>₆, will be increased by the magnitude Δ<i>I</i>.

0097In case M₇ measured is equal or substantially equal to M₆ targeted, the width of the window 12 at the level of the corresponding elastically flexible strand 3, having to have substantially the width<i>I</i>₆, will not be corrected, i.e. it will not be modified.

0098Each cell 36 can be associated with an individual degree of correction.

0099It is also possible to associate an identical mean degree of correction with a family of cells 36 at the level of which the individual degrees of correction obtained are close, for example comprised in a predefined interval which can for example correspond to a class of horological hairsprings. Such is the case in the manufacturing process 11. On the<figref idref="f0007">figure 8</figref>, the same degree of correction is applied at the level of the cells designated by the letter A. The same degree of correction is applied at the level of the cells designated by the letter B. The same degree of correction is applied at the level of the cells designated by the letter C. The same degree of correction is applied to the cells designated by the letter D.

0100The amount of correction applied at the A cell level is greater than the amount of correction applied at the B cell level. The amount of correction applied at the B cell level is greater than the amount of correction applied at the C cell level. applied at the C cell level is greater than the amount of correction applied at the D cell level.

0101On the<figref idref="f0007">figure 8</figref>, the degree of correction increases globally from inside to outside (cells A are more at the periphery while cells C are more at the center of the wafer plane 35). However, the<figref idref="f0007">figure 8</figref> is only an example and is not limiting. Indeed, the distribution of the degrees of correction on the wafer plane 35 can be any. In other words, the distribution of the degrees of correction on the insert plane 35 can be very different from that represented on the<figref idref="f0007">figure 8</figref> like being very similar.

0102Each degree of correction is a modification of at least one dimension of the window 12 of the corrected reusable mask 11, with respect to a window of the uncorrected reusable mask used in operation 522. In particular, a degree of correction can result by increasing or decreasing the width of the part of the corrected reusable mask 11 corresponding to an elastically flexible strand 3 of a watchmaker's hairspring 1. The change in width may be constant over the entire length of the part corresponding to an elastically flexible strand 3. The increase in width or the decrease in width may also not be constant over the entire length of the part corresponding to an elastically flexible strand flexible 3.

0103Operations 522, 524, 526 and 528 can be repeated several times so that several degrees of correction obtained experimentally are available for each cell 36 and so that an average degree of correction can be calculated for each cell 36 and determined a map 30 on the basis of the averages of degrees of correction each obtained for a cell 36 of the wafer plane 35.

0104In the manufacturing process 10, test watch hairsprings are cut from the test wafer, during step 526. However, during step 526, test structures can be cut from the test wafer which are not not clockwork hairsprings. These test structures can be configured to allow a measurement of the modulus of elasticity M and so that the variation of the moduli of elasticity between two wafers 22 is proportional to the correction to be made on the watch hairsprings 1. The test structures cut during operation 526 in the test wafer can also be geometric figures, in which case the measurements for correction carried out during operation 528 can be dimensional measurements on these geometric figures.

0105The preparatory step 500 includes a sub-step 540 which follows step 520. In the sub-step 540, the corrected reusable mask 11 is produced in such a way that the windows 12 of this corrected reusable mask 11 are sized according to of the mapping 30 produced in sub-step 520.

0106In the manufacturing method 10 according to a first embodiment of the invention, the correction integrated into the corrected reusable mask 11 constitutes a first correction, which aims to reduce the dispersion of the elastic couples of watch hairsprings 1 produced together and at the same time by etching in the same wafer 22, in an etching installation.

0107The manufacturing method 10 according to a first embodiment of the invention includes a second correction, which aims to reduce the heterogeneity between two etchings carried out in the same etching installation, by means of the same corrected reusable mask 11, but at two different times and each on a different wafer 22. In other words, the second correction aims to reduce the dispersion between the elastic couples of a first set of watchmakers' hairsprings 1 and of a second set of watchmakers' hairsprings 1, the watchmakers' hairsprings 1 of the first set having been engraved in a first wafer, while the watchmaker hairsprings 1 of the second set were engraved in a second wafer, before or after the watchmaker hairsprings 1 of the first set.

0108Because it includes the second correction, the manufacturing process 10 is a process for manufacturing a batch of watch springs 1 whose elastic torques have an average within a predetermined range. In order to be able to carry out the second correction, the corrected reusable mask 11 is produced in such a way that, in addition to being dimensioned according to the mapping 30 carried out in sub-step 520, the windows 12 are dimensioned so that at the step 102, the watch hairsprings 1 are cut by engraving according to dimensions greater than the dimensions necessary to obtain the batch of watch hairsprings 1 whose elastic torques have the average in the predetermined range.

0109In addition, still to perform the second correction, the manufacturing method 10 comprises two steps which follow step 102 and which are a step 110 and a step 120 following this step 110.

0110In step 110, a quantity of material to be removed from the watchmakers' hairsprings 1 produced in step 102 in the same wafer 22 is determined. This quantity of material to be removed is more precisely that which must be removed from these watchmakers' hairsprings 1, after step 102, to obtain the batch of watch springs 1 having elastic torques whose average is in the predetermined range.

0111In the case of the manufacturing method 10 according to a first embodiment of the invention, this quantity of material to be removed is a thickness of material to be removed from the watch hairsprings 1 made in step 102.

0112To perform step 110, one preferably proceeds as follows. One begins by detaching from the wafer 22 several watchmaking hairsprings 1 constituting a sacrificial sample. This sacrificial sample is qualified as "sacrificial" because the watchmakers' hairsprings 1 constituting it will be used to carry out measurements, after which, for the sake of efficiency and profitability, they may not be kept among the watchmakers' hairsprings 1 to which is applied step 120. The watch springs of the sacrificial sample can be 5 to 15 in number and are advantageously chosen at locations distributed over the whole of the wafer plane 35.

0113Once separated from the wafer 22, each of the watch springs 1 of the sacrificial sample is coupled to a predetermined inertia balance wheel in order to form therewith a mechanical oscillator whose frequency f is measured, still in step 110 After that, there are as many measurements of frequency f as there are watch hairsprings 1 in the sacrificial sample. The average of these frequencies f measured on the mechanical oscillators comprising the watch hairsprings 1 of the sacrificial sample is then calculated.

0114The average elastic torque of the watch springs of the sacrificial sample can be determined from the frequencies f measured and/or from the average of these frequencies 7 measured, by means of the following relationship:<maths id="math0004" num="(2)"><math display="block"><mi>f</mi><mo>=</mo><mfrac><mn>1</mn><mrow><mn>2</mn><mspace width="1ex" /><mi>π</mi></mrow></mfrac><msqrt><mrow><mi>M</mi><mo>/</mo><mi>I</mi></mrow></msqrt></math><img file="EP3845770B1_D0004.tif" /></maths> where: - f is the (natural) frequency of the balance-spring,<ul id="ul0010" list-style="dash" compact="compact"><li>l is the moment of inertia of the pendulum around its axis of rotation, and</li><li>M is the elastic torque of the watch balance spring.</li></ul>

0115Then, to determine the thickness of material to be removed, a correspondence table is used giving a thickness of material to be removed for each of several average elastic couples.

0116The aforementioned correspondence table was obtained experimentally. To establish this above-mentioned correspondence table, one can proceed as follows: first, one determines experimentally by how much shrinkage of a thickness of one micron over the entire surface of a watch balance spring reduces the class attributable to this watchmaker hairspring 1.

0117Then, using a rule of three, that is to say by proportionality, the number of microns of thickness to be removed is calculated for each of several average elastic couples.

0118As a variant, one can use a correspondence table indicating the thickness of material to be removed for each of several average frequencies<i><o ostyle="single">f</o></i>.

0119To determine the thickness of material to be removed, it is also possible to use a mathematical model instead of the correspondence table.

0120According to another embodiment variant in accordance with the invention, it is possible to determine the thickness of material to be removed from the watch hairsprings 1 by calculation from the frequencies f measured and/or from the average<i><o ostyle="single">f</o></i>, using formula (1) explained above.

0121Moreover, according to a variant embodiment, the frequency measurement can be performed on watch springs 1 which have not been detached from the wafer 22. In this case, the frequency measurement can be performed according to the teachings of the document<patcit id="pcit0007" dnum="EP2423764A"><text>EP 2 423 764</text></patcit>.

0122In addition, the thickness of material to be removed from the watch hairsprings 1 made in step 102 can be determined from a measurement of a quantity other than the frequency of an oscillator consisting of a watch hairspring 1 and 'a pendulum of predetermined inertia.

0123For example, the thickness of material to be removed from watch hairsprings 1 made in step 102 can be determined from dimensional measurements of portions cut by engraving in wafer 22, these portions cut by engraving by wafer 22 possibly being portions of watchmakers' hairsprings 1 or geometric figures cut out of the wafer in addition to watchmakers' hairsprings 1. The quantity of material to be removed from the watchmakers' hairsprings 1 produced in step 102 can also be determined from a stiffness measurement carried out on qualification structures which have been cut out of the wafer 22 at the same time as the watchmakers' hairsprings 1 .

0124On the<figref idref="f0008">figure 10A</figref> is shown the cross section of an elastically flexible strand 3 of a watch balance spring 1 which has just been cut out by engraving in step 102 but which has not yet undergone oxidation.

0125Whatever the method used for determining the thickness of material to be removed e from the watch springs 1 at the end of step 102, it can advantageously be taken into account for this determination that the height<i>h₁</i> of the elastically flexible strand 3 of a watch balance spring 1 at the end of step 102 is known with a fairly high precision since it is equal to the thickness of the wafer 22. In this way, the inaccuracy of a horological hairspring 1 at the end of step 102 can be considered as being mainly due to steps 100, 101 and 102, and mainly concern the width<i>I₁</i> of the elastically flexible strand 3 of this horological hairspring 1.

0126In step 120 in the case of the manufacturing method 10 according to a first embodiment of the invention, the thickness of material to be removed e determined in step 110 is removed from the watch springs 1 still attached to the wafer 22 and, for the sake of economy, it need not be removed from the watch springs 1 belonging to the sacrificial sample.

0127Step 120 can be carried out by following the teachings of the document<patcit id="pcit0008" dnum="WO2015113973A1"><text>WO 2015/113973 A1</text></patcit>. More specifically, in the case of the manufacturing method 10 according to a first embodiment of the invention, the watch hairsprings 1 still attached to the wafer 22 are collectively subjected, at the same time, to step 120. In step 120 in the case of the manufacturing method 10 according to a first embodiment of the invention, the thickness of material to be removed e determined in step 110 is removed over the entire surface of the elastically flexible strand 3 of each of the watch springs 1 made in step 102 and remained attached to the wafer 22.

0128In the case of the manufacturing method 10 according to a first embodiment of the invention, step 120 comprises a sub-step 122 and a sub-step 124 following step 122. For the record, in the case of the method 10 according to a first embodiment of the invention, the watch hairsprings 1 after step 102 are made of silicon, which is the silicon of the wafer 22.

0129In sub-step 122, at least some of the watch hairsprings 1 produced in wafer 22 in step 102 are subjected to oxidation such that the thickness of silicon transformed into silicon oxide is equal to the thickness of material to be removed e determined in step 110. The oxidation may in particular be a thermal oxidation carried out between 800° C. and 1200° C. under an oxidizing atmosphere, in a furnace where silicon dioxide is formed from the silicon. The thermal oxidation can be a wet oxidation obtained in the presence of water vapor in the oven or else a dry oxidation obtained in the presence of oxygen in the oven. The oxidation time can be determined by appropriate formulas well known to those skilled in the art or it can be determined from calculators available online, for example at the following address: http://lelandstanfordjunior.com/thermaloxide .html. The thickness of silicon oxide (silicon dioxide) formed varies slightly depending on the crystallographic orientation of silicon, but the differences are negligible. The thickness of material to be removed e typically corresponds to approximately 44% of the thickness (referenced e' on the<figref idref="f0008">figure 10B</figref> mentioned below) of silicon oxide formed.

0130In the manufacturing process 10, the watchmakers' hairsprings 1 that have remained attached to the wafer 22 are subjected together and collectively to oxidation, while they are still attached to the wafer 22. The watchmakers' hairsprings 1 of the sacrificial sample may not not be subjected to step 120 and the following steps, for the sake of efficiency and profitability. In the variant where none of the watchmakers' hairsprings 1 have been detached from the wafer 22, all of the watchmakers' hairsprings 1 made in step 102 in the wafer 22 are subjected together and collectively to oxidation while they are still attached to pad 22.

0131The elastically flexible strand 3 represented on the<figref idref="f0008">figure 10B</figref> is the same as that shown on the<figref idref="f0008">figure 10A</figref>. On this<figref idref="f0008">figure 10B</figref>, this elastically flexible strand 3 is superficially oxidized, after having undergone sub-step 122. On the<figref idref="f0008">figure 10B</figref>, the reference 40 designates the non-oxidized silicon and the reference 41 designates the silicon dioxide which is formed during the sub-step 122. The thickness e′ of the layer made of the silicon dioxide 41 resulting from the oxidation at the sub-step 122 is greater than the thickness e of the non-oxidized silicon 40 whose oxidation has led to this silicon dioxide 41.

0132In sub-step 124, the silicon dioxide 41 is removed from at least some of the watch hairsprings 1 cut from the wafer 22 during step 102. The silicon dioxide can be removed by etching, or by chemical etching , for example with hydrofluoric acid.

0133In the manufacturing process 10, the watchmakers' hairsprings 1 that have remained attached to the wafer 22 are submitted together and collectively to the substep 124. In the event that none of the watchmakers' hairsprings 1 produced in the wafer 22 is detached from this wafer 22 in step 110, all of the watch hairsprings 1 cut out by engraving in step 102 are submitted together and collectively to sub-step 124.

0134There<figref idref="f0008">figure 10C</figref> represents the same elastically flexible strand 3 as the<figref idref="f0008">figures 10A and 10B</figref>. On the<figref idref="f0008">figure 10C</figref>, this elastically flexible strand 3 is freed from silicon dioxide 41, after having undergone sub-step 124. The elastically flexible strand 3 of the<figref idref="f0008">figure 10C</figref> has a height<i>h₂</i> lower than height<i>h₁</i> and a width<i>I₂</i> less than the width<i>I₁.</i>

0135Step 120 may include sub-steps 122 and 124 also when wafer 22 is not made of silicon. In particular, step 120 may include sub-steps 122 and 124 when wafer 22 is made of a silicon-based material.

0136Step 120 can be performed in a manner other than that described above. The section reduction of the elastically flexible strand 3 of the watch hairsprings 1 can be achieved by means of a plasma, and it is while the watch hairsprings 1 are in the state of<figref idref="f0005">figure 6</figref>, that is to say not yet released from the support 20 and the stop layer 21, either while the watchmakers' hairsprings 1 or part of the watchmakers' hairsprings 1 are in the state represented on the<figref idref="f0006">figure 7</figref>, that is to say freed from the barrier layer 21 and from the support 20, but still attached to the wafer 22. The section reduction by means of a plasma can be carried out including when the sacrificial mask 18 is still present on one face of the watchmakers' hairsprings 1, in which case only the side flanks of the watchmakers' hairsprings 1 are damaged.

0137Variations at step 120 are possible. It is possible, for example, to oxidize the hairspring with an oxide thickness w before step 110. This oxide thickness w corresponds to the final thermocompensation thickness or to a chosen thickness. The hairspring is measured after oxidation. The elastic torque is reduced by partially or totally deoxidizing the hairspring and reoxidizing it to the value w.

0138In this regard, the<figref idref="f0011">figure 13</figref> represents the successive steps of a manufacturing method 10a according to a second embodiment of the invention. The manufacturing process 10a is a manufacturing process for a batch of watch hairsprings 1. The manufacturing process 10a comprises a manufacturing process 1000 according to an embodiment of the second manufacturing process. In the example shown in<figref idref="f0011">figure 13</figref>, manufacturing process 1000 is part of manufacturing process 10a. However, it may be otherwise. In other words, the manufacturing process 1000 can be implemented without implementing all or part of the other steps of the manufacturing process 10a.

0139The manufacturing process 1000 is a process for manufacturing a batch of watch hairsprings (1) whose elastic torques have an average within a predetermined range. The manufacturing process 1000 includes steps 150, 152 and 153, in addition to steps 102 and 110 already described above.

0140Step 150 follows step 102, at the end of which the elastically flexible strand 3 of each of the watch springs 1 cut out from the wafer 22 is as shown on the<figref idref="f0012">Figure 14A</figref>.

0141At the end of step 150, the elastically flexible strand 3 of each of the watchmakers' hairsprings 1 cut from the wafer 22 is as shown in the<figref idref="f0012">Figure 14B</figref>. In step 150, several or all of the watch hairsprings 1 are subjected to a first oxidation so as to be transformed into superficially oxidized watch hairsprings each in a zone where, from the silicon-based material, the first oxidation creates a portion thermal compensation 50'a provided to modify the sensitivity to temperature variations of the elastic torque of the corresponding watch spring 1. On the<figref idref="f0012">Figure 14B</figref>, the reference w denotes the thickness of the thermal compensation portion 50'a.

0142Step 150 is followed by step 110, in which, on the basis of at least one measurement on at least part of the oxidized watch springs 1, the quantity of silicon-based material (referenced w' on the<figref idref="f0012">Fig. 14C</figref>) in removing oxidized watch hairsprings 1, to obtain the batch of watch hairsprings 1 having the elastic torques whose average is in the predetermined range. Examples of measures that can be employed in step 110 have been described above.

0143Step 152 follows step 110. The elastically flexible strand 3 of each of the horological hairsprings 1 cut out from the wafer 22 is as shown on the<figref idref="f0012">Fig. 14C</figref> at the end of step 152, in which, from the thermal compensation portion 50′a of several or all of the watch hairsprings 1, a residual thickness is removed which corresponds to the quantity of silicon-based material to remove w'. In step 152, the residual thickness removed from the thermal compensation portion 50'a corresponds to the quantity of silicon-based material to be removed w' and it may not be equal to the thickness of this quantity of material silicon-based to remove w'.

0144Indeed, the residual thickness removed in step 152 is made of the material based on oxidized silicon, which constitutes the thermal compensation portion 50'a and which can be silicon dioxide 41 in the case where the material based of silicon is silicon. In other words, the residual thickness removed from the thermal compensation portion 50'a in step 152 is not made of the same material as the quantity of silicon-based material to be removed w'. The residual thickness removed from the thermal compensation portion in step 152 is made of the material resulting from the oxidation of the silicon-based material to be removed w'.

0145In the case where the silicon-based material to be removed is silicon (doped or undoped), the residual thickness removed from the thermal compensation portion 50'a in step 152 is made of silicon dioxide 41. In the case where the silicon-based material to be removed is silicon 40 (doped or undoped), the residual thickness removed from the thermal compensation portion 50'a in step 152 is equal to approximately 227% of the 'thickness of the amount of silicon-based material to be removed w'.

0146The residual thickness removed in step 152 is such that the amount of silicon-based material consumed during a second oxidation regenerating the thermal compensation portion in step 153 is equal to the amount of silicon-based material to be removed in step 152.

0147In the case where the thermal compensation portion 50'a is made of silicon dioxide 41, the residual thickness which corresponds to the quantity of silicon-based material to be removed w' can be removed from the thermal compensation portion 50' a by means of a chemical attack, for example by employing hydrochloric acid. The duration of this chemical attack is a controlled duration, previously determined according to the quantity of silicon-based material to be removed w′.

0148Step 153 follows step 152. The elastically flexible strand 3 of each of the horological hairsprings 1 cut out from the wafer 22 is as shown on the<figref idref="f0012">figure 14D</figref> at the end of step 153, in which several or all of the oxidized watch springs 1 are subjected to a second oxidation such that the thermal compensation portion is regenerated. On the<figref idref="f0012">figure 14D</figref>, the reference w designates the thickness of the thermal compensation portion 50a as it is after having been regenerated.

0149On the<figref idref="f0012">figures, 14A, 14B, 14C and 14D</figref>, the reference 40 designates the silicon-based material, which may in particular be doped or undoped silicon, which is the case in the manufacturing method 1000 according to an embodiment of the second method. On the<figref idref="f0012">figures, 14A, 14B, 14C and 14D</figref>, the reference 41 denotes the material based on oxidized silicon, which may in particular be silicon dioxide, which is the case in the manufacturing method 1000 according to an embodiment of the second method.

0150The manufacturing method 10a according to a second embodiment of the invention differs from the method 10 in that it comprises the succession of steps 150, 110, 152 and 153, instead of the succession of steps 110, 120 and 130 For the rest, the manufacturing process 10a can be identical to the manufacturing process 10, which is the case in the second embodiment of the invention.

0151In the case where it is determined in step 110 that there is no silicon-based material to be removed, steps 152 and 153 are not carried out.

0152Preferably, step 150 is carried out collectively on the watch springs 1 still attached to the wafer 22.

0153Preferably, step 152 is carried out collectively on the watch springs 1 still attached to the wafer 22.

0154Preferably, step 153 is carried out collectively on the watch springs 1 still attached to the wafer 22.

0155Preferably, the quantity of silicon-based material to be removed w′ is determined from a measurement carried out on a sacrificial sample taken from among the watch springs 1 of the wafer 22 and which is dissociated from the wafer 22.

0156Preferably, in step 110, the quantity of silicon-based material to be removed w' is determined by means of a correspondence table indicating the thickness of silicon-based material to be removed w' for each of several pairs average elastic torques or for each of several quantities related to such average elastic torques.

0157On the graph of<figref idref="f0009">figure 11A</figref> and on the graph of<figref idref="f0009">figure 11B</figref>, the elastic torque M is on the abscissa, while the number n of watch hairsprings 1 among all the watch hairsprings 1 made in the same wafer 22 at step 102 during an implementation of the manufacturing method 10 are on the ordinate .

0158On the graph of<figref idref="f0009">figure 11A</figref>, curves C3, C4 and C5 are normally histograms but have been smoothed for clarity. On the graph of<figref idref="f0009">figure 11B</figref>, the curves C'3, C'4 and C'5 are normally histograms but they have been smoothed for the sake of clarity.

0159On the graphs of<figref idref="f0009">figures 11A and 11B</figref>, increasing classes of elastic torque are also shown along the abscissa axis. In the example shown on the<figref idref="f0009">figures 11A and 11B</figref>, the number of classes is equal to 80, but it could be different with another segmentation into classes. For example, the number of classes could be equal to 20 as was the practice in the past.

0160The C3 curve on the<figref idref="f0009">figure 11A</figref> and the curve C'3 on the<figref idref="f0009">figure 11B</figref> are each a graphic representation of the dispersion of the elastic couples of watch springs 1 produced in the same first wafer 22, during a first implementation of the manufacturing method 10 or 10a in which the corrected reusable mask 11 is used. The measurements used for curve C3 were performed on watch hairsprings 1 before these watch hairsprings 1 were subjected to steps 110 and 120, or to steps 110, 152 and 153. The measurements used for curve C'3 were taken on the watchmakers' hairsprings 1 after these watchmakers' hairsprings 1 have been subjected to steps 110 and 120, or to steps 110, 152 and 153.

0161The C4 curve on the<figref idref="f0009">figure 11A</figref> and the curve C'4 on the<figref idref="f0009">figure 11B</figref> are each a graphic representation of the dispersion of the elastic couples of watch hairsprings 1 made in the same second wafer 22, during a second implementation of the manufacturing method 10 or 10a in which the same corrected reusable mask 11 is used as in the first implementation of the manufacturing process 10 or 10a. The measurements used for curve C4 were taken on the watchmakers' hairsprings 1 before these watchmakers' hairsprings 1 had been subjected to steps 110 and 120, or to steps 110, 152 and 153. The measurements used for curve C'4 were performed on the watch hairsprings 1 after these watch hairsprings 1 have been subjected to steps 110 and 120, or to steps 110, 152 and 153.

0162The C5 curve on the<figref idref="f0009">figure 11A</figref> and the curve C'5 on the<figref idref="f0009">figure 11B</figref> are each a graphic representation of the dispersion of the elastic couples of watch springs 1 made in the same third wafer 22, during a third implementation of the manufacturing method 10 or 10a in which the same corrected reusable mask 11 is used as in the first and the second implementation of the manufacturing process 10 or 10a. The measurements used for curve C5 were taken on the watchmakers' hairsprings 1 before these watchmakers' hairsprings 1 had been subjected to steps 110 and 120, or to steps 110, 152 and 153. The measurements used for curve C'5 were performed on the watch hairsprings 1 after these watch hairsprings 1 have been subjected to steps 110 and 120, or to steps 110, 152 and 153.

0163The measurements used for curve C3, curve C4 and curve C5 on the<figref idref="f0009">figure 11A</figref> were carried out on watchmakers' hairsprings 1 having benefited from the first correction incorporated in the corrected reusable mask 11. The measurements used for the curve C'3, the curve C'4 and the curve C'5 on the<figref idref="f0009">figure 11B</figref> were carried out on watch hairsprings 1 having benefited both from the first correction incorporated into the corrected reusable mask 11 and from the second correction resulting from steps 110 and 120 or from steps 110, 152 and 153. Consequently, a comparison of the<figref idref="f0009">figures 11A and 11B</figref> makes it easy to understand the effect of the second correction resulting from steps 110 and 120, or from steps 110, 152 and 153.

0164The watchmakers' hairsprings 1 having been produced in the first wafer 22 and having been subjected to steps 110 and 120, or to steps 110, 152 and 153, that is to say the watchmakers' hairsprings 1 on which the measurements employed have been carried out to produce the curve C′3, constitute a first batch of watch springs 1 whose elastic torques have an average (denoted M₃ on the<figref idref="f0009">figure 11B</figref>) in a predetermined range, which is the predetermined range P on the<figref idref="f0009">figure 11B</figref>.

0165The watchmakers' hairsprings 1 having been produced in the second wafer 22 and having been subjected to steps 110 and 120, or to steps 110, 152 and 153, that is to say the watchmakers' hairsprings 1 on which the measurements used have been carried out to produce curve C'4, constitute a second batch of watch springs 1 whose elastic torques have an average (denoted M₄ on the<figref idref="f0009">figure 11B</figref>) within the predetermined range P. As can be seen in the<figref idref="f0009">figure 11A</figref>, before having been subjected to steps 110 and 120, or to steps 110, 152 and 153, the watch hairsprings 1 having been produced in the second wafer 22, that is to say the watch hairsprings 1 on which have been carried out the measurements used to produce curve C4, did not constitute a batch of watch springs 1 whose elastic torques have an average in the predetermined range P.

0166The watchmakers' hairsprings 1 having been produced in the third wafer 22 and having been subjected to steps 110 and 120, or to steps 110, 152 and 153, that is to say the watchmakers' hairsprings 1 on which the measurements used have been carried out to produce curve C'5, constitute a third batch of watch springs 1 whose elastic torques have an average (denoted M₅ on the<figref idref="f0009">figure 11B</figref>) within the predetermined range P. As can be seen in the<figref idref="f0009">figure 11A</figref>, before having been subjected to steps 110 and 120, or to steps 110, 152 and 153, the watch hairsprings 1 having been produced in the third wafer 22, that is to say the watch hairsprings 1 on which have been carried out the measurements used to produce curve C5, did not constitute a batch of watch springs 1 whose elastic torques have an average in the predetermined range P.

0167As can be seen on the<figref idref="f0009">figure 11B</figref>, the watchmakers' hairsprings 1 having been produced in the first, second and third wafers 22 and having been subjected to steps 110 and 120, or to steps 110, 152 and 153, that is to say the watchmakers' hairsprings 1 on which have the measurements used to produce the curves C'3, C'4 and C'5, can all be classified each in one of the classes 0 to 40. However, when a watch balance spring is classified in any of the classes 1 to 40, it can be paired with a balance wheel belonging to one of the classes 1 to 40, which constitute a reduced number of classes.

0168Steps 110 and 120 can be repeated one or more times, until the average of the elastic torques of the watchmakers' hairsprings 1 made in the same wafer 22 is within the predetermined range.

0169Steps 110, 152 and 153 can be repeated one or more times, until the average of the elastic torques of the watch springs 1 made in the same wafer 22 is within the predetermined range.

0170As can be seen on the<figref idref="f0002">picture 3</figref>, step 120 can be followed by a step 130 in which, on each of several watch hairsprings 1 constituting at least a part of the watch hairsprings 1 produced in the wafer 22 in step 102, a thermal compensation portion is formed . On the<figref idref="f0010">figure 12</figref>, such a thermal compensation portion 50 has the form of a peripheral layer covering the elastically flexible strand 3 of a watch balance spring 1.

0171The thermal compensation portion 50 reduces, cancels or inverts the sensitivity to temperature variations of the elastic torque of the watch balance spring 1. In the case where there are no steps 110 and 120, step 130 can be carried out directly after step 102.

0172In step 130 in the case of the manufacturing method 10 according to a first embodiment of the invention, the thermal compensation portion 50 is formed on the watch springs 1 still attached to the wafer 22 and, for the sake of economy, it may not be formed on the watch springs 1 belonging to the sacrificial sample. In the case of the manufacturing method 10 according to a first embodiment of the invention, the watch springs 1 still attached to the wafer 22 are subjected collectively, together and at the same time, to step 130. In step 130 in the case of the manufacturing method 10 according to a first embodiment of the invention, the thermal compensation portion is formed over the entire length and the entire surface of the elastically flexible strand 3 of each of the watch hairsprings 1 made in step 102 and remained attached to plate 22.

0173For the record, in the case of the manufacturing method 10 according to a first embodiment of the invention, the watch hairsprings 1 after step 102 are made of silicon, which is the silicon of the wafer 22.

0174In step 130, at least some of the watch hairsprings 1 produced in the wafer 22 in step 102 are subjected to oxidation so as to be superficially oxidized over a thickness which depends on the degree of thermal compensation desired. The oxidation can in particular be a thermal oxidation carried out between 800° C. and 1200° C. under an oxidizing atmosphere, in a furnace where silicon dioxide is formed from the silicon. The thermal oxidation of step 130 can be a wet oxidation obtained in the presence of water vapor in the oven or else a dry oxidation obtained in the presence of oxygen in the oven.

0175In the manufacturing process 10, the watchmakers' hairsprings 1 that have remained attached to the wafer 22 are subjected together and collectively to the oxidation of step 130, while they are still attached to the wafer 22. The watchmakers' hairsprings 1 of the The sacrificial sample may not be submitted to step 130, for the sake of efficiency and cost-effectiveness. In the variant where none of the watchmakers' hairsprings 1 have been detached from the wafer 22, all of the watchmakers' hairsprings 1 produced in step 102 in the wafer 22 are subjected together and collectively to the oxidation of step 130 while they are still attached to wafer 22.

0176The thermal coefficient of the Young's modulus of a material is also called the thermoelastic coefficient of this material. There<figref idref="f0010">figure 12</figref> is a cross section of an elastically flexible strand 3 of a horological hairspring 1 as it is after step 130. On the<figref idref="f0010">figure 12</figref>, the elastically flexible strand 3 comprises a silicon core 40 and the thermal compensation portion 50 which coats this silicon core 40. The silicon 40 of the core has a thermoelastic coefficient which is negative. The silicon dioxide of the thermal compensation portion 50 has a thermoelastic coefficient which is positive. This is why the thermal compensation portion 50 reduces or cancels out or even reverses the sensitivity to temperature variations of the elastic torque of the watch balance spring 1.

0177After being detached from the wafer 22, the watch springs 1 are classified, for example each by means of an Omegametric type device (protected trademark) in a step 200, which follows step 130, or step 120 , or even step 110. After having been classified in step 200, the watch springs 1 coming from the same wafer 22 are paired with balance wheels 8, in a step 250. In this step 250, the watchmakers' hairsprings 1 coming from the same wafer 22 are paired with balances 8 selected from those of a batch that was obtained in a step 210 and which consists of balances 8 classified.