EP3592879A1

EP3592879A1 - Material comprising a thin layer of an alloy comprising titanium and gold and method for obtaining such a material

Info

Publication number: EP3592879A1
Application number: EP18714976.0A
Authority: EP
Inventors: Cyrill CATTIN; Ayat KARIMI; Guy Semon
Original assignee: LVMH Swiss Manufactures SA
Current assignee: LVMH Swiss Manufactures SA
Priority date: 2017-03-10
Filing date: 2018-03-09
Publication date: 2020-01-15
Also published as: FR3063675A1; WO2018162745A1

Abstract

The present invention relates to a material comprising a base substrate and a thin layer of an alloy with atomic formula Ti_1-xAux, 1-x and x being atomic fractions, x being comprised between 0.22 and 0.28. The present invention also relates to a method for obtaining such an alloy, said method comprising in particular, after having deposited a substrate to be covered, two target substrates made of pure titanium and a target substrate made of pure gold in a deposition chamber: adjusting the pressure in the deposition chamber; injecting an inert gas into the deposition chamber; bombarding the first target substrate of pure titanium by a first magnetron; bombarding said target substrate of pure gold by a second magnetron; bombarding the second target substrate of pure titanium by a third magnetron, so as to cause the formation of a plasma containing titanium ions and gold ions having predetermined stoichiometric ratios; and depositing a thin layer of the alloy on the substrate to be covered.

Description

Material comprising a thin layer of an alloy comprising titanium and gold and process for obtaining such a material

Field of the Invention

The invention relates to an alloy comprising titanium and gold, and is intended in particular to a material comprising a base substrate and a thin layer of such alloy comprising titanium and gold, as well as a method of manufacturing such a material.

State of the art

The background is the design of scratch- and abrasion-resistant materials. In the field of watchmaking in particular, as in the field of jewelery, eyewear or fashion accessories, these fields being given as non-limiting examples, those skilled in the art seek to develop new materials with such properties.

A general problem lies in the development of materials having a hardness greater than that of materials conventionally used in these fields, such as titanium or steel for example. To this end, developments are notably carried out to design new alloys having improved hardness characteristics. A particularly hard alloy has recently been developed, based on titanium and gold. This new alloy is particularly interesting biomedical research because it is a biocompatible alloy very hard and highly resistant to abrasion. This alloy has the atomic formula Ti ₃ Au and could be synthesized in β phase. This discovery was the subject of a published study: E. Svanidze et al., "High hardness in the biocompatible intermetallic compound 3-Ti ₃ Au".

As part of this study, exceptional hardness qualities of the 3-Ti ₃ Au alloy, up to 800 HV, were demonstrated. The publication shows that β- Ti ₃ Au is four times harder than titanium and eight times harder than gold.

For the authors, the intrinsic qualities of bio-integrability of titanium and gold make this alloy an interesting candidate for the production of prostheses.

In this context, researchers are encouraged to explore methods of producing such an alloy in the mass, that is to say in "bulk" according to the term in English known to those skilled in the art. However, on the one hand, the production of this 3-Ti ₃ Au alloy in bulk is delicate because this compound has in particular a relative instability. The exploitation of the intrinsic properties of a titanium-gold alloy in one of the abovementioned applications is therefore not obvious, particularly because of the difficulty in obtaining bulk formed parts in such an alloy, having an acceptable strength and assuring the integrity of said parts.

On the other hand, economically, the production of such a bulk alloy would be expensive.

The proposed solution consists in depositing a thin layer of a titanium and gold alloy comprising in particular between 22 at.% And 28 at.% Of gold (ie an atomic fraction of between 0.22 and 0.28). , in particular consisting of 3-Ti ₃ Au, on a substrate, in particular a substrate made of titanium, steel, brass or ceramic.

The present invention also relates to a method relating to the manufacture of such a material, in particular formed of 3-Ti ₃ Au deposited in a thin layer on a substrate.

Presentation of the invention

More specifically, the subject of the invention is a material comprising a base substrate and a thin layer of an alloy of the atomic formula Ti _x Au _x , 1-x and x representing respective atomic fractions of titanium and gold in the alloy, x being between 0.22 and 0.28.

Thanks to the material according to the invention, it is possible to design particularly hard and / or abrasion resistant parts.

According to one embodiment, said thin layer furthermore comprises a chemical element distinct from titanium and gold, or a combination of distinct chemical elements of titanium and gold, representing at most 15% of the layer. thin (corresponding to an atomic fraction of 0.15).

According to one embodiment, said chemical element or said combination of chemical elements comprises one of the metals or a combination of several of the following metals: Ag, Cu, Zn, Pt, Pd, Ni, Zn, Cd, Fe, Al , Ga, In.

According to one embodiment, said chemical element or said combination of chemical elements is a nonmetallic chemical element or a combination of non-metallic chemical elements. For example, said chemical element or said combination of chemical elements comprises nitrogen (N). In another example, said chemical element or said combination of chemical elements may comprise nitrogen and a metallic element such as copper. The presence of the chemical element or combination of chemical elements allows adjustment of the color of the alloy.

According to one embodiment, said alloy has a crystalline form. According to one embodiment, x is equal to 0.25.

Advantageously, said alloy may consist exclusively of Ti ₃ Au. In particular, said alloy may consist exclusively of Ti ₃ Au in phase

According to another embodiment, said alloy has an amorphous form.

Advantageously, the thin layer has a thickness less than or equal to 50 μηι.

According to one embodiment, the base substrate consists of titanium, for example grade 2 titanium, or steel, or brass or ceramic.

The present invention also relates to a watch movement part comprising the material briefly described above. This example of use can not be interpreted in a limiting way.

The present invention also provides a watch case comprising the material briefly described above. This example of use can not be interpreted in a limiting way.

Furthermore, the present invention provides a method for depositing a thin layer of an alloy comprising titanium and gold on a substrate, said method comprising the following steps:

placing a substrate to be coated, at least one pure titanium target substrate and at least one pure gold target substrate in a deposition chamber;

the regulation of the pressure in the deposition chamber;

injecting an inert gas to allow the formation of a plasma, said inert gas being argon, in the deposition chamber; bombarding said at least one pure titanium target substrate with a first magnetron;

the bombardment of said at least one target substrate in pure gold by a second magnetron; so as to cause the formation of a plasma comprising titanium ions and gold ions in determined stoichiometric proportions;

depositing a thin layer of an alloy of atomic formula Ti _{x x} Au _x , 1-x and x representing atomic fractions, x being between 0.22 and 0.28, on the substrate to be coated.

With this method, it is possible to deposit a thin layer of an alloy comprising titanium and gold on a base substrate. According to one embodiment, the method furthermore comprises heating the substrate to be coated at a temperature greater than or equal to 350 ° C., for deposition of the alloy in the crystalline phase.

According to one embodiment, the method furthermore comprises adjusting the distance between the target substrates and the surface of the substrate to be covered between 40 mm and 200 mm, for the deposition of the crystalline phase alloy.

Advantageously, the adjustment of the pressure in the deposition chamber consists of placing under a pseudo-vacuum at a pressure of between 1 × 10 ⁴ and 10 × 10 ⁴ Pa.

Advantageously, the power of each of said magnetrons is independently configured to obtain the deposition of said thin layer of the alloy comprising titanium and gold on the substrate to be covered.

According to one embodiment, a first and a second pure titanium target substrate and a pure gold target substrate being placed in the deposition chamber, three independent magnetrons are implemented, the first magnetron implementing a power included between 20.3 and 61.2 kW / m ² for bombarding the first pure titanium target substrate connected to a radiofrequency source, the second magnetron using a power of between 0.5 and 20.4 kW / m ² for bombarding the pure gold target substrate connected to a direct current source and a third magnetron implementing a power of between 20.3 and 61.2 kW / m ² for bombarding the second pure titanium target substrate connected to a current source drawn.

According to one embodiment, the power implemented by each of said magnetrons is configured to deposit a layer of Ti ₃ Au in β phase on said substrate to be covered.

Other features and advantages of the invention will become apparent from the following description made with reference to the accompanying figures given by way of non-limiting examples. Brief description of the drawings

Figure 1 illustrates a phase equilibrium diagram of Ti-Au compounds. Figure 2 shows a transverse view of β-T Au at scanning electron microscopy.

Figures 3 and 4 show the comparison between a raw surface of a substrate coated with a thin layer of 3-Ti ₃ Au (FIG 3) and a polished surface of the same substrate also covered with a thin layer of 3-Ti ₃ To polished (FIG 4).

FIG. 5 shows the hardness of the alloy obtained as a function of the percentage of gold in the deposited thin film.

Figure 6 shows the Young's modulus of the alloy obtained as a function of the percentage of gold in the deposited thin film.

DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION

The material according to the invention and the process for obtaining this material can be used in any field, for the manufacture of parts having a high hardness and / or resistance to abrasion.

When it comes to making a titanium-gold alloy, it must first be noted that titanium (Ti) and gold (Au) have an almost identical atomic size, but exhibit crystalline structures, electronegativities and different electronic structures. Titanium is a transition metal with a small number of electrons d compared to the noble metal gold, which has a larger number of electrons d. Therefore, when forming an alloy of these two elements, significant redistribution and overlap of the charges is expected, which can result in a wide variety of structures and physical properties.

With reference to FIG. 1, the equilibrium phase diagram of the compounds of

Ti-Au gives an overview of the stoichiometric structures that can be formed.

The phase diagram of the Ti-Au alloy thus reveals four equilibrium compounds: Ti ₃ Au, of cubic crystalline structure, TiAu, orthorhombic, T1AU2, tetragonal and TiAu4, otherwise tetragonal.

Among these four compounds, the aforementioned study (E. Svanidze et al.) Showed that Ti ₃ Au, in β phase, had the highest hardness, exceeding 800 HV (or about 7.85 GPa), which is, as already mentioned, a hardness four times greater than that of pure titanium and eight times higher than that of pure gold.

To explain the reasons for such a high hardness of the Ti ₃ Au compound, it has been hypothesised that this originated either from the intermetallic character of the structure crystal which imposes a unique arrangement of the atoms, or of its particular electronic structure, which is characterized by a high valence electron density, a reduced binding length and the formation of pseudo-gaps.

The Ti ₃ Au compound is formed in two distinct phases, a and β, both in cubic lattice structure.

The β phase is preferentially formed at elevated temperature and, like other intermetallic compounds of molecular formula A ₃ B, crystallizes in the form of a cubic network of type A15, space group No. 223, in which two atoms of 'or occupy the atomic positions (0, 0, 0; ½, ½, ½) and six titanium atoms occupy the atomic positions (¼, 0, ½ 0, 0, ½, ½, ¼, 0, ½, ¾, 0, 0, ½, ¼, 0, ½, ¾). The particular arrangement of titanium atoms at sites positioned at (¼, 0, ¼) generates non-interactive orthogonal chains with gold atoms located at the corner and center of the unit cells of the cubic lattice, but form linear chains mutually orthogonal running through the crystal lattice.

Phase a, which is favored at lower temperatures, develops as a L12-type cubic lattice, space group No. 221, where the gold atoms occupy the positioned sites (0, 0). , 0) and the titanium atoms occupy the positioned sites (0, ½, ½).

Therefore, the two phases a and β differ in the atomic environment of titanium and gold, respectively, and it can be expected that β-phase Ti ₃ Au has a higher hardness than a phase- ₃ Ti ₃ Au, on the one hand because titanium is coordinated 14 times in the β phase compared to 12 times in phase a, and secondly because the length of the titanium-gold bond is shorter in the β phase than in the phase at. In practice, in the remainder of the detailed description, reference is often made to the particular Ti ₃ Au alloy, in particular to the β phase. Nevertheless, even when reference is made to Ti ₃ Au, and unless it is explicitly stated that only this alloy is referred to in a particular embodiment, it should be understood that any alloy of the Th-xAux atomic formula can be adapted, 1-x and x representing the respective atomic fractions of Ti and Au in the alloy. Advantageously, x is between 0.22 and 0.28. In particular, for x = 0.25, the alloy obtained is Ti ₃ Au, in phase a or β. For other values of x, different atomic formulas can be obtained, including TiAu, T1AU2, TiAu4 or mixed phases composed of alloys comprising Ti ₃ Au and / or TiAu and / or T1AU2 and / or TiAu4. The traditional Ti _{x x} Au _x preparation by melting the stoichiometric amounts of the constituents requires high temperatures, for melting and eventual annealing of the samples. As mentioned in the preamble, the formation of Ti ₃ Au, in particular in the β-phase, mass, ie in bulk, is complicated by a great fragility of this material. However, the growth from the vapor phase, by means of a plasma, can be obtained at significantly lower temperatures.

In this context, it is proposed here the development of a titanium-based alloy gold, affixed in a thin layer on a substrate, by a method of mixing ions under energetic plasma. Thus, it is proposed to form a titanium and gold plasma, in the stoichiometric proportions and desired shape conditions, in particular to form a thin layer of Ti _x Au _x alloy, in particular with x included. between 0.22 and 0.28, deposited on a substrate to be coated.

Description of the process for deposition of a Ti _x Au _x thin film on a substrate:

To achieve the deposition of a thin layer of a Ti _x Au _x alloy, with x ranging from 0.22 to 0.28, said alloy being for example constituted of Ti ₃ Au in the β phase, a specific reactor and particular shaping conditions can be implemented.

With regard to the deposition reactor used, according to one embodiment, the latter consists of a cylindrical stainless steel chamber 400 mm in diameter and 500 mm in height. It is understood that other forms of deposition chambers and other dimensions may be quite suitable, particularly depending on the shape and amount of the substrate to be coated and / or target substrates.

Three sputtering sources, namely magnetrons, are preferably used. The number of magnetrons used can however be adapted according to the number of target substrates.

The three magnetrons typically have flexible heads, are equipped with flaps and are mounted symmetrically at 120 ^° each relative to the base plane of the deposition chamber.

In practice, the flexibility of the magnetron heads makes it possible either to co-spray in confocal positions or to form multilayer coatings by rotating the substrate to be covered alternately in front of each target. The magnetron target substrates may be connected to a DC source, a radio frequency source, or a pulsed power source.

According to one embodiment, the substrate to be coated may for example be introduced into the reactor chamber from an upper plate, as well as crosspieces for the power supply provided for heating and polarizing as well as for measuring the temperature of the substrate to be coated. Preferably, the presence of a linear displacement and alignment unit allows a precise adjustment of the distance between the target substrates, consisting respectively of pure titanium and pure gold, and the surface of the substrate to be coated. According to one embodiment, in the selected reactor, the substrate can be heated to 850 ° C and rotate at a speed of 1 to 60 revolutions per minute.

Consequently, various experiments have made it possible to deposit thin films of Ti _x Au _x on a substrate, such as a substrate made of silicon, titanium or steel in particular. It should be noted that the substrate to be covered may also be ceramic for example. In the case where the base substrate is ceramic, this material already having a very high hardness, the deposition of a thin layer of Ti _x Au _x has the advantage of improving the visual appearance of the material obtained. . In particular, thin layers of Ti _x Au _x , with x ranging from 0.22 to

0.28, were obtained from 50 mm target substrates made of pure titanium (99.995%) and pure gold (99.997%). As already indicated, the dimensions of these target substrates can of course be adapted. The deposition chamber is placed, according to one embodiment, at a pressure of between 1 .10 ⁴ and 2.10 ⁴ Pa. Then, an inert gas, such as argon, is introduced into the chamber as a gas. of plasma for sputtering and ionizing titanium and gold atoms.

According to a preferred embodiment, two pure titanium target substrates and a pure gold target substrate are arranged in the chamber. According to this embodiment, a titanium target substrate is connected to a radiofrequency source while the other titanium target substrate is connected to a pulsed current source at a frequency of between 10 kHz and 100 kHz, with a duration of drawdown from 2 to 5 microseconds, each titanium target substrate being each further bombarded by means of a magnetron, each magnetron applying a power of between 20.3 and 61.2 kW / m ² . According to this embodiment, the gold target substrate is connected to a direct current source with an applied power of between 0.5 and 20.4 kW / m ² .

According to one embodiment, by maintaining the power applied to the titanium target substrates constant and by varying the power applied to the gold target substrate, the stoichiometric composition of the Ti _x Au _X compound varies, x ranging between 0.15 and 0. , 40, preferably according to the invention, between 0.22 and 0.28.

Furthermore, according to the proposed embodiment, the temperature of the substrate to be covered has been adjusted between ambient temperature and 650 ° C., measured on the rear face. of the substrate to be coated, in order to form, in particular, the Ti ₃ Au compound in a quasi-amorphous or totally crystalline form in the β-phase.

According to one embodiment, the target substrates are also disposed at a distance of between 40 mm and 200 mm from the substrate to be coated in order to promote β-phase formation and to optimize the deposition rate and the adhesion of the layer. thin Th-xAux, with x between 0.22 and 0.28, on the substrate to be coated.

The thickness of the Ti _x Au _x deposit produced on the substrate to be coated was measured by means of a Tencor alpha step D500 type profilometer at a value between 2 and 10 μηι, depending on the substrate to be coated. It is understood that the thickness of the thin layer can be adapted to the need.

It should be noted that "thin" layer means a layer whose thickness is less than or equal to 50 μηι.

Previously, it has been described a method according to the invention for obtaining an alloy formed of a thin layer of titanium and gold deposited on a substrate to be coated.

In what follows, some experimental results obtained will be presented.

Experimental results on alloys produced using the process described above:

The results given below were obtained on the basis of tests carried out on a material produced in accordance with the process according to the invention in the particular configuration given by way of example above.

The hardness and Young's modulus of the samples obtained were determined from nanoindentation loading-unloading curves using a three-sided Berkovich diamond tip operating in continuous stiffness measurement mode. For each sample, a set of four times four indentations was applied at intervals of 35 μηι and for a depth of 1 μηι. Hardness and Young modulus were calculated as a function of depth of penetration or applied load using the method described by Oliver and Pharr in WC Oliver, GM Pharr, "Measurement of hardness and elastic modulus by instrumented indentation: Advances in the understanding and refinements to methodology, J. Mater. Res. 19 (2004) 3- 20. The range of indentation depths used was chosen so as not to exceed about 10% of the thickness of the deposited thin film, in order to minimize the effects of the substrate. For example, for a deposited thin film of about 2 μηι thickness, the indentations implemented have not exceeded, in the tests performed, about 200 nm.

In transverse view, the morphology of the various compounds of titanium-gold is variable. In particular, according to the preferred embodiment, wherein the gold represents 25 at.% (Corresponding to an atomic fraction of 0.25) of the thin layer in stoichiometric proportions, the compound being therefore Ti ₃ Au, the structures Columns are distinctly pronounced, as shown in Figure 2. Moreover, said columns seem to extend over the entire thickness of the thin layer.

The morphology of the surface after the deposition of the thin layers and the roughness obtained are important parameters of the thin layers because they connect the mechanisms of growth (random or privileged orientation, shading effects, mobility of the atom, ionic flux surface diffusion, etc.) to functional properties (mechanical, optical, etc.). For a given thin layer, for example Ti ₃ Au, the surface morphology and the roughness depend on the deposition rate of said thin layer, the texture of growth, the type of ion bombardment, the thickness of the layer performed and the profile of the underlying substrate. These parameters can be adjusted, according to the invention, to produce the desired material, consisting of a thin layer of T ^. _x Aux deposited on a substrate.

FIGS. 3 and 4 respectively show a scanning electron microscope view of a material formed of a grade 2 titanium base substrate covered with a thin layer of β-phase Ti ₃ Au deposited at a temperature greater than 350 ° C. In the case of Figure 4, the base substrate was polished before the deposition of the thin layer, unlike that of Figure 3. The sample obtained has crystallites having a certain location, since the deposition of the thin layer is done first to fill the holes and porosities of the sandblasted surface to finally generate a smoother surface than the original surface.

Thus, as shown in FIG. 4 in particular, thanks to the deposition of a thin layer of Ti ₃ Au on a substrate such as a titanium substrate of grade 2, it is possible to obtain a polished effect. At a minimum, the deposition of such a thin layer significantly reduces the surface roughness of a grade 2 titanium substrate, a material known to be difficult to polish. According to a preferred embodiment, the present invention proposes the production of a material consisting of the deposition of a thin layer of Ti ₃ Au in the β phase (β- Ti ₃ Au) on a base substrate, such as a substrate made of titanium, steel, brass or ceramic, for example.

To achieve such a deposition of a thin layer of 3-Ti ₃ Au stably, the method according to the invention can in particular comprise, on the one hand, the adjustment of the deposition parameters, essentially the powers applied to each of the three magnetrons, in order to obtain the ratio between titanium ions and gold ions in the plasma which is 75 at% of titanium ions per 25 at% of gold (corresponding to atomic fractions of 0, 75 and 0.25 respectively), required to obtain the Ti ₃ Au composition, and, secondly, the optimization of the fully crystalline β phase by adjusting the deposition temperature of the thin layer.

Advantageously, it is also possible to optimize the deposition conditions of the thin layer to obtain strongly adherent thin layers, without cracks, and hard.

In particular, the deposition temperature was determined to be greater than 350 ° C. to obtain the deposition of a totally crystalline thin film of 3-Ti ₃ Au. It should be noted that, as already mentioned, according to the preferred embodiment, three magnetrons are actually implemented, two magnetrons being used to bombard respectively two pure titanium target substrates, the third magnetron being used to bombard a single target substrate. in pure gold.

In order to obtain the deposition of a thin layer of Ti _x Au _x adhering optimally to the substrate to be covered, the parameterization of said three magnetrons can be optimized. In particular, the third magnetron is configured to allow the production of high energy gold ions and this reduces the distance between the target substrates and the substrate to be coated. Rotation of the substrate to be coated also favors the reduction of the distance between the target substrates and the substrate to be coated, compared to the confocal spray. Furthermore, the use of a radiofrequency energy source on a first titanium target substrate, and the use of a power source pulsed on the second titanium target substrate makes it possible to regulate the energy of the titanium ions. This also ensures proportionality between titanium ions and gold ions since the gold sputtering rate is significantly higher than that of titanium. In addition, the application of a negative bias on the substrate to be coated also favors the deposition of a desired Ti- _x Au _x thin film, depending on all the above parameters. Finally, the negative bias of the substrate to be coated can also be optimized to minimize the risk of cracking of the alloy obtained. By adjusting this negative bias of the substrate, the adhesion of the thin layer to the substrate is further enhanced.

To measure the hardness of the materials obtained by means of the method described above, different types of indentation were implemented, based respectively on a constant load, a constant relative depth and the continuous stiffness measurement.

According to the indentation mode constant load or constant relative depth, several charges were applied to measure the hardness and Young's modulus, in particular in order to highlight any effects of the substrate and the probable change in hardness. function of the thickness of the thin layer. These measurements are averaged over four times four indentation tests for each set of measurements.

As shown in FIGS. 5 and 6, the measured values of hardness and Young modulus have a maximum for the 3-Ti ₃ Au compound, especially up to more than 12 GPa for the hardness. FIG. 5 shows in particular that for an alloy of the atomic formula Ti _{x x} Au _x , with x being between 0.22 and 0.28, corresponding to the gray zone 10, the hardness of the material obtained is significantly greater than 1 1 GPa.

In summary, the present invention relates to the production of a material comprising a thin layer of a titanium-gold alloy, in particular of the atomic formula of Ti _x Au _x , 1-x and x representing the respective atomic fractions. titanium and gold in the alloy, where x is between 0.22 and 0.28. In particular, the alloy may consist exclusively of Ti ₃ Au, particularly in the β phase, deposited on a base substrate, in particular a substrate made of titanium, steel, brass, or ceramic.

Experimental results have shown that such a material has an exceptional hardness, well above 8 GPa, and up to more than 12 GPa according to the tests conducted, as shown in Figure 5. Still with reference to Figure 5, the The hardness of the obtained material is thus greater than 1 1 GPa in the case of the deposition on a substrate of a thin film of Ti _x Au _x with x between 0.22 and 0.28. Such a material can in particular be used in the field of watchmaking, either to manufacture particularly robust watch cases, with a titanium base substrate for example, or to manufacture watch movement parts that are particularly resistant to watchmaking. abrasion, such as gears or bearings, with a brass base substrate for example. The previous examples are of course given as illustrations and can not be considered as limiting.

In other areas, where the production of scratch-resistant or abrasion-resistant parts is desired, such as in jewelery, eyewear or fashion accessories, for example, the material according to the invention can also be advantageously exploited. .

Furthermore, it should be noted that, in the context of the present invention, the thin film deposited on a substrate may comprise, in addition to titanium and gold, a metal or a combination of metals, the addition of which allows in particular to adjust the color of the alloy, or even more generally, a chemical element or a combination of metallic and / or non-metallic chemical elements.

According to the invention, the thin layer deposited on the substrate therefore has a generic atomic formula Tii- _x - _y Au _x My, x, y and 1 -xy being atomic fractions, with 0.22 <x <0.28 . y is at most 0, 1, 5. Preferably, y <0.05.

The chemical element or the combination of chemical elements M is integrated in the thin layer and is housed in the interstices or at the grain boundary of the molecules of the alloy Ti

At.

As indicated, M is a chemical element or a combination of chemical elements. More specifically, M is Ag, Cu, Zn, or a combination of these metals, in particular to obtain a yellow tint of the alloy, M is Cu, in particular to obtain a red tint of the alloy, M is Ag, Cu, or a combination of these metals, in particular to obtain pink and bright pink hues of the alloy, M is Pt, Pd, Ni, Zn, or a combination of these metals, in particular to obtain a white color of the alloy. alloy, M is Ag, Cu, Cd, or a combination of these metals, in particular to obtain a green tint of the alloy, and M is Fe, Al, Ga, In, or a combination of these metals, in particular to obtain blue and purple shades of the alloy.

M may also comprise a chemical element that is not necessarily metallic: M may for example comprise nitrogen (N), making it possible to obtain more vivid shades. M can also be a combination of nitrogen and a metal element. For example M can be a combination of nitrogen and copper, to obtain a bright red hue.

It is furthermore specified that the present invention is not limited to the examples described above and is capable of variants accessible to those skilled in the art.

Claims

1. A material comprising a base substrate and a thin layer of an alloy of the atomic formula Ti _x Au _x , 1-x and x representing respective atomic fractions of titanium and gold in the alloy, where x is between 0, 22 and 0.28.

The material of claim 1, said thin film further comprising a chemical element separate from titanium and gold, or a combination of distinct titanium and gold chemical elements, representing at most 15 at. the thin layer.

The material of claim 2, wherein said chemical element or said combination of chemical elements comprises one of the metals or a combination of more than one of the following metals: Ag, Cu, Zn, Pt, Pd, Ni, Zn, Cd , Fe, Al, Ga, In.

The material of claim 2 or 3, wherein said chemical element or combination of chemical elements comprises nitrogen.

The material of claim 1 wherein x is 0.25.

6. Material according to the preceding claim, said alloy consisting exclusively of T13AU.

7. Material according to the preceding claim, said alloy consisting exclusively of Ti ₃ Au β phase.

8. Material according to one of the preceding claims, wherein the thin layer has a thickness less than or equal to 50 μηι.

9. Material according to one of the preceding claims, wherein the base substrate is made of titanium, for example grade 2 titanium, or steel, or brass or ceramic.

10. Horological movement piece comprising the material according to one of the preceding claims.

Watch case comprising the material according to one of claims 1 to 9.

A method of depositing a thin film of an alloy comprising titanium and gold on a substrate, comprising the steps of:

adjusting the pressure in the deposition chamber;

bombarding said at least one pure gold target substrate with a second magnetron;

so as to cause the formation of a plasma comprising titanium ions and gold ions in determined stoichiometric proportions;

depositing a thin layer of an alloy of atomic formula Ti _x Au _x , 1-x and x representing atomic fractions, x being between 0.22 and

0.28, on the substrate to be coated.

13. Method according to the preceding claim, further comprising heating the substrate to be coated at a temperature greater than or equal to 350 ° C for the deposition of the crystalline phase alloy.

14. Method according to one of claims 12 to 13, further comprising the adjustment of the distance between the target substrates and the surface of the substrate to be covered between 40 mm and 200 mm, for the deposition of the crystalline phase alloy.

15. Method according to one of claims 12 to 14, wherein the adjustment of the pressure in the deposition chamber consists of placing under pseudo-vacuum at a pressure between 1 .10 ⁴ and 10.10 ⁴ Pa.

The method according to one of claims 12 to 15, wherein the power of each of said magnetrons is independently configured to obtain the deposition of said thin layer of the alloy comprising titanium and gold on the substrate. cover.

17. Method according to one of claims 12 to 16, wherein, a first and a second pure titanium target substrates and a pure gold target substrate being placed in the deposition chamber, three independent magnetrons are implemented. , the first magnetron implementing a power of between 20.3 and 61.2 kW / m ² for bombarding the first pure titanium target substrate connected to a radiofrequency source, the second magnetron using a power of between 0.5 and 20, 4 kW / m ² to bombard the target substrate in pure gold connected to a DC power source and a third magnetron using a power of between 20.3 and 61.2 kW / m ² to bombard the second titanium target substrate pure connected to a source of pulsed current.