Installation for depositing films onto a substrate

Abstract

An installation, comprising a chamber comprising two ends, a transport unit and a support unit which introduce a two-sided substrate into the chamber, a stabilized high-voltage high-frequency power supply of at least 200 kW, comprising an HF transformer comprising a primary and a secondary circuit connected to terminals, at least two electrodes being connected to the terminals of the secondary circuit, said electrodes being placed on each side of the substrate, at least one dielectric barrier placed between the at least two electrodes; a power supply regulation/control unit placed upstream of the HF transformer that is capable of increasing an active power/reactive power ratio, an introducing unit for introducing at least one reactive substance into the chamber, and an extracting unit for extracting residual substances, wherein an adjustable inductor is placed in the secondary circuit of the transformer in parallel with a circuit comprising the at least two electrodes, and the adjustable inductor enables a phase shift between a voltage generated between the electrodes and a total current delivered by the high-voltage source to be modulated, and the power supply regulation/control unit, placed on the primary circuit of the transformer, and/or a unit for controlling the inductor being capable of generating harmonics extending a time during which a current flows between the electrodes, wherein the installation is suitable for depositing a film onto an inorganic substrate.

Claims

1. An installation, comprising: a chamber having two ends; a stabilized high-voltage high-frequency power supply of at least 200 kW, having a HF transformer including a primary and a secondary circuit having terminals, at least two electrodes being connected to the terminals of the secondary circuit, said electrodes being placed on each side of the substrate; at least one dielectric barrier placed between the at least two electrodes; a power supply regulation unit placed on the primary side of the HF transformer and configured to increase an active power/reactive power ratio; and an introducing unit for introducing at least one reactive substance into the chamber; wherein an adjustable inductor is placed in the secondary circuit of the transformer in parallel with a circuit having the at least two electrodes, and the adjustable inductor enables a phase shift between a voltage generated between the electrodes and a total current delivered by the high-voltage source, wherein the installation further comprises a control system for adjusting the inductance of the adjustable inductor and the control system is configured to cause the installation to generate third-order and fifth-order harmonics thereby extending a time during which a current flows between the electrodes, and wherein the installation is suitable for depositing a film onto an inorganic substrate.

2. The installation according to claim 1, wherein the chamber is open at both of the two ends.

3. The installation according to claim 2, wherein the chamber is incorporated into a float glass production line, and a support unit includes a bath of molten tin.

4. The installation according to claim 3, wherein the bath of molten tin is one of the electrodes.

5. The installation according to claim 1, wherein the chamber is closed at both of the two ends.

6. The installation according to claim 1, which is incorporated into a production line comprising an annealing lehr, wherein the chamber is placed in the annealing lehr, and a support unit includes at least one roller.

7. The installation according to claim 1, incorporated into a tempering line.

8. The installation according to claim 1, incorporated into a deposition line working at low pressure.

9. The installation according to claim 1, wherein the plasma is generated in two separate zones lying on each side of the substrate, in such a way that a film is deposited onto each side of the substrate simultaneously.

10. The installation according to claim 1, wherein the adjustable inductor includes: (A) a coil having a bundle of conducting elements, wherein the conducting elements are insulated from one another, and the coil is wound around a mandrel; (B) a magnetic plunger core placed inside the mandrel and isolated from the mandrel; and (C) a positioning device connected to the magnetic plunger core.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) Other advantages and features of the invention will become apparent from the following detailed description of particular embodiments of the invention, reference being made to the figures in which:

(2) FIG. 1 is a schematic side view of an installation for depositing films onto a glass substrate;

(3) FIG. 2 is an equivalent circuit diagram for the installation of FIG. 1 before plasma formation;

(4) FIG. 3 is an equivalent circuit diagram for the installation of FIG. 1 after plasma generation;

(5) FIG. 4 is an equivalent circuit diagram for the installation according to the invention;

(6) FIG. 5 is a conventional voltage/current oscillogram;

(7) FIG. 6 is a voltage/current oscillogram specific to the installation;

(8) FIG. 7 is a more detailed equivalent circuit diagram of the power supply system for the installation of the invention;

(9) FIG. 8 is a schematic side view of one embodiment of an installation open at both its ends for film deposition onto a glass substrate according to the invention;

(10) FIG. 9 is a schematic side view of an embodiment of an installation in the case of an insulating substrate, it being possible, under the conditions prevailing in the deposition chamber, for the substrate itself to form a dielectric barrier, thereby giving the possibility of not using an additional dielectric barrier;

(11) FIG. 10 is a schematic side view of an induction coil for an installation according to the invention; and

(12) FIG. 11 is a cross-sectional view of a strand of the winding wire used in the induction coil shown in FIG. 11.

(13) The figures are not necessarily drawn to scale.

(14) In general, similar elements are denoted by similar references in the figures.

DETAILED DESCRIPTION OF PARTICULAR EMBODIMENTS

(15) FIG. 1 is a schematic view of the installation according to the invention, which here is applied to the continuous production of glass by the float glass process. In particular, the treatment chamber is placed above the bath of molten tin. The substrate onto which it is intended to deposit a surface layer is here a continuously cast sheet of glass 2 moving over a bath of liquid tin 4. The direction of movement corresponds to the plane of the sheet in the drawing. During its running movement, the glass sheet 2 enters a chamber 6 open at both its ends (entry and exit). Using the well-known CVD technique, a reactive mixture 8 is introduced into the chamber 6. It should be noted that the way of introducing the reactants (counter-currently in FIG. 1) is given by way of example. Any other form of introduction (perpendicular to the substrate, etc.) is not excluded.

(16) Since the solidified glass sheet 2 is still at relatively high temperature, it provides the mixture 8 with additional thermal energy promoting deposition of a film of the desired composition. Depending on the position of the installation, the temperature of the glass sheet will be between 600 C. and 750 C. To further increase the energy available for the reaction, two electrodes are placed in the chamber 6. One of these electrodes is none other than the bath of liquid tin 4 (which is earthed), the other electrode 10 extending along an axis perpendicular to the run direction of the glass sheet 2. The shape of the electrode depicted in FIG. 1 is given by way of example. Any other geometry is not excluded.

(17) Since a high-frequency high voltage is applied between these electrodes 4, 10, a plasma 12 (shown schematically by parallel lines) is generated, from which the reactants 8 introduced into the chamber draw increased energy, making it possible for a large variety of compounds to be deposited onto the glass sheet. The voltage is preferably between 1 kV and 200 kV peak to peak, more preferably between 5 kV and 100 kV peak to peak and even more preferably between 10 kV and 40 kV peak to peak. The frequency is preferably between 10 kHz and 1000 kHz, more preferably between 20 kHz and 400 kHz and even more preferably between 50 kHz and 200 kHz.

(18) To reduce the possible risk of forming electric arcs directly between the two electrodes, a dielectric barrier 14 may be placed in the chamber between the positions of the two electrodes 4 and 10. Since the chamber 6 is of the open type, it is necessary to also use powerful extraction means which remove the pyrolysis residues and the dust generated by the deposition process. It goes without saying that what has been described above in the bath of molten tin applies mutatis mutandis in the annealing lehr, the bath of molten tin being replaced with a metal electrode placed for example between the rollers and earth. In this situation, the temperature of the substrate may be varied between 20 C. and 600 C.

(19) The problem that generally arises in this type of process, whenever it is desired to take it from the experimental stage to industrial production, is the low efficiency obtained with regard to the energy consumed to generate the plasma. As a consequence, this efficiency must be improved so as to make the process not only energetically profitable but also to allow the process to generate sufficient active energy to obtain high deposition rates while improving the properties of the films deposited. A thorough study of all the factors involving energy was therefore undertaken, thereby making it possible to reduce, very schematically, the installation in question to two equivalent circuit diagrams, as shown in FIGS. 2 and 3.

(20) FIG. 2 is a very simplified equivalent circuit diagram for the installation before ignition, a high voltage being applied between the electrodes 4, 10. Installing the discharge in the chamber 6 essentially amounts to adding capacitances in parallel and in series, namely C.sub.p (parasitic capacitance in parallel with a parasitic resistance R.sub.p), C.sub.d (capacitance of the dielectric), C.sub.v (capacitance of the glass) and C.sub.g (capacitance of the gas).

(21) FIG. 3 shows the same circuit diagram when the plasma is generated. At this moment, C.sub.g is shunted by a resistance R.sub.g, which represents the resistance of the plasma.

(22) In the absence of a discharge (i.e. as long as the voltage applied between the electrodes is below the ignition voltage), the value of R.sub.g is extremely high, and the total current delivered by the source is in practice purely capacitive, the reactive part being essentially dependent on the dielectric loss in the insulator of the upper electrode and/or the lower electrode and on the substrate. During discharge, the useful current I.sub.g flowing through the plasma always remains low compared with its capacitive component. The use of the voltage source is therefore limited, the delivered power being dissipated in producing a very high reactive current, whereas only the active component, delivering the watted (i.e. in-phase) power to the discharge (P.sub.w=R.sub.gI.sub.g.sup.2), is useful.

(23) Firstly to compensate for the lack of watted power, consideration was given to placing an induction coil L acting as energy reservoir in parallel with the installation, making it possible to generate a current in phase opposition with the energy absorbed by the capacitive load. This allows almost complete recovery of the energy involved. An equivalent circuit diagram as shown in FIG. 4 is therefore obtained.

(24) However, it should be pointed out that this type of compensation is not similar to the compensation obtained for example by placing an induction coil in parallel with a current distribution line, nor to an installation for generating a relatively low-power plasma (glow-discharge plasma), as used for coating polymer sheets. This is because what is involved here is not a fixed capacitive component, as is the case in a distribution network, but a load eminently variable according to the frequency (here, kilohertz frequency), the thickness of the substrate and the reactants introduced into the chamber (which induce variations in the electrical and dielectric properties of the gas and the plasma, etc.). As a consequence, it is necessary to employ a very particular type of induction coil, capable not only of withstanding the loading conditions generated in a high-power installation (in the order of several hundred kW), at high voltage, of course, but also at high frequency, and also having the possibility of being adjusted relatively finely according to the imposed conditions during each type of manufacture. This is because the resultant load will vary, in particular according to the various process parameters such as, for example, the nature of the reactants, the thickness of the glass, the gas gap, etc. The gas gap is preferably between 0.5 mm and 100 mm, more preferably between 1 mm and 20 mm and even more preferably between 3 mm and 6 mm.

(25) Various trials showing the possibility of employing the process of the invention in a concrete practical manner brought to light an advantageous and unexpected consequence of this process.

(26) FIG. 5 shows that another phenomenon is responsible in part for the mediocre efficiency of a DBD plasma film deposition installation: when an HF high voltage is applied, for each half-period, a discharge can be sustained only over the time period t.sub.1 when the applied voltage is above an ignition voltage V.sub.1. This time interval is intimately linked to the parameters described above. Of course, this phenomenon is repeated each half-period. The efficiency of the process is therefore limited by the ratio of t.sub.1 to the length of a half-period.

(27) According to Fourier's law, if a source supplies a non-linear dipole, the resulting current will not be linear and will have a complex form which may be decomposed into a superposition of several curves, i.e. those having a fundamental frequency and a sum of harmonics.

(28) In the present case, it has been found that interposing an induction coil in the circuit gives rise to a distortion of the curve corresponding to the flow of current through the plasma, as shown in FIG. 6. This curve may be decomposed using the principle of Fourier series into a fundamental and a series of harmonics, the most significant ones of which, owing to their amplitude, are the 3.sup.rd and 5.sup.th odd harmonics. As may be seen in FIG. 6, the curve corresponding to the current flow has a kind of plateau over a time interval t.sub.2 much longer than the interval t.sub.1 observed on the curve shown in FIG. 5. The length of this interval may be optimized by varying the characteristics of the circuit, and in particular the frequency and the inductance of the inductor L placed in the secondary of the VHV transformer. As a consequence, in the installation of the invention, by interposing an adjustable induction coil of suitable characteristics, it is possible to obtain, all other things being equal, not only an increase in active power but also a longer discharge time and, as a consequence, a much better energy efficiency.

(29) FIG. 7 is a more complete equivalent circuit diagram than that sketched in FIG. 4, and better demonstrates the particular features of the installation itself, if it is compared with the prior art. Referring to this circuit diagram, it may be seen that all the adjustments (filtering, compensation, etc.) making it possible to have a stabilized and optimally compensated voltage/current curve (cos ) are essentially performed on the primary 601 of the supply transformer 602. As a consequence, the sole adjustment means necessary for achieving the phase shift shown in FIG. 6 in the secondary circuit 604 of this transformer 602 is the variable induction coil 606, designed especially to work at very high voltage and placed in parallel with the plasma generator.

(30) The power supply is therefore controlled in the following manner: an aperiodic generator is used consisting of an inverter 608 (which converts the DC supply current to an AC current), a parallel oscillating circuit and a variable induction coil LV for adjusting the operating frequency and providing the correct active power. Placed in the primary circuit of the very high-power transformer there is a power controller 610 and its associated safety circuits (P/S) 612.

(31) Thanks to the circuit diagram shown in FIG. 7, it is very simple thereafter to adjust the inductance of the induction coil 606 in such a way that the load formed by 606 and the added capacitances in parallel and in series (see FIG. 4) remains non-linear so as to promote the third-order and fifth-order harmonics that enable the stable plasma to be sustained for an appreciably longer time per half-period (see FIGS. 5 and 6).

(32) The operations performed on the primary 601 and on the secondary 604, respectively, of the transformer therefore work in apparent contradiction: the aim is firstly (in the primary) to increase cos of the installation (thereby increasing its apparent efficiency) and, moreover, in the secondary, this optimum value is degraded so as to generate harmonics, which thus paradoxically increase the efficiency of plasma deposition.

(33) If it is added that the very high-power induction coil inserted into the secondary circuit is raised to a very high voltage, the installation thus designed comprises a series of features that are paradoxical to those skilled in the art.

(34) The active power is increased preferably by at least 10%, more preferably by at least 25% and even more preferably by at least 50%. The discharge time is increased preferably by at least 15%, more preferably by at least 30% and even more preferably by at least 60%. It should also be noted that, to determine the optimum inductance of the induction coil, it is necessary to take into account the intrinsic inductance of the power supply circuit (which includes a transformer), said intrinsic inductance not necessarily being negligible. Since the power supply circuit has its own resonant frequency, the inductance of L may, under certain conditions, be greatly reduced.

(35) It goes without saying for a person skilled in the art that it is also possible to use a capacitive voltage tripler in the primary circuit so as to obtain a VHV by reducing the number of turns of the transformer 602, the overall size of which is thus appreciably reduced.

(36) Among the advantages of the process as described, mention may be made of the following: owing to the increase in deposition efficiency, it is possible to reduce the amount of chemical reactants used. As a consequence, apart from a reduction in production costs and in environmental impact, it is observed that there is less fouling of the installation, thereby generating additional cost savings; an increase in deposition rate, with the corollary that the treatment time is reduced. As a consequence, it is possible for substrates moving at higher speed to be continuously treated. Conversely, the width of the treatment chamber may be reduced, hence a not insignificant space saving. Finally, there is the possibility of obtaining much thicker films in a single pass, which may prove to be advantageous in particular from the standpoint of the properties of these films; better decomposition of the precursors is observed during the reactions taking place within the plasma. As a consequence, the presence of organic residues in the films is avoided. Furthermore, the films deposited will be more dense and better crystallized, hence an improvement in both optical and mechanical properties of the films deposited; and it is also possible to increase the variety of species deposited onto the substrate in film form, again with a lesser environmental impact.

(37) Finally, it is also possible, as shown in FIG. 8, by a judicious choice of the characteristics, to work simultaneously on both sides of the glass 2, even depositing thereonto, as the case may be, different species, since there is the possibility, using various tricks (physical separation or extraction apparatus suitably positioned), of introducing different reactive substances 108, 208 into the chamber 106 on either side of the glass 2 in the two plasma zones (112, 212). Furthermore, the distance between the substrate 2 to be coated and the two electrodes (110, 210) covered with dielectrics (14, 114) may also be adjusted according to the desired deposition criteria. It goes without saying that the equivalent circuit diagram for such an installation is more complex and that it is possible to control the characteristics thereof only by the presence of the adjustable inductor characteristic of the installation according to the invention. In addition, the presence of two gaps acting as capacitors in series a priori reduces the discharge current, hence the benefit of the present invention.

(38) It goes without saying that what has been described above for a continuous glass casting installation applies mutatis mutandis to an open installation relating to discontinuous substrates, such as precut volumes of glass (the installation may for example be incorporated into a toughening line). The chamber of FIG. 8 may be replaced by a closed chamber designed for a process for depositing a discontinuous film on separate glass volumes. In this case, one or two closure devices make it possible either to work at atmospheric pressure or to work at pressures well away from atmospheric pressure (typically between 10.sup.1 Pa and 110 kPa) (in the case of the installation shown in FIG. 1, it is necessary to use powerful extraction devices to move away from ambient pressure). In the case of a process operating at reduced pressure, reactants (108, 208) may also be used that have lower vapour pressures and/or have a more toxic character, without in any way endangering the health of the operators. Such an installation may for example be incorporated into a film deposition line working at low pressure, of the magnetron sputtering type.

(39) The advantages associated with generating filamentary plasma on both sides of a substrate are numerous. In fact, the number of technical applications for a substrate treated on both sides is ever increasing.

(40) FIG. 9 is a variant of the installation shown in FIG. 7. If the substrate is insulating, it is possible to dispense with additional dielectrics (14, 114).

(41) FIG. 10 is a simplified representation of one embodiment of the compensating induction coil 20 for the installation of the invention. This induction coil 20 is essentially made up of a winding 22 wound around a mandrel 24. Since the voltage across its terminals may be 60 kV, the choice of material used for the mandrel supporting the winding is very important. Advantageously, Acculon was used. A plunger core 26, carefully insulated and mechanically connected to a positioning device 28 controlled by a control system, is placed inside this mandrel 24. In view of the particular operating conditions that this induction coil must face in use, a series of innovations in its practical construction has been adopted. Thus, the winding 22 is made with a bundle of copper wires (see FIG. 11), which are insulated so as to increase the flow cross section for the HF current (taking into account the skin effect) and also to reduce heating. Thus, it is possible to divide the total HF current by a factor of 50 by producing a conductor bundle consisting of 50 mutually insulated strands. The winding pitch is fixed so that the risk of inter-turn arcing is as low as possible. A winding made of a single ply is therefore preferable, although it has the consequence that the device in its entirety is large. The position of the magnetic core 26, and therefore the inductance of the induction coil 20, is adjusted by remote control so that this operation can be carried out without danger to the operator.

(42) It should be obvious to a person skilled in the art that the present invention is not limited to the exemplary embodiments illustrated and described above. The invention comprises each of the novel features and also combinations thereof. The presence of reference numbers cannot be considered to be limiting. The use of the term comprises or the term includes can in no way exclude the presence of other elements, other than those mentioned. The use of the indefinite article a or an to introduce an element does not exclude the presence of a plurality of these elements. The present invention has been described in relation to specific embodiments, which are purely illustrative and must not be considered to be limiting.