The invention relates to a device for injecting into a chamber at least one liquid precursor or one precursor in solution of an element to be deposited on a support arranged in the chamber, said device comprising:
In the field of chemical vapor deposition (CVD, with continuous or pulsed gas flows or with a combination of pulsed and continuous gas flows) or of atomic layer deposition (ALD), the devices for entering the elements to be deposited or the precursors of said elements into the deposition chamber are more and more often constituted by devices for injecting liquid droplets. The liquid droplets are injected either directly into the deposition chamber or into a thermostated chamber coupled with the deposition chamber.
Such injection devices enable a spray to be formed constituted by fine droplets evaporating without the precursor or the element to be deposited having previously come into contact with the thermostated chamber or with the reaction chamber. This limits the risks of fouling and generation of particles. These devices also enable new types of precursors to be used, for example organo-metallic, liquid or solid elements which may be not very volatile and are often difficult to implement, as they are by nature chemically or thermally unstable. These precursors can be used pure when they are in liquid form or dissolved in a solvent when they are in liquid or solid form. New materials, constituted by elements, which are for example transition metals, alkaline earths or lanthanides, can thus be obtained by CVD and/or ALD.
The Patent Application EP-A-0730671 describes for example a device for entering precursor of elements to be deposited on a substrate into a CVD chamber by discontinuous injection of droplets. As represented in
Such devices operate in open loop. Thus, for given experimental data such as the type of precursor, the temperature of the chamber, the temperature of the liquid to be injected, or the thrust pressure, the injector 3 is for example controlled such as to open periodically, i.e. at a certain frequency Finj with a previously set opening time tinj, in such a way as to obtain droplets of a given volume. On outlet from the injector 3, the liquid is then pulsed at the control frequency Finj.
The level of reproducibility of such devices does however depend to a great extent on the stability of the experimental conditions such as the temperature, the thrust pressure, the pressure in the chamber. It also depends on the reproducibility of operation of the injector 3, itself dependent on its temperature, on the level of fouling of the pipe arranged between the tank 2 and the injector 3 or of the injection head. Moreover, in certain cases, it is experimentally observed that the mean liquid flowrate can vary several percent over a few tens of minutes without the injection control parameters having been modified.
The object of the invention is to obtain a device for injecting into a chamber at least one liquid precursor or one precursor in solution of an element to be deposited on a support arranged in the chamber, which device remedies the shortcomings mentioned above and is more particularly reliable and reproducible.
According to the invention, this object is achieved by the fact that the device comprises:
According to a first development of the invention, an additional mechanical low-pass filter is arranged between the tank and the device for measuring the flowrate.
According to a second development of the invention, the mechanical low-pass filter is formed by a pulse damper.
According to another development of the invention, the mechanical low-pass filter is a restriction that is constituted by a portion of a pipe arranged between the tank and the injector, said portion having a smaller transverse cross-section than that of the rest of the pipe in such a way as to form a throttling.
According to another development of the invention, the mechanical low-pass filter is constituted by a connection designed to form a buffer volume.
According to a preferred embodiment, the control circuit comprises a correction circuit connected to the regulation input and taking account of the transfer function of the mechanical low-pass filter.
According to another particular embodiment, the device comprises a pressure regulation circuit comprising at least first and second inputs respectively connected to the output of the control circuit associated with the tank and to a device for measuring the pressure in the tank.
According to another feature, the pressure regulation circuit comprises at least first and second outputs respectively connected to an inlet valve and an outlet valve respectively controlling inlet and outlet of a compressed gas to and from the tank.
Other advantages and features will become more clearly apparent from the following description of particular embodiments of the invention given as non-restrictive examples only and represented in the accompanying drawings, in which:
According to the invention, periodic injection into an chamber such as a CVD or ALD deposition chamber or a thermostated chamber coupled with said deposition chamber, of at least one liquid precursor or one precursor in solution of an element to be deposited on a support arranged in the chamber, is achieved by an injection device 1 such as the one represented in
A flowrate measuring device or flowmeter 6 is arranged between the tank 2 and the injector 3 in such a way as to measure the mean flowrate (Qmmeas) upstream from the injector 3. The flowmeter 6 is for example a mass liquid flowmeter such as a Coriolis effect flowmeter or a thermal flowmeter, or a volumetric liquid flowmeter, with instantaneous read-out, or a flowmeter based on measurement of the pressure difference at the boundaries of a restriction in which the liquid precursor flows.
Such flowmeters are however at present not suited to the injection frequencies used. Thus, for a relatively low injection frequency, for example 5 Hz, the signal from the flowmeter and the pressure upstream therefrom are pulsed at the injection frequency. Under these conditions, even with a pressure regulation system, the signal measured by the flowmeter oscillates greatly and is liable to exceed the predetermined maximum measurement value and to stray outside the linearity range of the flowmeter. In this case, the mean value of the measured flow is no longer representative of the mean flow in the pipe 5. Moreover, the behaviour of periodic injection devices in pulsed mode of liquid precursors or precursors in solution, and more particularly the variation of the mean flow of liquid to be injected from one deposition to the other (reproducibility), can not be anticipated and corrected. It is generally highlighted indirectly and a posteriori by analyzing for example the thickness of the thin layers obtained by CVD or ALD. Likewise, for these systems, the variation of the mean flow of liquid to be injected in the course of a deposition (repeatability) can not be anticipated or corrected and can only be highlighted a posteriori by analyzing for example, in the case of depositions of multimetallic materials obtained from homometallic precursors injected into the chamber via different injection lines, the stability of the composition of the layer over the thickness thereof.
For illustration purposes,
The curve A1 is made up of a succession of rectangular pulses of predetermined period whereas the curve C1, in a dotted line, is made up of a succession of pulses substantially dampened by the presence of the flowmeter. The curves B1 and D1 correspond respectively to mean values that are substantially constant in time but different from one another. This therefore illustrates the difficulty of measuring the mean flowrate correctly, with periodic injection devices, even when the flowrate is integrated over an injection period.
As represented in
Like the curve A1 of
The mechanical low-pass filter 7, also called mechanical element acting as low-pass filter, is for example formed by a pulse damper and/or by a restriction which is formed by a portion of the pipe 5 the transverse cross-section whereof is smaller than the rest of the pipe 5 in such a way as to form a throttling and/or a branch connection designed to form a buffer volume. The mechanical low-pass filter 7 preferably has a low cut-off frequency with respect to the control frequency of the injector Finj, said cut-off frequency being determined by the choice of the mechanical low-pass filter and by the choice of the dimensions of the tank 2 and pipe 5.
Periodic injection of droplets of precursor into the chamber is controlled by a control circuit 4. The control circuit 4 comprises outputs respectively connected to the tank and to the injector to control at least one of the control parameters chosen from the pressure P in the tank and more particularly the thrust pressure Pgas on which the pressure P in the tank depends, the injector opening time tint, also called injection time, and the injection frequency Finj. The control circuit 4 further comprises a regulation control input connected to the output of the flowmeter 6 in such a way as to control at least one of the control parameters, i.e. the thrust pressure Pgas and/or the injection time tinj and/or the injection frequency Finj, so that the mean flowrate measured Qmmeas by the flowmeter 6 no longer oscillates and corresponds to a flowrate setpoint Qmc(t) which can for its part vary with time. The mean injection flowrate is thereby regulated around a predetermined set-point Qmc from measurement of the flowrate Qmmeas.
In a particular embodiment represented in
A device such as the one represented in
The curve E1 is made up of a series of rectangular pulses the period whereof shifts from T1 to T2 when the frequency is modified. The curve E2 is made up of two portions of straight lines invariant with time and offset from one another when Finj is modified. It can also be observed that, when the injection frequency Finj is modified, the variation of the flowrate measured by the flowmeter (curve F1) is slowed down in comparison with the mean flowrate over an injection period, at the level of the injector (Curve E2). It is the mechanical low-pass filter that causes this slowing-down. Taking account of the transfer function H1 of the mechanical low-pass filter enables the variation of the flowrate measured by the flowmeter to be corrected and therefore speeded up to mathematically reconstitute a corrected mean flowrate (Curve F2), by means of the correction circuit 8, which is close to the mean flowrate at the level of the injector (Curve E2).
The injection device 1 can also comprise a regulation circuit of the pressure in the tank 2 and more particularly of the thrust pressure Pgas. Precise control of the thrust pressure does in fact enable the stability and control of the mean injected liquid flowrate to be improved, whatever the type of mean flowrate regulation chosen: both when a constant thrust pressure Pgas is maintained and the injector control parameters tinj and Finj are varied, and when the thrust pressure Pgas is varied and the injector control parameters tinj and Finj are kept constant.
As illustrated in
The valves 14 and 15 are for example fast-acting piezoelectric valves or injectors like the one used for injecting the droplets into the chamber, the switching time of such valves being very fast, for example less than 1 ms. The valves are preferably controlled in Pulse Width Modulation (PWM) manner in such a way as to inlet or remove predetermined small quantities of gas to and from the tank 2. The pressure regulation circuit 12 comprises for example a difference logic circuit supplying an error signal between the set-point Pgas and the measured pressure Pm. The error signal is then corrected by two digital correctors respectively controlling the inlet and outlet valves.
The digital correctors in practice calculate the opening time of the valves from the difference between the pressure set-point and the pressure measured in the tank.
The digital correctors preferably depend on the gas volume situated above the precursor in liquid form contained in the tank 2, on the effective fluid conductances of the inlet and outlet valves, on the thrust gas pressure, on the pressure in the tank, on the pressure at the level of the outlet valve, and on the iteration frequency of the regulation loop. Optimization of the digital correctors according to these different parameters thus enables the thrust pressure of the liquid to be maintained very precisely and typically to within a few ppm.
Such an injection device enables discontinuous or mode pulsed injection of precursor droplets into the chamber to be obtained, with a variable droplet volume, in the following cases:
The invention is not limited to the embodiments described above. Thus, as represented in
Number | Date | Country | Kind |
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0408704 | Jun 2004 | FR | national |
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/FR05/02049 | 8/5/2005 | WO | 00 | 1/26/2009 |