Method and apparatus for sequential plasma treatment

Abstract: The apparatus for plasma treatment of a non-conductive hollow substrate (1), comprises a plurality of ionisation energy sources (7-10) disposed adjacent to each other all along the part of the substrate to be treated. The apparatus further comprises a processing means (11) for sequentially powering the plurality of ionisation energy sources from a radio frequency power source (6). Each ionisation energy source (7) is comprised of two parts (7a, 7b) sandwiching the substrate. The ionisation energy sources can be capacitively or inductively coupled plasma sources.

Description: FIELD OF THE INVENTION The present invention relates to a method and an apparatus for substrate treatments using plasma. such as, for example, polymer treatment for biomedical devices or food and pharmaceutical packaging devices. In particular, the present invention relates to plasma treatment or deposition in non conductive hollow substrates having large aspect ratio such as small diameter tubes, flat boxes... BACKGROUND OF THE INVENTION Hollow substrates with a large aspect ratio are commonly used in various technological fields such as catheters or endoscopes for medical materials and packaging for food or pharmaceutical applications. The expression "large aspect ratio" means that the hollow substrate has at least one dimension that is much larger than another one, and more particularly that the length of the substrate is much larger than a dimension of the substrate aperture. Figure 4 shows two examples of hollow substrates which have a large aspect ratio L/a, where L is the length of the substrate and a is the smallest dimension of the substrate aperture. A tube 1 comprises an inner cavity having a large length L with respect to the diameter a of the tube. Large aspect ratio substrates may also have a form of a flat box 101 which exhibits a little aperture height a in comparison with its length L. A general difficulty of the use of plasma treatment is the complexity to treat internal walls of such substrates. Indeed, plasma treatment of this kind of substrate is difficult to perform since the plasma creation into large aspect ratio hollow substrates generally presents a lack of plasma uniformity and thus of treatment. A uniform treatment is ensured only if, for the whole substrate length, the gas precursor concentration, the local plasma density and the pressure are rigorously constant. The creation of the plasma inside the substrate is carried out by applying electrical energy to the process gas. The electrons are accelerated by an electric field and ions are created from inelastic collisions between gas molecules and the accelerated electrons. The electrical energy to accelerate electrons in the gas is generally performed by a varying electric field, a varying magnetic field, or both. Two main problems occur when the aim is to treat or to deposit plasma along a hollow substrate. The first problem concerns the difficulty to create a uniform plasma density along the substrate length. Indeed, to achieve this condition, a constant electrical energy must be applied to the substrate, which becomes less feasible over a certain size. The second problem is that uniformity of treatment along the whole length can be ensured only if a constant quantity of precursor reacts all along the substrate length. Even if a special energy source arrangement can be implemented to create uniform plasma density along the substrate length, the precursor concentration will decrease irremediably as soon as the gas precursor has flowed the substrate, since higher precursor consumption will occur at the substrate gas inlet. To remedy this problem, several solutions have been developed. One of them, described in US patent 4 692 347 and illustrated in figure 5, consists of shifting a tube 502 to be treated with respect to a fixed plasma source 505 in a vacuum chamber 501. The tube 502 to be coated is initially wound on a reel 508 with an extremity in communication with a monomer source 503 via a flow controller 504. The plasma is created inside the tube 502 by continuously passing the tube in a glow discharge zone formed by the fixed reactance coupling source 505 formed from two electrodes radio frequency powered. The tube part whose interior wall has been coated is wound on a receiving reel 509. A low absolute pressure is maintained inside the tube by evacuating means 506 and 507 connected to the other extremity of the tube. However, such a solution has drawbacks. To roll and unroll thin tubes of low or high stiffness can lead to local shrinking or folding, that is to say irreversible tube deformations. Moreover, the structure and implementation of the evacuating means are complex and it is difficult to guarantee a good pressure control along the tube. These difficulties affect not only the reliability of the plasma treatment of a tube but also the costs and the rapidity of the treatment. Conversely, another solution is to attach the plasma source to a motion mechanism for shifting the plasma source with respect to the tube to be treated. However, such a mechanism is complex and does not permit to control the parameters for a plasma uniform treatment in the substrate. The velocity and the precision of the plasma source motion required for uniform plasma treatment leads to develop electronic control system sensibly increasing the cost of the treatment. Moreover, such a device is limited to single tube treatment. OBJECT AND SUMMARY OF THE INVENTION In view of such aspects, an object of the present invention is to provide a method and an apparatus in which the above-mentioned problems can be solved. In other words, an object is to provide a method and an apparatus which allow a plasma treatment of hollow substrates in uniform way all-over the inside parts of the substrates. To this end, there is provided a method for plasma treatment of a hollow substrate as defined in claim 1. Thus according to the present invention, uniform plasma density can be created along the substrate while having a constant gas concentration reacting along the tube. According to an aspect of the present invention, the plurality of ionisation energy sources are either capacitively coupled plasma sources or inductively coupled plasma sources. According to another aspect of the invention, the ionisation energy sources are powered in a pulsed fashion. The step of injecting a process gas inside the substrate can be also performed in a pulsed fashion. Although the process gas can be pulsed without using a pulsed ionisation energy source and conversely, according to an aspect of the present invention, the gas flow can be pulsed in accordance with the sequences of powering the ionisation energy sources. This ensures that the process gas and therefore the precursor, is renewed in front of the ionisation energy sources between each powering sequence. The precursor consumed after a sequence of powering is replaced so as to maintain a constant precursor concentration each time the plasma is created in the substrate. According to another aspect of the invention, the process gas is permanently flowed in the substrate at a constant precursor rate. Therefore, in this case, the step of injecting the process gas inside the substrate is continuously performed during the entire plasma treatment of the substrate. More precisely, the substrate is a hollow substrate with a large aspect ratio. In an embodiment, the plurality of ionisation energy sources (107-112) are placed according to an array of two dimensions. The present invention also provides an apparatus for plasma treatment of a non-conductive hollow substrate as defined in claim 9. According to an aspect of the invention, the radio frequency power supply means is of a pulse generator type for powering the ionisation energy sources in a pulsed fashion. The apparatus of the present invention may also comprise a gas flow controller for controlling the kinetic of the process gas flowing into the substrate. The gas flow controller may also serve for injecting the process gas in a pulsed fashion. Although the process gas can be pulsed without using a pulsed ionisation energy source, according to an aspect of the invention, the gas flow controller can be connected to output means of the processing means in order to command the gas flow in accordance with the sequences of powering the ionisation energy sources. This ensures that the process gas and therefore the precursor is renewed in front of the ionisation energy sources between each powering sequence. The precursor consumed after a sequence of powering is replaced so as to maintain a constant precursor concentration each time the plasma is created in the substrate. The plurality of ionisation energy sources may be capacitively coupled plasma sources or inductively coupled plasma sources. Specifically, each ionisation energy source comprises electromagnetic means for producing through the substrate a magnetic flux perpendicular to a direction of a substrate length. According to an embodiment of the invention, the apparatus further comprises a plasma chamber provided with two oppositely facing field admission windows and, as electromagnetic means, first and second opposite coil arrangements located on an outer surface of the first and second windows respectively, the first and second coil arrangements being connected to power supply line such that a current of a same direction flows simultaneously in the first and second coil arrangements. The first and second coil arrangements comprises each an inductor having a serpentine form. Advantageously, the first and second coil arrangements further comprises a magnetic core associated with the inductors of the coil arrangements, the magnetic core presenting a pole face structure adapted to be applied against or close to the field admission windows. The radio frequency power supply means deliver power at a frequency around 10 kHz to 100 MHz, preferably at a frequency of 13.56 MHz. According to another embodiment of the invention, the plurality of ionisation energy sources are disposed at each side of the substrate according to an array of two dimensions. BRIEF DESCRIPTION OF THE DRAWINGS The invention and its advantages will be better understood from the following description, given as non-limiting examples, of preferred embodiments with reference to the appended drawings, in which: figure 1 is a schematic cross-sectional view of an apparatus for plasma treatment according to a first embodiment of the invention; figure 2 is schematic perspective view of a coil arrangement according to an embodiment of the invention; figure 3 is schematic perspective view of an apparatus for plasma treatment according to a second embodiment of the invention; figure 4 is a perspective view of two substrates examples; and figure 5 is a schematic view of a conventional apparatus for plasma substrate treatment; DESCRIPTION OF THE PREFERRED EMBODIMENTS The method and apparatus for plasma treatment of a non-conductive hollow substrate according to the present invention will be described in relation with a first embodiment illustrated in figure 1. A tube 1 having a length L and a diameter a is connected at one extremity to a process gas source 2 through a gas flow controller 3. The process gas supplied from the source 2 contains a precursor, such as acrylic acid, in order to create plasma. The quantity of precursor supplied to the internal cavity of the tube is controlled by the gas flow controller 3 which sets the kinetic of the gas injected in the tube. The opposite extremity of the tube 1 is in communication with a device 4 connected to a vacuum pump 5. Four ionisation energy sources 7 to 10 are disposed adjacent to each other along the substrate length L. The ionisation energy sources, which will be referred hereinafter as plasma sources, each comprises a first and second electrodes 7a, 7b (respectively 8a, 8b; 9a, 9b; and 10a, 10b) facing each other with the substrate therebetween. The electrodes of each plasma source have dimensions adapted to produce an electric field therebetween covering at least the diameter or the width of the tube. Although figure 1 shows an embodiment comprising a set of four plasma sources, the number of plasma sources is not limited to this value. The apparatus of the present invention may comprise more or less plasma sources depending on the dimensions of the substrate to be treated. Moreover, according to the present invention, the plasma sources are of a size which ensures generating a uniform electric field while being suitably disposed along the substrate to be treated. The source are controlled by a processing means so that the motion of either the tube or a single source, carried out in the prior art, may be recreated from a set of static plasma sources, thus avoiding the drawbacks of the prior art solutions. The plasma sources 7 to 10 are connected to a radio frequency (RF) power source 6 through corresponding supply lines 17 to 20. The supply lines 17 to 20 each comprise a switch SW. The switches SW1 to SW4 are independently controlled by a processing device 11 such as a micro controller through corresponding output terminals S1 to 54. The plasma source can be either a capacitively coupled plasma source or an inductively coupled plasma source. In figure 1, for example, the sources illustrated are of a capacitively coupled plasma source type. An electric field 12 is created between the electrodes 8a and 8b of the source 8 by reactance coupling when the electrodes are powered by the RF power supply 6. The four ionisation plasma sources 7 to 10, which can be a capacitively coupled plasma source or an inductively coupled plasma source, define four plasma creation zones P1 to P4 delimited by the specific electric field produced from each source. Accordingly, the plasma creation can be controlled for each plasma creation zone P1 to P4 through the processing means 11 which controls the open/close state of the switches SW1 to SW4 provided in the supply lines 17 to 20 of the sources 7 to 10. Each plasma source is powered by a common RF power source. The plasma is thus created along the tube by the set of sources 7 to 10 sequentially powered. A main advantage of this configuration is the possibility to regulate the "plasma source motion" with required velocity, frequency and direction. Indeed, since the powering of the source can be independently initiated by the processing means, the velocity of the plasma source motion along the tube 1 is regulated by the frequency at which the switches are sequentially closed. The direction of the plasma source motion is determined by the order according to which the switches are closed under the control of the processing means. Furthermore, in the same way, the frequency of the plasma source motion is determined by the number of times the processing means causes the sources to be powered. In view of this, the velocity, the direction and/or the frequency of the plasma source motion can be set to a fixed or variable value depending on the sequence programmed in the processing means. According to an implementation of the method plasma treatment of the invention, the process gas is permanently flowed in the substrate at a constant precursor rate while the plasma sources are sequentially powered. In this case, a fixed programmed sequence of source powering may be suitable. Nevertheless, the sequence of source powering can be programmed in such a way that the frequency, the velocity and/or the direction of the plasma source motion can be controlled according to the process gas flow injected inside the substrate. The process gas flow may be monitored by the processing means 11 which receives a gas flow value signal GFV from the gas flow controller 3. Accordingly, if the process gas is not constantly flowed in the substrate, the processing means is able to correct this irregularity by modulating one or more parameters with regards to the control of the source motion accordingly. This provides means for ensuring the plasma to have a local density uniform all along the substrate. Alternatively, the plasma creation inside the substrate can be obtained in a pulsed way. In order to do this, the RF power source 6 is of a pulse generator type. Furthermore, the gas flow can be also pulsed by the gas flow controller 3. When the process gas containing the precursor is not permanently flowed in the substrate, it must be renewed at least between each powering sequence of the sources in order to maintain a constant precursor concentration in front of the sources when plasma is created. Therefore, if the process gas is supplied in the substrate in a pulsed way, the gas flow controller 3 can be slaved to the powering sequences of the plasma sources so that the injection of the process gas is synchronized with the powering of each plasma source. To this end, the processing means 11 has a control_output terminal Spc through which a control signal is sent to the gas flow controller 3. The output terminal Spc may also be used for commanded the flowing of process gas according to a specific program loaded in the processing means 11. In view of the above, a pulsed energy source can be implemented with or without a pulsed gas flow while, in the same way, a pulsed gas flow can be implemented with or without pulsed energy source. The plasma can be also created inside the substrate from sources of an inductively coupled plasma type. In this case, the plasma sources are comprised of two coil arrangements which can be disposed in the vicinity of the substrate substantially in the same configuration as the pair of electrodes illustrated in figure 1. An embodiment of one of two coil arrangements, which are similar, is illustrated in figure 2. The arrangement 7a' comprises an inductor 71 disposed according to a serpentine form in such a way that the inductor presents a series of opened linked loops. In another embodiment, the arrangement can comprise a series of superimposed linked loops formed by a single inductor. Such an arrangement allows the inductive energy produced by the inductor to be increased. The coil arrangements in the present invention are not limited to the two above examples and a man skilled in the art could obviously imagine various embodiments for the coil arrangement without any difficulties. The inductor may be associated with a magnetic core in order to increase and homogenize the magnetic field produced by the inductor. This technical aspect of such an association as also its various embodiments have already been described in detail in European Patent Application EP 0 908 923. Referring to figure 2, a magnetic core 72 includes a pole face structure 73 to ensure that the magnetic field minimizes the "dead area" at the intervals between the loops formed by the inductor. Accordingly, the combination of the magnetic core and the inductor form a coil arrangement which allows an homogenized magnetic flux all over the area of the substrate which is covered by the source constituted by two coil arrangements. The inductor 71 is comprised in a lower part of the magnetic cores 72 respectively so as to be close to the substrate to be treated. However, according to the nature of the material constituting the magnetic core or the magnetic flux expected, the inductor may be located at different positions in the magnetic core. The magnetic core may be easily matched to the shape and dimensions desired. With a plasma source comprising two coil arrangements as described above, a transversal magnetic flux, which is substantially perpendicular to a substrate cavity length L, is produced. The coil arrangements are both supplied by a RF power source which generates an electrical current I flowing in the same direction in both inductors of the coil arrangements respectively. Accordingly, the magnetic flux is produced transversally and perpendicularly to the substrate in a sense determined by the direction of the current flowing in the coils arrangements. As the substrate is non-conductive, the magnetic flux generates an electric field which is produced in the substrate plan perpendicularly to the direction of the magnetic flux. As the magnetic flux is perpendicular and transverse to the cavity length of the substrate, the electric field circles in a loop all over the substrate plan. Accordingly, the path for accelerating the electrons is longer and an efficient plasma creation can therefore be obtained. As a result, the electrical flux is created in the whole area covered by the source which ionises the process gas in the corresponding substrate volume. This configuration is particularly suitable for plasma treatment of thin hollow substrates because of its good efficiency criterion which is, for a transversal flux, about R ≈ 0.3, as explained in detail in the European patent application EP 00 400 445 .3. Moreover, the propagation of the magnetic field is independent of the substrate parts placed in the chamber since they are non-conductive. Figure 3 illustrates a second embodiment of an apparatus for plasma treatment according to the present invention. In this embodiment, the set of plasma sources is comprised of an array of six plasma sources 107 to 112 disposed according two directions. Indeed, the substrate to be treated is a flat box 101 as that represented in figure 4. As can be seen from figure 3, three plasma sources 107 to 109 are disposed adjacent to each other according to a first row while the sources 110 to 112 are respectively aligned with the sources 107 to 109 according to a second row. The disposition of the plasma sources 107 to 112 according to an array of two dimensions matches the form of the flat box 101 which, contrary to a tube, presents a width W shown in figure 4. As shown for the plasma source 107, each source comprises two parts 107a and 107b sandwiching the flat box 101 to be treated. The two parts of each source may be reactance electrodes or, as represented in figure 3, two coils arrangements having the structure described above. As illustrated only for plasma source 109 in order to simplify the figure, both coil arrangements 109a and 109b are connected to a RF power source 106 via a switch SW3 which is on/off controlled by the processing means 211 through an output terminal S3. Therefore, both coil arrangements of the plasma sources 107 to 112 are sequentially powered by the source 106 via respective switches SW1 to SW6 which are on/off controlled by the processing means 211 through output terminals S1 to S6 respectively. The coil arrangements may be driven at a frequency of around 10 kHz to 100 MHz. For example, the typical operating frequency of 13.56 MHz, delivered by the power supply devices commonly used, is sufficient to treat numerous types of thin hollow substrates with an optimum efficiency. When a plasma source is powered, a transversal magnetic flux 130, which is substantially perpendicular to a substrate length L is produced by the two coil arrangements of the source. Accordingly, the magnetic flux 130 is produced transversally and perpendicularly to the substrate 101 in a sense determined by the direction of the current flowing in the coils arrangements. As the substrate 101 is non-conductive, the magnetic flux 130 generates an electric field 131 which is produced in the substrate plan perpendicularly to the direction of the magnetic flux 130. The apparatus comprises a classical plasma chamber 102 in which a plasma processing can be implemented. The chamber 102 includes a sealed area which can be evacuated and controlled in pressure by evacuating means such as those shown in figure 1. The chamber is filled with a process gas via a process gas source and a gas flow controller (not shown). As the substrate is included in the sealed area of the chamber 102, the process gas can be ionised inside and/or outside the substrate allowing plasma creation inside and/or outside the substrate. The plasma chamber further comprises a first and a second field admission windows 102a and 102b made of quartz or other dielectric material such as to allow an energy field to enter inside the chamber by inductive coupling and thereby create or sustain the required plasma processing conditions. The space defined between the two windows substantially corresponds to the thickness dimension of the plasma chamber volume occupied by the flat box 101. The form and the dimensions of the plasma chamber and so the field admission windows depend on the form and the size of the substrate to be treated. For example, the field admission windows have to cover at least the whole widest face of a parallelepipedic hollow substrate or the cylindrical part of a tubular substrate. As for the first apparatus embodiment described in relation to figure 1, the processing means 211 are specifically programmed so as to control sequentially the on/off state of the switches SW1 to SW6, thus determining the direction, the velocity and/or the frequency of the plasma source all over the substrate. The difference with the first embodiment is that the plasma source motion can be controlled with respect to two dimensions. The gas flow inside the substrate may be also slaved to the processing means 211 through the output terminal Spc.

Claims: Method for plasma treatment of a hollow substrate (1; 10), comprising the steps of: a) placing a plurality of ionisation energy sources (7-10; 107-112) all along the part of the substrate to be treated, b) injecting a process gas inside the substrate, said gas containing a precursor for plasma creation, and c) maintaining pressure inside the tube within a predetermined range, characterised by comprising the further step of: d) powering from a single radio frequency power source (6; 106) the ionisation energy sources, in sequence, for selectively creating plasma inside the substrate at a location corresponding to the respective source powered, said step b) of injecting the process gas being repeated at least before the powering of each ionisation energy source, said single radio frequency power source delivering power at a frequency around 10 kHz to 100 MHz. Method for plasma treatment according to claim 1, characterised in that said step b) is commanded in accordance with the sequences of powering the ionisation energy sources. Method for plasma treatment according to claim 1, characterised in that in said step b) of injecting a process gas inside the substrate, the process gas is continuously injected inside the substrate at a constant precursor rate. Method for plasma treatment according to any one of claims 1 to 3, characterised in that the plurality of ionisation energy sources are capacitively coupled plasma sources (7-10). Method for plasma treatment according to any one of claims 1 to 3, characterised in that the plurality of ionisation energy sources are inductively coupled plasma sources (107-112). Method for plasma treatment according to any one of claims 1 to 5, characterised in that the ionisation energy sources are powered in a pulsed fashion. Method for plasma treatment according to any one of claims 1 to 6, characterised in that the substrate (1; 101) is a hollow substrate with a large aspect ratio (L/a). Method for plasma treatment according to any one of claims 1 to 7, characterised in that , in said step a), the plurality of ionisation energy sources (107-112) are placed according to an array of two dimensions. Apparatus for plasma treatment of a non-conductive hollow substrate (1; 101), comprising generation means for generating a plasma in the substrate, said generation means comprising a plurality of ionisation energy sources (7-10; 107-112) disposed adjacent to each other all along the part of the substrate to be treated, characterised in that said apparatus further comprises a processing means (11; 211) for sequentially powering the plurality of ionisation energy sources from a single radio frequency power supply means (6; 106), said single radio frequency power source delivering power at a frequency around 10 kHz to 100 MHz. Apparatus according to claim 9, characterised in that the radio frequency power supply means is of a pulse generator type for powering the ionisation energy sources in a pulsed fashion. Apparatus according to claims 9 or 10, characterised in that the processing means comprises output means (Spc) for commanding a gas flow controller (3) in accordance with the sequences of powering the ionisation energy sources. Apparatus according to any one of claims 9 to 11, characterised in that the plurality of ionisation energy sources are capacitively coupled plasma sources (7-10). Apparatus according to any one of claims 9 to 11, characterised in that the plurality of ionisation energy sources are inductively coupled plasma sources (107-112). Apparatus according to claim 13, characterised in that each ionisation energy source (109) comprises electromagnetic means (109a; 109b) for producing through the substrate (101) a magnetic flux (130) perpendicular to a direction of a substrate length (L). Apparatus according to claim 14, characterised in that it further comprises a plasma chamber (102) provided with two oppositely facing field admission windows (102a, 102b) and, as electromagnetic means (109a; 109b), first and second opposite coil arrangements located on an outer surface of the first and second windows respectively, the first and second coil arrangements being connected to power supply line (119) such that a current (I) of a same direction flows simultaneously in the first and second coil arrangements. Apparatus according to claim 15, characterised in that said first and second coil arrangements comprises each an inductor (71) having a serpentine form. Apparatus according to claim 16, characterised in that said first and second coil arrangements further comprises a magnetic core (72) associated with the inductors of said coil arrangements, the magnetic core presenting a pole face structure adapted to be applied against or close to the field admission windows. Apparatus according to any one of claims 9 to 17, characterised in that said plurality of ionisation energy sources are disposed at each side of the substrate (101) according to an array of two dimensions.

Inventors: COLPO PASCAL, ROSSI FRANCOIS, COLPO, PASCAL, ROSSI, FRANCOIS, Rossi, François
Applicants: EUROP ECONOMIC COMMUNITY, EUROPEAN COMMUNITY
Application year: 2001
Main classification: C23C16
IPC codes: H01J37, A61J1, B01J19, H05H1, C23C16, A61M25