EP4347917A1

EP4347917A1 - Deposition head for tubular/non-planar coatings

Info

Publication number: EP4347917A1
Application number: EP22731599.1A
Authority: EP
Inventors: David Munoz Rojas; Fidel TOLDRA REIG
Original assignee: Centre National de la Recherche Scientifique CNRS; Institut Polytechnique de Grenoble
Current assignee: Centre National de la Recherche Scientifique CNRS; Institut Polytechnique de Grenoble
Priority date: 2021-06-02
Filing date: 2022-06-01
Publication date: 2024-04-10
Also published as: WO2022253904A1; FR3123661A1; FR3123661B1

Abstract

The invention relates to a head for the chemical vapor deposition of a tubular substrate, comprising: - a first opening for receiving a first precursor, - a second opening for receiving a second precursor, - a third opening for receiving an inert gaseous stream, - a first network of distribution ducts connecting the first opening to a first group of orifices extending over an internal section of the head, - a second network of distribution ducts connecting the second opening to a second group of orifices extending over at the internal section of the head, - a third network of distribution ducts connecting the third opening to a third group of orifices extending over the internal section of the head, an orifice of the first or second group of orifices being adjacent on either side to an orifice of the third group of orifices, the first, second and third networks of distribution ducts respectively having at least a first, second and third expansion pre-chamber, the tubular substrate performing a back-and-forth relative movement.

Description

DESCRIPTION

Title of the invention: Deposition head for tubular/non-planar coatings.

The invention relates to a vapor phase thin film deposition head, and more particularly to a deposition head adapted to the implementation of the SALD technique - spatial atomic layer deposition (from the English " Spatial Atomic Layer Deposition”). The invention also relates to a thin film deposition system comprising such a head.

Atomic Layer Deposition (ALD) is a chemical vapor deposition (CVD) technique developed in the 1960s. -70 which offers the unique possibility of depositing high quality thin layers at low temperatures, with precise thickness control, exceptional uniformity and excellent coverage even in the presence of steps having a large aspect ratio. This is due to the spontaneously self-limiting nature of growth by ALD, which takes place directly and selectively on the sample surface upon sequential exposure of different precursors carried by inert gas streams (typically N ₂ or Ar). Thus, while in the traditional techniques of chemical vapor deposition the precursors are injected at the same time react on the substrate by thermal or plasma activation, in the case of ALD the precursors are injected by consecutive pulses, separated in the time by purges with inert gas or "vacuum", thus allowing for the surface selective and self-limiting nature of the technique.

[0003] Since the 1990s, ALD has become the technique of choice in the semiconductor and large screen industries. Later, the advent of nanoscience and nanotechnology expanded the use of ALD to research laboratories.

[0004] Despite its unique advantages, ALD has two major drawbacks which have limited its industrial application: the slowness of deposition and the need to operate under vacuum. As a result, ALD is today only used in industries where no other technique is available. [0005] Spatial ALD (SALD) provides a solution to the problem of the slowness of “conventional” ALD. This technique, initially proposed by TS Suntola et al. in US Patent 4,389,973, consists in separating the precursors in space rather than in time. Thus, in SALD, precursors are continuously delivered in correspondence of different portions of the substrate surface, separated by an area of inert gas, while the sample moves from the location of one precursor to the other. passing through the inert gas zone. This allows the deposition rate to be increased by up to two orders of magnitude. Furthermore, it has been demonstrated that by arranging the SALD deposition head in the immediate vicinity (100 μm or less) of the deposition surface and by equipping it with gas suction openings, it is possible to operate at ambient pressure, and therefore outside a vacuum chamber. This is referred to as SALD at ambient pressure (AP-SALD).

[0006] Nevertheless, today space ALD has a limitation since this deposition technique is mainly suitable for application on a flat or partially flat surface, that is to say a flexible surface that can be flattened and for the deposition powder. However, depositing thin layers on substrates of non-planar shape and, more particularly of tubular shape, is very advantageous since tubular substrates have several advantages compared to planar substrates. Indeed, the surface/volume ratio is higher, reflecting a better application of the coating, and these types of substrates can easily be used in a modular configuration, favoring the industrial applicability of the latter. However, the deposition of thin layers on tubular substrates by the traditional techniques, namely traditional ALD and space ALD, of thin layer deposition is complex and expensive. Also, using a spatial SALD or ADL design adapted to the tubular design would allow the advantages of this type of technology to be used for these types of non-planar substrates. However, today, no technology based on spatial ALD is suitable for coating tubes.

[0007] In the case of sputtering and pulsed laser deposition, a special configuration must be added to the system to ensure total deposition of the surface. This involves a rotating element and a heating source that keeps the temperature of the substrate constant to be embedded. In addition, these techniques involve the use of "vacuum" for deposition. In the case of ALD, if a tube is used, steps additional steps must be taken because the entire chamber is exposed to the precursors. The tubes must then be sealed to prevent deposition on the outside and inside.

[0008] Conversely, other techniques make it possible to replace ALD and space ALD for tubular substrates. Techniques such as dip coating, spray coating or electrodeposition offer a less expensive procedure for depositing macroscale films on tubes, but they require post-thermal treatments for sintering the films and films are not completely homogeneous, consistent and dense. Finally, these technologies are limited in terms of the minimum achievable thickness of the coating. Moreover, as stated previously, these techniques are only applicable for the deposition of films at the macroscopic scale on tubes.

[0009] The invention aims to overcome all or part of the problems mentioned above by proposing a new deposition head for tubular and non-planar coatings which can be used for deposition in the processes of vapor deposition (CVD) and ALD atomic layer deposition including spatial ALD. This deposition head has the particular advantage of being able to operate in the open air and without requiring a vacuum around the substrate. The invention makes it possible to deposit conformal thin layers on tubular substrates with perfect control of thickness and homogeneity. The invention thus proposes a simple and inexpensive device providing high quality films to meet industrial requirements.

[0010] To this end, the subject of the invention is a head for the chemical deposition of a tubular substrate in the vapor phase comprising: a first opening for receiving a first gaseous flow at the inlet carrying a first precursor, a second opening for receiving a second inlet gas stream carrying a second precursor, a third opening for receiving a third inert inlet gas stream, a first network of distribution ducts connecting the first opening of the first gas stream to a first group of orifices extending over a internal section of the deposition head, a second network of distribution ducts connecting the second opening of the second gas stream to a second group of orifices extending over the internal section of the deposition head, a third network of distribution ducts connecting the third opening of the third gas stream inert to a third group of orifices extending over the internal section of the deposition head, an orifice of the first or of the second group of orifices being adjacent on either side to an orifice of the third group of orifices according to an axis of revolution R of the deposition head, the first, second and third networks of distribution ducts having respectively at least a first, second and third expansion prechamber included in the deposition head, the tubular substrate performing a relative movement of back and forth along the axis of revolution R of the deposition head.

According to one aspect of the invention, the at least one first, second and third expansion prechamber extend successively in a direction of the axis of revolution R of the deposition head.

According to one aspect of the invention, the at least one first expansion prechamber of the first network of distribution ducts is connected to the first group of orifices via a first channel, the internal volume of the first channel being less than the volume of the at least one first expansion prechamber of the first network of distribution ducts, the at least one second expansion prechamber of the second network of distribution ducts is connected to the second group of orifices by the intermediate a second channel, the internal volume of the second channel being less than the volume of the at least one second expansion prechamber of the second network of distribution ducts, in which the at least one expansion prechamber of the third network of ducts distribution is connected to the third group of orifices via a third channel, the internal volume of the third channel being less than the volume of the at least one third expansion prechamber of the third network of distribution ducts.

[0013] According to one aspect of the invention, the first, second and third distribution ducts do not intersect with each other.

According to one aspect of the invention, the deposition head comprises a fourth distribution duct connected to a fourth group of orifices extending over the section internal of the deposition head, the fourth duct allowing the evacuation of the third inert gas flow towards a fourth evacuation opening of the deposition head.

According to one aspect of the invention, the orifices of the first, second and third groups of orifices are rectilinear slots parallel to each other.

According to one aspect of the invention, a deposition distance between the orifices of the first, second and third groups of orifices and the tubular substrate, inserted into the deposition head, is less than two hundred micrometers.

According to one aspect of the invention, a deposition distance between the orifices of the first, second and third groups of orifices and the tubular substrate, inserted in the deposition head, is greater than fifty micrometers.

According to one aspect of the invention, the deposition head comprises a first flux receiving face comprising the first, second and third openings and a second flux receiving face comprising a first, second and third secondary openings flow, respective mirrors of the first, second and third opening of the first receiving face along a plane P perpendicularly crossing the axis of revolution R of the deposition head.

According to one aspect of the invention, the first gas stream is an oxidizing precursor.

[0020] According to one aspect of the invention, the first gas stream is a metal precursor.

The invention also relates to a system for the chemical deposition of a tubular substrate in the vapor phase comprising at least two deposition heads.

The invention also relates to a computer program product comprising computer-executable instructions which, when executed by a processor, cause the processor to control an additive manufacturing apparatus to manufacture the deposition head.

The invention also relates to a method for manufacturing the deposition head by additive manufacturing, the method comprising the following steps: obtaining an electronic file representing a geometry of a product in which the product is the deposition head and controlling an additive manufacturing apparatus to manufacture, on one or more additive manufacturing steps, the product according to the geometry specified in the electronic file.

The invention will be better understood and other advantages will appear on reading the detailed description of an embodiment given by way of example, description illustrated by the attached drawing in which:

[0025] [Fig.1] Figure 1 shows a schematic view of a deposition head according to the invention;

[0026] [Fig.2] Figure 2 shows a schematic sectional view of the deposition head according to the invention;

[0027] [Fig.3] Figure 3 shows a schematic side view of the deposition head according to the invention;

[0028] [Fig.4] Figure 4 shows a schematic view of the deposition head according to a variant of the invention;

[0029] [Fig.5] Figure 5 shows a method of manufacturing the deposition head according to the invention.

[0030] For the sake of clarity, the same elements will bear the same references in the various figures.

[0031] Figure 1 shows a schematic view of a chemical deposition head 1 capable of depositing, in the vapor phase, a coating layer on a tubular substrate 2 according to the invention. The deposition head 1 takes the form of a cylinder of radius R1 extending along an axis of revolution R and one section of which is between an internal surface 15 (as shown in FIG. 2) and an external surface 13 (as shown in FIG. 4) allowing the insertion of the tubular substrate 2. The deposition head 1 comprises: a first opening 10 to receive a first gas flow at the inlet transporting a first precursor, preferably a gas charged with a first precursor, for example a precursor oxidant such as water vapor (H ₂ 0), a second opening 12 for receiving a second gaseous flow at the inlet carrying a second precursor, preferably a gas charged with a second precursor, for example a metallic precursor or an organometallic compound such as AI(CH ₃ ) ₃ , a third opening 14 to receive a third inert gas flow or an inert gas as input, such as nitrogen N ₂ or argon Ar.

The deposition head 1 may also include a fourth opening 18 for discharging a fourth gas flow. More precisely, the fourth opening 18 allows the evacuation of the inert gas introduced into the third opening 14.

The first 10, second 12, third 14 and fourth 18 openings are included on a first reception face 16, of circular shape. In a preferred configuration, the first receiving face 16 is perpendicular to the axis of revolution R. The first opening 10, the second opening 12 and the third opening 14 each respectively precede a first entry volume 101, a second volume input volume 121 and a third input volume 141. The first input volume 101, the second input volume 121 and the third input volume 141 take the form of a hollow cylinder starting against the first face of reception 16 respectively at the level of the first opening 10, the second opening 12 and the third opening 14 and extending parallel to the axis of revolution R.

[0034] In addition, the deposition head 1 can include a fifth or a sixth opening (not shown) in the case of deposition of more complex materials with different metals, so that different precursors can be injected.

In addition, the deposition head 1 comprises an insertion hole 20 of the tubular substrate 2 positioned in the center of the first receiving face 16 and coincides with the axis of revolution R. This insertion hole 20 is therefore continues in the deposition head 1 so as to take the form of an "empty cylinder" allowing the complete insertion of the tubular substrate 2. For information, the insertion orifice 20 takes a shape similar to the tubular substrate 2 Thus, for a tubular substrate 2 of cylindrical shape, the insertion orifice 20 can have a circular shape so as to obtain the hollow cylinder mentioned above. Nevertheless, it may be envisaged to have an insertion orifice 20 of octagonal or oval shape in order to have a complementary shape with a tubular substrate 2 of potentially octagonal or oval shape.

The deposition head comprises, as shown in Figure 2, also a first network of distribution ducts 100 connecting the first opening 10 of the first gas stream to a first group of orifices 102, a second network of distribution ducts 120 connecting the second opening 12 of the second gas stream to a second group of orifices 122 and a third network of distribution ducts 140 connecting the third opening 14 of the third inert gas stream to a third group of orifices 142. Each orifice of the first 102, second 122 and third 142 groups of orifices extends over an internal section 15 of the deposition head 1 and is aligned along the axis of revolution R. As an indication, the first inlet volume 101, the second input volume 121 and the third input volume 141 are respectively included in the first network of ducts 100 for distribution, the second network of ducts 120 for distribution and the third network of ducts 140 for distribution. The first 100, second 120 and third 140 distribution ducts do not intersect with each other.

In addition, an orifice of the first 102 or of the second 122 group of orifices is only adjacent, on either side along the axis of revolution R, to an orifice of the third group 142 of orifices. Thus, each orifice of the first group 102 of orifices is adjacent along the axis of revolution R to two orifices, on either side, of the third group 142 of orifices. And similarly, each orifice of the second group 122 of orifices is adjacent along the axis of revolution R to two orifices, on either side, of the third group 142 of orifices.

Indeed, this arrangement of the orifices makes it possible to ensure the separation between the first precursor and the second precursor by the action of the inert gas. Thus, when the first precursor is affixed against the tubular substrate 2 via the first group of orifices 102, the first precursor is limited on each side by the inert gas, which becomes a spatial limiter, itself affixed against the tubular substrate 2 through the third group of orifices 142. And, similarly, when the second precursor is affixed against the tubular substrate 2 through the second group of orifices 122, the second precursor is limited by each side by the inert gas itself affixed against the tubular substrate 2 via the third group of orifices 142. Thus, the first precursor and the second precursor are never brought into contact when the latter are affixed to the substrate tubular 2.

The first 100, second 120 and third 140 distribution duct networks respectively have at least a first 104, second 124 and third 144 expansion prechamber included in the deposition head 1. The first expansion prechamber 104, the second expansion prechamber 124 and the third expansion prechamber 144 take the form of a hollow ring arranged inside the deposition head 1 and having a radius R2 smaller than the radius R1 of the hollow cylinder formed by the deposition head 1. Thus, the at least one first expansion prechamber 104 is directly connected to the first opening 10 via the first inlet volume 101 so as to be able to expand the first precursor which has previously been introduced through the first opening 10 and which has passed through the first inlet volume 101. Similarly, at least one second expansion prechamber 124 is directly connected to the second opening 12 via the second inlet volume 121 of so as to be able to expand the second precursor which has previously been introduced through the second opening 12 and which has passed through the second inlet volume 121 and the at least one third expansion prechamber 144 is directly connected to the third opening 14 via the second inlet volume 141 so as to be able to expand the inert gas which has previously been introduced through the third opening 14 and which has passed through the third inlet volume 121.

As an indication, the at least one first expansion prechamber 104, the at least one second expansion prechamber 124 and third expansion prechamber 144 extend successively in the direction of the axis of revolution R of the deposition head 1 and thus form a succession of hollow rings of the same radius R2 along the axis of revolution R.

In addition, the at least one first expansion prechamber 104 of the first network of distribution ducts 100 is connected to the first group of orifices 102 via at least one first channel 106. Similarly, the at least one second expansion prechamber 124 of the second network of distribution ducts 120 is connected to the second group of orifices 122 via at least one second channel 126 and the at least one third expansion prechamber 144 of the third network of distribution ducts 140 is connected to the third group of orifices 142 via at least one third channel 146.

The concentric prechambers, namely the first expansion prechamber 104, the second expansion prechamber 124 and the third expansion prechamber 144, are necessary to ensure good homogenization of the pressure of the gas and its correct distribution in each channel, namely the first channel 106, the second channel 126 and the third channel 146.

In addition, it may be envisaged to determine adequate ratios between the volumes of the first expansion prechambers 104, second expansion prechambers 124 and third expansion prechambers 144 and the output volumes of the first channels 106, second channels 126 and third 146 channels to provide optimum gas pressure distributions.

To this end, the internal volume of the at least one first channel 106 is less than the volume of the at least one first expansion prechamber 104 of the first network of distribution ducts 100, the internal volume of the at least one at least one second channel 126 is less than the volume of the at least one second expansion prechamber 124 of the second network of distribution ducts 120, and the internal volume of the at least one third channel 146 is less than the volume of the at least one least a third expansion prechamber 144 of the third network of ducts 140 for distribution. It is then possible, for a person skilled in the art, to be able to define a first ratio between the volume of the at least one first channel 106 and the volume of the at least one first expansion prechamber 104, a second ratio between the volume of the at least one second channel 126 and the volume of the at least one second expansion prechamber 124 and a third ratio between the volume of the at least one third channel 146 and the at least one third expansion prechamber 144 The first, second and third ratios can thus be identical or different depending on the configuration of the deposition head 1 , knowing that an equality between the first and the second ratio does not mean an equality of the volumes of the first 106 and second 126 channels and first 104 and second 124 expansion prechamber.

[0045] In addition, for a constant flow rate applied in the first expansion prechambers 104, second expansion prechambers 124 and third expansion prechambers 144. Experience reveals that a small prechamber volume produces a very inhomogeneous gas distribution along the first channels 106, second channels 126 and third channels 146 and particularly at the level of the first groups of orifices 102, second groups of orifices 122 and third groups of orifices 142. By way of indication, it may be envisaged to have a constant flow in the first expansion prechambers 104, second expansion prechambers 124 and third expansion prechambers 144 of approximately 100 mL/min.

However, the calculations also show that the homogeneity of the gas flow distribution can be considerably improved by increasing the volume of the first expansion prechambers 104, second expansion prechambers 124 and third expansion prechambers 144 and that a very good homogeneity can be obtained for the large volumes of first expansion prechambers 104, second expansion prechambers 124 and third expansion prechambers 144 with, by way of indicative example, radii of 1.4 and 2 mm. Consequently a volume ratio or ratio between the volume of the first expansion prechambers 104, second expansion prechambers 124 and third expansion prechambers 144 and volume of the first channels 106, second channels 126 and third channels 146 of at least 0.7 must be respected.

As an indication, in order to have a homogeneous distribution of the pressure in the first 100, second 120 and third 140 distribution ducts, the first, second and third ratio must be greater than or equal to 0.71 and can be comprised, in a preferred configuration, between 1.36 and 41.89. In this way, a homogeneous distribution of the pressure makes it possible to ensure a homogeneous distribution of the first and second precursors and of the inert gas in the first 100, second 120 and third 140 distribution ducts so that all the first 106, second 126 and third 146 canals are all irrigated. Nevertheless, the dimensions of this configuration are indicative. Indeed, this distribution is also a function of the number of ducts and the size of the deposition head 1

The first group of orifices 102, the second group of orifices 122 and the third group of orifices 142 can take the form of rectilinear slots parallel to each other. The first group of orifices 102, the second group of orifices 122 and the third group of orifices 142 thus face the tubular substrate 2 when the tubular substrate 2 is inserted into the insertion orifice 20 of the deposition head 1. In this way, the first precursor can be affixed, via the first group of orifices 102, against the tubular substrate 2. Just like the second precursor, which can be affixed against the tubular substrate 2 via of the second group of orifices 122 and inert gas which can be affixed against the tubular substrate 2 via the third group of orifices 142.

Furthermore, in order to optimize the coating of the tubular substrate 2 by the first and/or the second precursor, limited by the inert gas, the orifices of the first 102, second 122 and third 142 groups of orifices and the substrate tube 2, inserted in the deposition head 1, are separated by a deposition distance less than two hundred micrometers and greater than fifty micrometers in order to allow the first and/or second precursor to be affixed. Furthermore, this deposition distance is also a function of the flow rate of precursor or of inert gas, of the dimensioning of the tubular substrate 2 or else of the deposition technique such as for example in CVD or in ALD. Depending on the desired configuration, the deposition head 1 can be adapted. Thus, the deposition distance of the precursors and of the inert gas and the dimensioning of the first 100, second 120 and third 140 distribution ducts are adjusted to control the type of deposition desired on the tubular substrate 2, namely to make ALD deposition or CVD deposit.

The deposition head 1 also comprises a fourth distribution duct 180 connected to the fourth discharge opening 18. More specifically, the fourth distribution duct 180 is formed of at least a fourth channel 186 allowing the excess gas inert material located at the level of the tubular substrate 2 to be evacuated via a fourth group of orifices 182 connected to the at least one fourth channel 186 and extending over the internal section 15 of the deposition head 1. At the other end of the at least a fourth channel 186 is a tank 184 for venting the inert gas which is itself connected to the fourth opening 18 for venting the inert gas. Like an expansion prechamber, the reservoir 184 comprises a hollow volume capable of containing the excess inert gas before it is discharged through the fourth discharge opening 18 as shown in FIG. 3. In general, an orifice of the fourth group of orifices 182 is placed between a orifice of the first 102 or the second 122 group of orifices and a orifice 142 of the third group of orifices. In this way, there is always an evacuation of the excess inert gas and/or precursors.

[0051] In addition, the tubular substrate 2, installed in the deposition head 1 via the insertion orifice 20, must perform a relative movement back and forth along the axis of revolution. R of the deposition head relative to the head of deposit 1. This back and forth movement results in a transverse oscillation along the axis of revolution R and more precisely, and successively, a first translation T1 in a direction of the axis of revolution R and of a second translation T2 in a direction opposite to the direction of the axis of revolution R. Indeed, this back and forth movement relative to the deposition head 1 is necessary in order to allow optimal covering of the tubular substrate 2 inserted into the deposition head 1 by the first and the second precursor separated by the inert gas. Thus, the tubular substrate 2 can undergo this "back and forth" movement while the deposition head 1 is fixed or else, according to another covering configuration, the deposition head 1 can undergo this "back and forth" movement. back and forth” in order to cover the tubular substrate 2 which is then fixed. It can also be envisaged that the deposition head 1 and the tubular substrate 2 undergo this “to and fro” movement out of phase. In a certain case of covering, a single "back and forth" movement may be necessary to deposit the coating on the tubular substrate 2 as for example in the case of adding a thin coating against the tubular substrate 2.

According to a configuration of the deposition head 1, the deposition head 1 comprises the first receiving face 16 of flow comprising the first 10, second 12, third 14 and fourth 18 openings and a second receiving face 160 flow of identical shape to the first receiving face 16, perpendicular to the axis of revolution R and parallel to the first receiving face 16. The second receiving face 160 can comprise, like the first reception face 16, a first secondary opening, a second secondary opening and third secondary opening of the flow, respective mirrors of the first 10, second 12 and third 14 openings of the first reception face 16 according to a plane P crossing perpendicularly the axis of revolution R of deposition head 1.

Thus, the first secondary opening allows the introduction of the first precursor, the second secondary opening allows the introduction of the second precursor and the third secondary opening allows the introduction of the inert gas. This configuration thus makes it possible to limit the pressure necessary to introduce the various flows into the deposition head since each flow is introduced according to the two ends, namely the first reception face 16 and the second reception face 160, of the head deposit 1 and no longer just one end. According to another configuration of the deposition head 1 shown in Figure 4, requiring a coating of an internal part 40 of a hollow tubular substrate 4, it can be envisaged that the deposition head 1 is inserted into the substrate hollow tubular 4. In this case, the orifices of the first group of orifices 102, of the second group of orifices 122 and of the third group of orifices 142 are positioned on an external face 13, extending over the section of the cylinder represented by the deposition head 1, so as to always face the hollow tubular substrate 4 when the deposition head 1 is inserted therein. Therefore, the back and forth movement necessary for depositing the first and the second precursor being relative between the deposition head 1 and the hollow tubular substrate 4, the person skilled in the art can choose between carrying out a back and forth movement -comes on the hollow tubular substrate 4 by keeping the deposition head 1 stationary or on the deposition head 1 by keeping the hollow tubular substrate 4 stationary.

The deposition head 1 according to the invention therefore comprises a surface, namely the internal surface 15 or the external surface 13, configured to allow the deposition of the first gas stream, the second gas stream and the third inert gas stream against the tubular substrate 2. The inner surface 13 and the outer surface 15 both have a cylindrical shape or similar to the associated tubular substrate. Thus, it can be envisaged, as indicated previously, to use a tubular substrate 2 octagonal or oval.

Thus, when the deposition takes place via the internal surface 15 against the tubular substrate 2, via the orifices of the first group of orifices 102, of the second group of orifices 122 and of the third group of orifices 142 positioned on the internal surface 15, the tubular substrate 2 is inserted into the deposition head 1 via the entry orifice 20.

And, when the deposition takes place via the external surface 13 against the tubular substrate 2, via the orifices of the first group of orifices 102, of the second group of orifices 122 and of the third group of orifices 142 positioned on the external surface 13, it is the deposition head 1 which is inserted into the tubular substrate 2, which is advantageously hollow.

In addition, the deposition head 1 according to the invention also has the advantage of being able to be stacked with another deposition head 1 along the axis of revolution R in such a way to form a chemical deposition system for a tubular substrate 2 in the vapor phase comprising at least two deposition heads 1. Thus, it can be envisaged to align along the axis of revolution R and to stack several deposition heads 1 in order to adjust the chemical vapor deposition system to tubular substrates 2 having different lengths.

Thus, for a hollow tubular substrate 4, it may be envisaged to introduce a deposition head 1 into the internal part 40 and to use another deposition head 1 allowing, as shown in FIG. hollow tubular substrate 4 is introduced in order to perform a covering along two faces, namely an internal face in the internal part 40 and an external face of the hollow tubular substrate 4.

[0060] In addition, the deposition head 1, according to the invention, can be made in one piece by additive manufacturing. The use of additive manufacturing allows in particular greater freedom in the shape of the distribution ducts, namely the first and second precursors and the inert gas, and of the evacuation of the flows, which are simple hollows made in the deposition head. 1. It also makes it possible to avoid assembly and welding tasks, which are time-consuming and sources of defects, and to obtain further miniaturization of the deposition head 1.

An object of the invention is also a manufacturing process 500 of the deposition head 1 by additive manufacturing represented in FIG. 5. The manufacturing process 500 comprises the following steps: obtaining (step 501) an electronic file representing a geometry of a product in which the product is the deposition head, controlling (step 502) an additive manufacturing apparatus to manufacture, on one or more additive manufacturing steps, the product according to the geometry specified in the electronic file.

Thus, as stated previously, depending on the desired configuration, that is to say ALD or CVD operation, the deposition head 1 can be adapted via additive manufacturing of the product.

[0063] Examples according to the disclosure can be formed using an additive manufacturing process. A common example of additive manufacturing is 3D printing. However, other additive manufacturing methods are available. Rapid prototyping or rapid manufacturing are also terms that can be used to describe additive manufacturing processes. As used herein, "additive manufacturing" generally refers to manufacturing processes in which successive layers of material(s) are laid on top of each other to "build" layer by layer or "additively manufacture", a three-dimensional component. This is compared to some subtractive manufacturing processes (such as milling or drilling), in which material is successively removed to make the part. Successive layers usually fuse together to form a monolithic component which may have a variety of sub-components integrated. In particular, the manufacturing process may allow an example of the disclosure to be integrally formed and include a variety of features that are not possible when using prior manufacturing processes. The additive manufacturing processes described herein allow manufacturing to any suitable size and shape with various features that may not have been possible using prior manufacturing processes. Additive manufacturing can create complex geometries without using any type of tools, molds or fixtures, and with little or no waste. Instead of machining components from solid billets of plastic or metal, much of which is cut out and discarded, the only material used in additive manufacturing is what is needed to shape the part, namely the head of deposit 1.

Suitable additive manufacturing techniques according to the present disclosure include, for example, Fused Deposition Modeling (FDM), Selective Laser Sintering (SLS), 3D printing such as by inkjet and laserjet, stereolithography (Sterolithography or SLA), direct selective laser sintering (Sterolithography or DSLS), electron beam sintering (Electron Beam Sintering or EBS), electron beam sintering (Electron Beam Sintering or EBM), laser net shaping (Laser Engineered Net Shaping or LENS), electron beam additive manufacturing (Electron Beam Additive Manufacturing or EBAM), laser net shape manufacturing (Laser Net Shape Manufacturing or LNSM ), direct metal deposition (Direct Metal Deposition or DMD), digital light processing (DLP), continuous digital light processing (Continuous Digital Light Processing or CDLP), direct selective laser fusion (Direct Selective Laser Melting or DSLM), selective laser melting (Selective Laser Melting or SLM), direct metal laser melting (Direct Metal Laser Melting or DMLM), direct metal laser sintering (Direct Metal Laser Sintering or DMLS), material jetting (Material Jetting or MJ), projection of nanoparticles (NanoParticle Jetting or NPJ), deposition on demand (Drop On Demand or DOD), jetting of binder (Binder Jetting or BJ), Multi Jet Fusion (MJF), manufacture of laminated objects (Laminated Object Manufacturing or LOM) and other known processes. The additive manufacturing processes described here can be used to form components using any suitable material. For example, the material can be plastic, composite, polymer, epoxy, photopolymer resin, metal or any other suitable material which can be in solid, liquid, powder, sheet, wire or any other suitable form or combinations thereof. More specifically, according to exemplary embodiments herein, the additively fabricated components described herein may be formed in part, in whole, or in some combination of materials. These materials are examples of materials suitable for use in additive manufacturing processes that may be suitable for the manufacture of the examples described herein.

As noted above, the additive manufacturing process described here allows a single component to be formed from multiple materials. Thus, the examples described herein can be formed from any suitable mixture of the above materials. For example, a component may include multiple layers, segments, or parts that are formed using different materials, processes, and/or on different additive manufacturing machines. In this way, components can be constructed that have different materials and material properties to meet the requirements of any particular application. Additionally, although the components described herein are constructed entirely by additive manufacturing processes, it should be appreciated that in alternate embodiments, some or all of these components may be formed by casting, machining and/or any other process. of appropriate manufacture. Indeed, any suitable combination of materials and manufacturing processes can be used to form these components. Additive manufacturing processes typically manufacture components based on three-dimensional (3D) information, such as a three-dimensional computer model (or design file), making up. Accordingly, the examples described herein include not only products or components as described herein, but also methods of manufacturing such products or components via additive manufacturing and computer software, firmware or hardware for controlling the manufacture of such products via additive manufacturing.

[0066] The structure of the product, namely of the deposition head 1, can be represented digitally in the form of a design file. A design file, or computer-aided design (CAD) file, is a configuration file that encodes one or more surface or volumetric configurations of the product shape. Simply put, a design file represents the geometric layout or shape of the product. Design files can take any file format now known or later developed. For example, design files can be in Stereolithography or “Standard Tessellation Language” (.stl) format which was created for 3D Systems CAD stereolithography programs, or in Additive Manufacturing File (.amf) format, which is a American Society of Mechanical Engineers Standard (ASME) which is an Extensible Markup Language (XML) based format designed to allow any CAD software to describe the shape and composition of any three-dimensional object to be manufactured on any additive manufacturing printer. Other examples of design file formats include AutoCAD files (.dwg), Blender files (.blend), Parasolid files (.x_t), 3D Manufacturing Format files (.3mf), Autodesk files (3ds ), Collada files (.dae), and Wavefront files (.obj), although many other file formats exist. Design files can be produced using modeling software (e.g. CAD modeling) and/or by scanning the surface of a product to measure the surface configuration of the product.

[0067] Once obtained, a design file can be converted into a set of computer-executable instructions which, when executed by a processor, cause the processor to control an additive manufacturing apparatus to produce the deposition head 1 according to the geometric layout specified in the design file. The conversion can convert the design file into slices or layers that need to be formed sequentially by the additive manufacturing device. Instructions (also known as geometric code or “G-code”) can be calibrated to the specific additive manufacturing device and can specify the precise location and amount of material to be formed at each stage of the manufacturing process. As discussed above, forming can be by deposition, sintering, or any other form of additive manufacturing process. Code or instructions can be translated between different formats, converted into a set of data signals and transmitted, received as a set of data signals and converted into code, stored, etc., if necessary. Instructions can be an input to the additive manufacturing system and can come from a part designer, intellectual property (IP) provider, design company, operator or owner of the manufacturing system additive, or other sources. An additive manufacturing system can execute instructions to manufacture the product using any of the technologies or processes described herein. Design files or computer-executable instructions may be stored in any computer-readable storage medium (transient or not) (e.g., memory, storage system, etc.) storing code, or computer-readable instructions, representative of the product to be manufactured. As noted, the computer readable code or instructions defining the product which can be used to physically generate the deposition head 1, upon execution of the code or instructions by an additive manufacturing system. For example, the instructions can include a precisely defined 3D model of the product and can be generated from one of many well-known computer-aided design (CAD) software systems such as AutoCAD®, TurboCAD®, DesignCAD 3D Max, etc. Alternatively, a model or prototype of the component can be scanned to determine the component's three-dimensional information.

Another object of the invention is a computer program product, the computer program comprising computer-executable instructions which, when executed by a processor, cause the processor to control an additive manufacturing apparatus to make the deposition head 1.

[0069] Accordingly, by controlling an additive manufacturing apparatus according to the computer-executable instructions, the additive manufacturing apparatus can be instructed to print one or more parts of the deposition head 1. These can be printed as assembled or unassembled form. Preferably, the deposition head 1 is printed in assembled form or in a single piece. For example, different sections of the product can be printed separately (as a kit of unassembled parts) and then assembled. Alternatively, and preferably, the different parts can be printed in assembled form. In light of the foregoing, embodiments include additive manufacturing manufacturing methods. This includes the steps of obtaining a design file representing the product and instructing an additive manufacturing device to manufacture the product in an assembled or unassembled form according to the design file. The additive manufacturing apparatus may include a processor that is configured to automatically convert the design file into computer-executable instructions for controlling manufacturing of the product. In these embodiments, the design file itself may automatically cause the product to be produced once entered into the additive manufacturing device. Accordingly, in this embodiment, the design file itself can be viewed as computer-executable instructions that cause the additive manufacturing apparatus to manufacture the product. Alternatively, the design file may be converted into instructions by an external computer system, with the resulting computer executable instructions being provided to the additive manufacturing device. In view of the foregoing, the design and manufacture of subject implementations and the operations described in this specification may be performed using digital electronic circuits, or in computer software, firmware, or hardware, including structures described in this specification and their structural equivalents, or combinations of one or more of them. For example, the hardware may include processors, microprocessors, electronic circuits, electronic components, integrated circuits, etc. Implementations of the subject matter described in this specification may be made using one or more computer programs, i.e., one or more modules of computer program instructions, coded onto a computer storage medium for execution by or to control the operation of a data processing device. Alternatively or additionally, the program instructions may be encoded onto an artificially generated propagated signal, for example, a machine-generated electrical, optical or electromagnetic signal to encode information for transmission to a suitable receiving apparatus for execution by a data processing device. A computer storage medium may be, or be included in, a computer-readable storage device, a computer-readable storage substrate, an array or random or serial access memory device, or a combination of one or more of them. Additionally, while a computer storage medium is not a propagated signal, a computer storage medium may be a source or destination of computer program instructions encoded in an artificially generated propagated signal. The computer storage medium may also be, or be included in, one or more separate physical components or media (eg, multiple CDs, discs or other storage devices). Although additive manufacturing technology is described here as enabling the manufacture of complex objects by building objects point by point, layer by layer, typically in a vertical direction, other manufacturing processes are possible and within the scope of this topic. For example, although the description herein refers to the addition of material to form successive layers, those skilled in the art will appreciate that the methods and structures described herein can be practiced with any additive manufacturing technique or other manufacturing technology. Mention may also be made of injection molding or manufacture by casting low-pressure elastomer.

Claims

1. Chemical deposition head (1) of a tubular substrate (2) in the vapor phase comprising: a first opening (10) for receiving a first gaseous flow at the inlet carrying a first precursor, a second opening (12) for receiving a second inlet gas stream carrying a second precursor, a third opening (14) for receiving a third inert inlet gas stream, a surface (13, 15) configured to allow deposition of the first gas stream, the second gas stream and the third inert gas flow against the tubular substrate (2), the surface (13, 15) having a cylindrical shape so as to allow the insertion of the tubular substrate (2) in the deposition head (1) or of the deposition head ( 1) in the tubular substrate (2), a first network of distribution ducts (100) connecting the first opening (10) of the first gas flow to a first group of orifices (102) extending over the surface (13, 15) of the deposition head (1), a second network of ducts distribution (120) connecting the second opening (12) of the second gas stream to a second group of orifices (122) extending over the surface (13, 15) of the deposition head (1), a third network of distribution ducts (140) connecting the third opening (14) of the third inert gas flow to a third group of orifices (142) extending on the surface (13, 15) of the deposition head (1), an orifice of the first or second group of orifices (102; 122) being adjacent on either side to an orifice of the third group of orifices (142) along an axis of revolution R of the deposition head (1), the first, second and third networks of ducts (100, 120 , 140) distribution having respectively at least a first, second and third expansion prechamber (104, 124, 144) included in the deposition head (1), the tubular substrate (2) performing a relative movement back and forth comes along the axis of revolution R of the deposition head (1).

2. deposition head (1) according to claim 1, wherein the at least one first, second and third expansion prechamber (104, 124, 144) extend successively in a direction of the axis of revolution R of the deposition head (1).

3. deposition head (1) according to claim 1, wherein the at least one first expansion prechamber (104) of the first network of distribution ducts (100) is connected to the first group of orifices (102) by the intermediary of a first channel (106), the internal volume of the first channel (106) being less than the volume of the at least one first expansion prechamber (104) of the first network of distribution ducts (100), in which the at least one second expansion prechamber (124) of the second network of distribution ducts (120) is connected to the second group of orifices (122) via a second channel (126), the internal volume of the second channel (126) being less than the volume of the at least one second expansion prechamber (124) of the second network of distribution ducts (120), in which the at least one expansion prechamber (144) of the third network of distribution ducts (140 ) is connected to the third group of orifices (142) via a third channel (146), the internal volume of the third channel (146) being smaller than the volume of the at least one third expansion prechamber (144 ) of the third network of distribution ducts (140).

4. Deposition head (1) according to one of claims 1 to 3, wherein the first, second and third distribution ducts (100, 120, 140) are not intersecting with each other.

5. Deposition head (1) according to one of claims 1 to 4, comprising a fourth conduit (180) for distribution connected to a fourth group of orifices (182) extending over the internal section (15) of the deposition head (1), the fourth duct (180) allowing the evacuation of the third inert gas flow towards a fourth evacuation opening (18) of the deposition head (1).

6. Deposition head (1) according to one of claims 1 to 5, wherein the orifices of the first, second and third groups of orifices (102, 122, 142) are rectilinear slots parallel to each other.

7. Deposition head (1) according to one of the preceding claims, in which a deposition distance between the orifices of the first, second and third groups of orifices (102, 122, 142) and the tubular substrate (2), inserted into the deposition head (1), is less than two hundred micrometers.

8. Deposition head (1) according to one of the preceding claims, in which a deposition distance between the orifices of the first, second and third groups of orifices (102, 122, 142) and the tubular substrate (2), inserted into the deposition head (1), is greater than fifty micrometers.

9. deposition head (1) according to one of the preceding claims, comprising a first reception face (16) of flux comprising the first, second and third openings (10, 12, 14) and a second reception face (160) of the flow comprising a first, second and third secondary openings of the flow, respective mirrors of the first, second and third opening (10, 12, 14) of the first reception face (16) according to a plane P crossing perpendicularly the axis of revolution R of the deposition head (1).

10. Deposition head (1) according to one of the preceding claims, in which the first gas stream is an oxidizing precursor.

11. deposition head (1) according to one of the preceding claims, wherein the second gas stream is a metal precursor.

12. System for chemical deposition of a tubular substrate (2) in the vapor phase comprising at least two deposition heads (1) according to one of the preceding claims.

13. A computer program product, said computer program comprising computer-executable instructions which, when executed by a processor, cause the processor to control an additive manufacturing apparatus to manufacture the deposition head according to one any of claims 1 to 11.

14. Method for manufacturing the deposition head according to any one of claims 1 to 11 by additive manufacturing, the method comprising the following steps: obtaining (step 501) an electronic file representing a geometry of a product in which the product is the deposition head and command (step 502) an additive manufacturing device to manufacture, over one or more additive manufacturing steps, the product according to the geometry specified in the electronic file.