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    • 专利摘要:
    Procedure for obtaining a solid material with gaseous aggregates by means of cathodic sputtering by magnetron under static or quasi-static conditions to reduce gas consumption. The present invention refers to a process for obtaining a solid material with gaseous aggregates embedded in it, where said aggregates are embedded inside nanopores and/or at the grain boundaries of the solid, by cathodic spraying by magnetron, in a static or quasi-static regime. The present invention is framed in processes of the metallurgical industry, and/or processes of obtaining materials with other embeds (nanocomposites) by spraying. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2761148A1
    申请号:ES201831107
    申请日:2018-11-15
    公开日:2020-05-18
    发明作者:CAMACHO Mª ASUNCION FERNANDEZ；Dirk Hufschmidt；Godinho Vanda Cristina Fortio；DE HARO Mª CARMEN JIMENEZ
    申请人:Consejo Superior de Investigaciones Cientificas CSIC；
    IPC主号:
    专利说明:

    [0002] Procedure for obtaining a solid material with gaseous aggregates by means of cathodic spraying by magnetron in static or quasi-static conditions to reduce gas consumption
    [0004] The present invention refers to a process for obtaining a solid material with gaseous aggregates embedded in it, where said aggregates are embedded inside nanopores and / or at the grain boundaries of the solid, by cathodic spraying by magnetron, in a static or quasi-static regime. The present invention is framed in processes of the metallurgical industry, and / or processes of obtaining materials with other embeds (nanocomposites) by spraying.
    [0006] BACKGROUND OF THE INVENTION
    [0008] Layer deposition by magnetron sputtering, or "magnetron sputtering", is based on the intense bombardment of a material with the ions produced in an electrical discharge in the form of plasma. When the energy of the incident ions is sufficiently high , the interaction with the surface of the material (through the exchange of the kinetic moment) causes the atoms of the surface to be removed, to pass to the vapor phase. The atoms removed travel to the surface of the substrate and there they condense. In general, a working gas is used at reduced pressure or under vacuum to produce the discharge. In the vast majority of cases, a determined working pressure is adjusted with a working gas flow. With the controlled gas flow and the connection to the Vacuum pump establishes a dynamic equilibrium The advantages, a priori, of this method are the easy control of the pressure, the constant renewal of the working gas and the elimination of contaminations.
    [0010] Previously, it has been reported that it is possible to make solid materials (typically silicon) with gaseous aggregates (typically He) contained in them by dynamically spreading magnetron sputtering. See references: i) R. Schierholz; B. Lacroix; V. Godinho; J. Caballero-Hernández; M. Duchamp and A. Fernández. "STEM-EELS analysis reveals stable high-density He in nanopores of amorphous Silicon coatings deposited by magnetron sputtering ”. Nanotechnology, Volume 26, Number 7 (2015) 075703. ii) A. Fernández and V. Godinho, Procedure for obtaining coatings by sputtering and coating obtainable by said procedure, ES2347123 (B1).
    [0012] Helium spraying of W and C in a dynamic regime with incorporation of He has also been described (V. Tiron, C. Andrei, AV Nastuta, GB Rusu, C. Vitelaru and G. Popa, XXIIIrd Int. Symp. On Discharges and Electrical Insulation in Vacuum -Bucharest - 2008).
    [0014] In contrast to the advantages of the dynamic working method, described above, the main disadvantage of this is the high consumption of working gas when using a constant process gas renewal flow (typically a flow of between 20 mL / min and 120 mL / min). This is a major problem when it is necessary to incorporate gases whose content in nature is scarce, which are expensive, toxic, explosive and / or radioactive. These gases can be, for example, hydrogen, nitrogen or the noble gases (helium, neon, etc.) and especially their isotopes (deuterium, tritium, helium-3, neon-21, etc.). Specifically, the materials made up of these isotopes incorporated into a solid matrix could be used to investigate, for example, the properties of nuclei far from the stability line ("exotic" nuclei), as well as in general, in the study of reactions. nuclear.
    [0016] The standard procedure for magnetron sputtering deposition always recommends working in a dynamic regime (RVStuart, Vacuum Technology, Thin Films, and Sputtering, Academic Press, 1983) in order to maintain greater cleanliness in the deposition chamber. On the other hand TH Baum, CE Larson and RL Jackson in "Laserinduced chemical vapor deposition of aluminum", Applied Physics Letters 55, 1264 (1989) have described the use of static conditions in a different deposition method, such as the CVD technique ( chemical deposition from vapor phase) assisted by laser, which has also not been applied to obtain materials that incorporate gas aggregates. Finally DW Hoffman in "A sputtering wind", Journal of Vacuum Science & Technology A 3, 561 (1985) describes a Mo sputtering process with Ar process gas working in a static vacuum regime, but only for the purpose of studying the gas convection currents in the chamber. In no case is the effect of the process conditions on the material compared obtained or the methodology is not related to low consumption processes for special gases.
    [0018] There is, therefore, a need in view of the state of the art, associated with the high consumption of working gases, especially in the manufacture of layers containing aggregates of special gases, and which until now has not been resolved.
    [0020] DESCRIPTION OF THE INVENTION
    [0022] The present invention deals with a procedure under static or quasi-static conditions, of deposition of layers by sputtering by magnetron to obtain a solid material with gas aggregates, where said aggregates are embedded inside nanopores and / or at the borders grain of the solid. Said procedure is carried out in a magnetron sputtering deposition chamber under static or quasi-static conditions. The method thus minimizes the expense of working gas by avoiding constant gas renewal.
    [0024] Additionally, the following advantages of this static (or quasi-static) cathodic spray deposition procedure have been found with respect to the state of the art:
    [0025] - the consumption in the amount of the working gas is reduced in the method of the present invention with respect to that described by the traditional methods of dynamic gas flow. The gas consumption in the process presented here reaches at most 0.5% of the consumption in the dynamic regime. This allows its application for work gases whose content is scarce in nature, expensive, toxic, explosive and / or radioactive.
    [0026] - the content of trapped working gas presents values in atoms / cm2 comparable (even higher in some cases) to the values described operating in the traditional mode in dynamic flow;
    [0027] - the highest deposition rate that is achieved with the method of the present invention compared to those described in the state of the art (dynamic);
    [0028] - the content of impurities and residual contaminations in the layers obtained by the process of the present invention, surprisingly equals or even improves in some cases, with respect to the processes described in the state of the art of dynamic gas flow;
    [0030] In a first aspect, the present invention refers to a process for obtaining a solid material with gaseous aggregates where said aggregates are embedded inside nanopores and / or at the grain boundaries of the solid, by cathodic sputtering by magnetron in conditions static or quasi-static, characterized in that it is carried out in a deposition chamber comprising
    [0031] • a magnetron, located in the upper zone of the deposition chamber and configured to generate a controllable magnetic field;
    [0032] • a target, attached to the magnetron, configured to house a solid element for use as a target;
    [0033] • a sample holder, located at a distance of between 8 and 10 cm from the target, configured so that a substrate is on it;
    [0034] • a shutter located between the target and the specimen holder and configured to move transversely to the direction between the target and the specimen holder;
    [0035] • a pressure sensor located on one of the sides of the chamber and configured to send a signal that indicates the internal pressure in the chamber;
    [0036] • valve located in an inlet line to the deposition chamber from a working gas bullet, configured to control the flow of working gas entering the deposition chamber;
    [0037] • valve connected to an outlet line to the vacuum pump, configured to control the gas that leaves the vacuum pump; and where said procedure comprises the following stages
    [0038] (a) introducing a solid element to be used as a target in the magnetron sputtering chamber, and a substrate selected from silicon, NaCl, metal foils, and SiC, on the sample holder;
    [0039] (b) close all the valves of the deposition chamber and vacuum the chamber after placing the solid as a blank in step (a) up to a pressure of at least 1-10 "4 Pa;
    [0040] (c) heating the deposition chamber once the necessary vacuum has been reached in step (b) to a temperature of between 80 ° C and 110 ° C for a time of between 6 h and 8 h, and then let it cool down to a temperature between 10 ° C and 30 ° C;
    [0041] (d) close the valve connected to the chamber vacuum pump, introduce the working gas into the deposition chamber after the heating stage (c) where said working gas is selected from 3He, 4He, He, 20Ne , 21Ne, 22Ne, Ne, H2, N2, Ar and any mixture of the above up to a working pressure of between 3 Pa and 7 Pa;
    [0042] (e) once the pressure described in the previous step (d) has been reached, and maintaining said working pressure in the chamber, the working gas flow is reduced, totally or partially closing the inlet and outlet valves, to and from the deposition chamber until a flow selected from
    [0043] • a flow of zero mL / min; or
    [0044] • a flow between 0.001 mL / min and 0.1 mL / min.
    [0045] (f) depositing the target material on the substrates by sputtering by generating a plasma by applying a discharge potential with a power of between 50 W and 300 W in radio frequency (rf) or continuous mode (dc), maintaining the working gas flow established in step (e), and the working pressure reached in step (d),
    [0046] (g) and remove the shutter from the deposition chamber if it is inserted, maintaining the deposition for times that can range from 1 to 6 h, depending on the target material to be deposited and the working gas;
    [0047] (h) turn off the electric current applied in the previous stage (f), keep the chamber empty (valve 3 closed and valve 2 open) for at least 12 h, and then, fill the chamber with Ar and O2 slowly and remove the solid material with gaseous aggregates.
    [0049] In the present invention, "nanopore" is understood to mean any closed pore in the final obtained material whose diameter is less than 100 nm. A closed pore is an occluded pore inside the material without communication with the external surface.
    [0050] In the present invention, "magnetron sputtering" is understood as the technique known in English as "magnetron sputtering". It is a deposition method based on the intense bombardment of a target with the ions produced in an electric discharge in the form of plasma. This bombardment causes the atoms of the target material to be “sputtered” to the surface of a substrate where they condense, growing a material.
    [0052] This procedure is carried out in a generalized way with a continuous entry of the working gas into the chamber, in equilibrium with a continuous pumping, and maintaining the required working pressure in the so-called dynamic regime. This methodology produces the consequent expense of working gases.
    [0054] In the present invention, “static conditions or static equilibrium” are understood to be those in which deposition by sputtering by magnetron is performed with the valves connected to the working gas line and to the vacuum pump line, and that In the present invention, these are valves 2 and 3 in Fig. 1, practically closed during the entire process with small adjustments to compensate for fluctuations in internal pressure, making gas flow through these two valves insignificant. versus the total volume of the gas in the chamber. The principle of this method is therefore to fill the chamber with a volume of working gas until reaching the determined pressure. A static balance is established in the chamber and only this volume of gas is operated. If there are fluctuations in internal pressure due to the spraying process itself, due to thermal effects and others, they are also regulated with the valves connected to the gas tank and the vacuum pump.
    [0056] In the present invention, "quasi-static or stationary equilibrium conditions" are understood to be those in which the entire deposition process by sputtering by magnetron is carried out with low flows, that is, adjustable between 0.001 mL / min and 0.1 mL / min at most at the working gas inlet while controlling the working pressure by carefully opening valve 3 to increase the pressure and valve 2 to lower it. In this way, it is possible to maintain the deposition conditions with minimum inflows or minimum outflows, avoiding the constant flow of gas renewal. If there are fluctuations in internal pressure due to the spraying process itself, Thermal and other effects are also regulated with the valves connected to the gas tank and the vacuum pump.
    [0058] The static (or quasi-static) balance method requires several modifications to the conventional configuration of the magnetron sputtering device:
    [0059] - Placement of a very fine control needle valve (valve 3, Fig. 1) at the gas inlet to the chamber. A second on-off valve can be optionally placed next to the needle valve for safety. The valve that controls the gas that goes out to the vacuum pump (valve 2, Fig. 1) is a component of the conventional set-up necessary in any working mode.
    [0060] - Placement of a small volume tank for the working gas (tank in Fig. 1). This tank optimizes the control of gas consumption but can be optional.
    [0061] - Introduce the automatic control of the working pressure by combining the signal from the pressure sensor (8 in Fig. 1) with the automatic control of valves 2 and 3 (Fig. 1). This modification is optional, but it would allow optimizing the process minimizing gas consumption.
    [0063] In the present invention, "He or He gas" is understood to mean the natural composition that mainly has 4He.
    [0065] In the present invention, "3He" is understood to mean the corresponding pure isotope.
    [0067] In the present invention, "4He" is understood to mean the corresponding pure isotope.
    [0069] In the present invention, the term "Ne or Ne gas" is understood to mean the natural composition that presents mostly 20Ne.
    [0071] In the present invention, "20Ne" is understood to mean the corresponding pure isotope.
    [0073] In the present invention, "21Ne" is understood to mean the corresponding pure isotope.
    [0075] In the present invention, "22Ne" is understood to mean the corresponding pure isotope.
    [0076] In the present invention, a “solid element to be used as a target” is understood to mean any element that has a melting point higher than 500 ° C, where said temperature range is determined because the targets are going to be subjected to high temperatures by ion bombardment during the deposition process, but below those 500 ° C, so that these elements are kept in a solid state.In the present invention, these elements are selected, but not limited to, from Si, Cu, Co, Ti, Au, Al, W, Pt, Ta, B and C.
    [0078] In a preferred embodiment, the procedure for obtaining a solid material with gaseous aggregates comprises, additionally after step (b) and prior to step (c), purging the chamber and the working gas inlet lines with emptying-filling cycles and final pressurization of the lines. In this way, an efficient removal of impurities and contaminants in the gas lines is carried out to improve the quality of the material obtained by the present procedure.
    [0080] In another preferred embodiment, the process for obtaining a solid material with gaseous aggregates also includes an additional step for cleaning the target after step (c) and prior to step (d), for which a shutter is placed between the target and the sample holder, a flow of 20 mL / min of Ar is introduced into the chamber up to a pressure of between 4 Pa and 5.5 Pa, we maintain this flow for 5 min, and lower it to 5 mL / min, up to a pressure of 2 Pa Applying a power to the magnetron of between 150 and 250 W for a time of between 0.4 h and 0.6 h, we proceed to clean the target before establishing the deposition conditions (static or quasi-static) and at the beginning of the deposition with removal of the shutter. This additional cleaning is aimed at the efficient removal of impurities and contaminants in the "sputtering" target and thus improve the quality of the material obtained by the present procedure.
    [0082] In another preferred embodiment of the method of the present invention, two movable shutters configured to be placed between white and substrate are used, one just in front of the magnetron and the other on the substrate. This arrangement optimizes the suppression of deposits on the substrate during the processes of cleaning the target and establishing the deposition conditions.
    [0083] In another preferred embodiment of the process of the present invention, the working gas of step (d) is 3He. Working in static conditions minimizes the consumption of expensive and scarce gases such as 3He and 21Ne. The manufacture of the solid targets of these elements, and their isotopes, is not evident as they are noble gases that do not form solid bonds. The present invention makes it possible to have these solid targets with advantages for use, for example, in neutron detectors or for the study of nuclear reactions.
    [0085] In another preferred embodiment of the process of the present invention, the solid element used as a target can be selected from Si, Cu, Co, Ti, Au, Al, W, Pt, Ta, B and C. In a more preferred embodiment the solid element used as a target is Yes. In another more preferred embodiment the solid element used as the target is W.
    [0087] In another preferred embodiment of the process of the present invention, the distance between the solid element to be used as a target and the sample holder is 10 cm to optimize the growth rate and the homogeneity of the layer.
    [0089] In another preferred embodiment of the process of the present invention, the substrate of step (a) is NaCl, where the use of said NaCl substrate has the advantage that the final obtained solid material with gaseous aggregates is peeled off as a self-supporting layer by detachment in water and can later be supported on a frame.
    [0091] In another preferred embodiment of the method of the present invention, in the event of fluctuations in the working pressure above 10%, said working pressure is adjusted to the desired value using the valve located in an inlet line to the deposition of the working gas to increase said working pressure and connected to an outlet line to the vacuum pump to reduce said working pressure. This procedure guarantees the homogeneity of the coating.
    [0093] In another preferred embodiment of the method of the present invention, in step (d) the working gas is introduced into the deposition chamber from a tank located between the working gas bale and the deposition chamber and this tank is previously refilled with working gas. In this way the control is optimized on gas consumption.
    [0095] In another preferred embodiment of the method of the present invention, in step (d) the working gas is introduced into the deposition chamber by automatic control of the working pressure by combining the signal from the pressure sensor with the automatic control of the valves . This allows to optimize the process minimizing the consumption of working gas.
    [0097] In another preferred embodiment of the process of the present invention, in the event that the final solid material with gaseous aggregates is more than 1 pm thick, depending on the deposition rate of each material, the process can be carried out by repeating stages (d) to (f) during successive depositions, or in stages over several days, turning off the magnetron discharge at the end of each deposition. In a more preferred embodiment, a white cleaning is applied prior to each stage of filling the working gas in step (d), before the start of each deposition to optimize the removal of impurities and improve the quality of the layer.
    [0099] Throughout the description and claims, the word "comprises" and its variants are not intended to exclude other technical characteristics, additives, components or steps. For those skilled in the art, other objects, advantages, and features of the invention will emerge in part from the description and in part from the practice of the invention. The following examples and figures are provided by way of illustration, and are not intended to be limiting of the present invention.
    [0101] BRIEF DESCRIPTION OF THE FIGURES
    [0103] FIG. 1 Representative diagram of the experimental equipment designed for the deposition process in static or quasi-static regime for low gas consumption.
    [0105] FIG. 2 Si and 4He layers grown at 150 W of power in rf mode, with working gas pressure of 5 Pa, with a distance of 10 cm between the target and the sample holder: (left) with dynamic procedure for 10 hours and (right) with static procedure for 3 hours.
    [0107] FIG. 3 Layers of W and 4He grown to 200 W of power in rf mode, with pressure of 5 Pa working gas, with a distance of 10 cm between the target and the sample holder for 5.5 hours: (left) with dynamic procedure and (right) with static procedure.
    [0109] FIG. 4 W and 3He layer grown on silicon substrate, for 10 hours by quasi-static procedure, at 200 W of power in rf, at working gas pressure of 5 Pa and with a distance of 10 cm between the target and the sample holder. On the left is a high resolution micrograph obtained by transmission electron microscopy (TEM) showing pores with various sizes containing the gas. The pores in TEM appear with whiter contrast.
    [0111] FIG. 5 Si and 3He layer grown on silicon substrate with SiC interlayer, for 12 hours by quasi-static procedure, at 150 W of power in rf, at working gas pressure of 5 Pa and with a distance of 10 cm between the target and the sample holder. On the right is an enlarged scanning electron microscope (SEM) micrograph showing the pores containing the gas.
    [0113] EXAMPLES
    [0115] Next, the invention will be illustrated by means of tests carried out by the inventors, which demonstrate the effectiveness of the product of the invention.
    [0117] Example 1
    [0119] Preparation under static conditions of W layers with He
    [0121] For illustrative purposes of the different components of the experimental system used, reference is made to the scheme represented in FIG. 1 which shows the different components and terms used throughout the description of the present invention.
    [0123] W's blank is placed in the chamber 10 cm away from the sample holder with silicon substrates and metal foil. A vacuum is made in the chamber up to 10-5 Pa as well as in the gas lines if necessary, with the knife gate valve (2) fully open. Then raise the pressure to 8 Pa with Argon (16), lower the pressure to at least 10 "4 Pa, and repeat 3 times. The pressure is lowered to the minimum, for 24 h and heated up to 110 ° C, with the help of a heater (13) and controlling the temperature with the temperature sensor (11-12) for 7 h and then let it cool completely.
    [0125] Place the shutter (7) in position between the target and the sample holder and establish a flow of 12 mL / min of Ar up to a pressure of 5 Pa, we maintain this flow for 5 min, and we lower it to 5 mL / min, up to a pressure 2 Pa. Turn on the plasma with an electric current power of 200 W RF and thus clean the target for 30 min. Turn off the discharge and cut off the Ar flow, lowering the pressure to 10-4 Pa.
    [0127] Subsequently, a static pressure of 5 Pa is established, measured with a pressure sensor (8), closing the knife valve (2) and entering the working gas (15). Previously, the ball valve (4) has been opened and the working gas has been introduced into a tank (10), which is a 50 mL tank, where it is checked with another pressure sensor (9). Subsequently, with the valve (3) and the guillotine valve (2) practically closed during the entire process, the desired pressure is established in the deposition chamber.
    [0129] Apply a discharge current at 200 W in RF to ignite the plasma in the magnetron with its target (5). In case it does not turn on add a small volume of Ar until reaching a chamber pressure of 6-7 Pa by carefully opening the shut-off valve (1) of the Ar line (16) (with the remaining pressure in the line ) and apply the discharge current again. Increase the pressure with the working gas to 8-9 Pa with the needle valve (3), then lower it to 4 Pa and raise it again by repeating this cycle 5 to 10 times until the plasma color is completely green-white , at which time the desired working pressure is established by keeping the plug inserted.
    [0131] To start the deposition process, the plug (7) is removed from between the blank and the sample holder (6), regulating the pressure with the needle valve (3) (raise) and the knife valve (2) (lower) to the value Default to 5 Pa in case of fluctuations.
    [0133] If the deposition is of long time, the time is divided into several days, repeating the process every day since the shutter is placed before the beginning of the deposition.
    [0134] To finish the deposition, turn off the plasma, close the needle valve (3) and fully open the sash valve (2) and wait a minimum of 12 h before flooding the chamber with Argon to remove the sample.
    [0136] Example 2
    [0138] Comparison example: Preparation under dynamic conditions of W layers with He
    [0140] Initial procedure the same as in the static process.
    [0142] The target is cleaned with Ar as in static with the shutter in position between the target and the specimen holder.
    [0144] The plasma and Ar flow are turned off, lowering the pressure to 10-4 Pa.
    [0146] A dynamic He pressure of 5 Pa is established with the gas inlet of up to 120 mL / min with the valve (3) open and the outlet controlling the guillotine valve (2) partially open. The plasma is turned on by applying a discharge current power of 200 W RF. If it does not turn on, add a small volume of Ar and stabilize by removing all of the Ar slowly. Maintain the He plasma with shutter for 30 min to complete cleaning of the target and removal of Ar residues.
    [0148] It goes to growth conditions of 60 mL / min of He input and pressure control of 5 Pa with the guillotine valve (2) partially open.
    [0150] To start the deposition process, the shutter is removed from between the blank and the sample holder, maintaining the growth conditions for the desired time.
    [0152] To finish the deposition, turn off the plasma, close the valve (3) and fully open the sash valve (2) and wait a minimum of 12 h before flooding the chamber with Argon to remove the sample
    [0153] Example 3.
    [0155] Example of comparison of the obtaining speed and composition of the silicon materials with He obtained with the static and dynamic deposition processes
    [0157] Static and dynamic depositions of silicon layers with He have been carried out in equal conditions of material, power, gas and working pressure. A conventional bottle of He was used which is therefore mostly 4He. A comparative study of the growth rate, the He content and the level of impurities has been carried out as described below.
    [0159] A layer was grown under dynamic conditions following the procedure described in Example 2 with the following conditions: Si target, working pressure 5Pa, magnetron power 150W in RF, working distance 10 cm, deposition time 10 hours. The resulting layer is shown in Fig. 2 (left). The thickness of the layer has been determined by scanning electron microscopy (SEM), resulting in a growth rate of 5.5 nm / min. The incorporation of He and the impurities present have been determined by IBA analysis (characterization with ion beams), finding atomic ratios of He / Si = 0.5 and O / Si = 0.09. Other impurities have been found well below the oxygen values: Fe / Si = 0.01, C / Si = 0.006, N / Si = 0.01.
    [0161] A layer was grown under static conditions following the procedure described in Example 1 with the following conditions: Si blank, working pressure 5Pa, magnetron power 150W in RF, working distance 10 cm, deposition time 3 hours. The resulting layer is shown in Fig. 2 (right). The thickness of the layer has been determined by scanning electron microscopy (SEM), resulting in a growth rate of 6.5 nm / min. The incorporation of He and the impurities present have been determined by IBA analysis (characterization with ion beams), finding atomic ratios of He / Si = 0.6 and O / Si = 0.08. Other impurities have been found well below the oxygen values: Fe / Si = 0.01. C and N contents have been determined below 2% at.
    [0162] Static work, other things being equal, gives improvements in the speed of growth which favors low gas consumption. Likewise, comparable (even higher) He content values are obtained while the impurity contents remain similar and in some cases they have presented improvements by reducing the amount of oxygen.
    [0164] Example 4.
    [0166] Example of comparing the speed of obtaining the tungsten materials with He obtained with the static and dynamic deposition processes
    [0168] Static and dynamic depositions of tungsten layers with He have been carried out in equal conditions of material, power, gas and working pressure. A conventional bottle of He was used which is therefore mostly 4He. A comparative study of growth rate has been carried out.
    [0170] A layer was grown under dynamic conditions following the procedure described in Example 2 with the following conditions: W blank, working pressure 5Pa, magnetron power 200W RF, working distance 10 cm, deposition time 5.5 hours. The resulting layer is shown in Fig. 3 (left). The thickness of the layer has been determined by scanning electron microscopy (SEM), resulting in a growth rate of 0.4 nm / min.
    [0172] A layer was grown under static conditions following the procedure described in Example 1 with the following conditions: W blank, working pressure 5Pa, magnetron power 200W RF, working distance 10 cm, deposition time 5.5 hours. The resulting layer is shown in Fig. 3 (right). The thickness of the layer has been determined by scanning electron microscopy (SEM), resulting in a growth rate of 2 nm / min.
    [0174] Static work under equal conditions gives very important improvements in growth speed, which favors low gas consumption.
    [0175] Example 5.
    [0177] Example of manufacturing a tungsten layer containing 3He in a quasi-static process with low consumption
    [0179] Given the importance of the low gas consumption working method for scarce and very expensive gases, but of great strategic relevance such as 3He, an example of the embodiment of the invention is presented for the case of a tungsten layer containing 3He. The solid target of W: 3He would have application for studies of nuclear physics and for neutron detectors.
    [0181] A layer was grown under quasi-static conditions following the general procedure described under the following conditions: W blank, silicon substrate, working pressure 5Pa of 3He gas, magnetron power 200W in RF, working distance 10cm, deposition time 10 hours. Throughout the deposition process, flows of less than 0.1 mL / min were maintained at the working gas inlet while controlling the working pressure by carefully opening valve 3 to increase the pressure and valve 2 to lower it.
    [0183] The microstructure of the layer has been studied by transmission electron microscopy (TEM) and scanning (SEM). Two representative micrographs are shown in Fig. 4 where the porous structure of the coating can be seen. A thickness of 620 nm has been obtained, note that this layer is grown with 3He instead of 4He, therefore the expected growth rate is less than that of its analog layer grown with 4He. This solid white obtained has been characterized by EBS and ERD techniques (IBA techniques) resulting in an estimated gas mass thickness (3He) of 2.65x1017 at / cm2 and metal mass thickness (W) of 23.45x1017 at / cm2. This corresponds to an effective thickness of 1.33 pg / cm2 of 3He. Regarding impurities, this sample contains 2.3 at% of 4He and presents atomic ratios O / W = 0.14; H / W = 0.17; C / W = 0.05 and N / W = 0.0
    [0185] This sample has been irradiated with a 64Zn beam at 275 MeV with an intensity of 5 pnA for 12 hours without significant visual signs of sample damage.
    [0186] Example 6.
    [0188] Example of manufacturing a layer of silicon containing 3He in a quasi-static process with low consumption
    [0190] Given the importance of the low gas consumption working method for scarce and very expensive gases, but of great strategic relevance such as 3He, an example of the embodiment of the invention is presented for the case of a silicon layer containing 3He. The solid white of Si: 3He would have application for studies of nuclear physics and for neutron detectors.
    [0192] A layer was grown under quasi-static conditions following the general procedure described under the following conditions: Si blank, Si substrate with SiC interlayer, 5Pa working pressure of 3He gas, magnetron power 150W in RF, working distance 10cm, deposition time 12 hours. Throughout the deposition process, flows of less than 0.1 mL / min were maintained at the working gas inlet while controlling the working pressure by carefully opening valve 3 to increase the pressure and valve 2 to lower it.
    [0194] The microstructure of the layer has been studied by scanning electron microscopy (SEM). Two representative micrographs are shown in Fig. 5 where the porous structure of the coating can be seen. A thickness of 1.9 pm has been obtained, note that this layer is grown with 3He instead of 4He, so the expected growth rate is less than that of its analogous layer grown with 4He. This solid white obtained has been characterized by the EBS technique (IBA technique), resulting in an estimated gas mass thickness (3He) of 1.28x1018 at / cm2 and matrix mass thickness (Si) of 6.38x1018 at / cm2. This corresponds to an effective thickness of 6.4 pg / cm2 of 3He. Regarding impurities, this sample contains 2.0 at% of 4He and presents atomic ratios O / Si = 0.0 and C / Si = 0.04
    权利要求:
    Claims (14)
    [1]
    1.- Procedure for obtaining a solid material with gaseous aggregates where said aggregates are embedded inside nanopores and / or at the grain boundaries of the solid, by cathodic spraying by magnetron in static or quasi-static conditions, characterized in that carried out in a deposition chamber comprising
    • a magnetron, located in the upper zone of the deposition chamber and configured to generate a controllable magnetic field;
    • a target, attached to the magnetron, configured to house a solid element for use as a target;
    • a sample holder, located at a distance of between 8 and 10 cm from the target, configured so that a substrate is on it;
    • a shutter located between the target and the specimen holder and configured to move transversely to the direction between the target and the specimen holder;
    • a pressure sensor located on one of the sides of the chamber and configured to send a signal that indicates the internal pressure in the chamber;
    • valve located in an inlet line to the deposition chamber from a working gas bullet, configured to control the flow of working gas entering the deposition chamber;
    • valve connected to an outlet line to the vacuum pump, configured to control the gas that leaves to a vacuum pump; and where said procedure comprises the following stages
    (a) introducing a solid element to be used as a target in the magnetron sputtering chamber, and a substrate selected from silicon, NaCl, metal foils, and SiC, on the sample holder;
    (b) close all the valves of the deposition chamber and vacuum the chamber after placing the solid as a blank in step (a) up to a pressure of at least 1-10 "4 Pa;
    (c) heating the deposition chamber once the necessary vacuum has been reached in step (b) to a temperature of between 80 ° C and 110 ° C for a time of between 6 h and 8 h, and then let it cool down to a temperature between 10 ° C and 30 ° C;
    (d) close the valve connected to the chamber vacuum pump, introduce the working gas into the deposition chamber after the heating stage (c) where said working gas is selected from 3He, 4He, He, 20Ne , 21Ne, 22Ne, Ne, H2, N2, Ar and any mixture of the above up to a working pressure of between 3 Pa and 7 Pa;
    (e) once the pressure described in the previous step (d) has been reached, and maintaining said working pressure in the chamber, the working gas flow is reduced, totally or partially closing the inlet and outlet valves to and from the deposition chamber until a flow selected from
    • a flow of zero mL / min; or
    • a flow between 0.001 mL / min and 0.1 mL / min;
    (f) depositing the target material on the substrates by sputtering by generating a plasma by applying a discharge potential with a power of between 50 W and 300 W in radio frequency (rf) or continuous mode (dc), maintaining the working gas flow established in step (e), and the working pressure reached in step (d);
    (g) and remove the shutter from the deposition chamber if it is inserted, maintaining the deposition for times that can range from 1 to 6 h, depending on the target material to be deposited and the working gas;
    (h) turn off the electric current applied in the previous stage (f), keep the chamber empty (valve 3 closed and valve 2 open) for at least 12 h, and then, fill the chamber with Ar and O2 slowly and remove the solid material with gaseous aggregates.
    [2]
    2.- Procedure for obtaining a solid material with gaseous aggregates according to claim 1, characterized in that it also comprises a step after step (b) and prior to step (c) of carrying out purges of the chamber and of the working gas inlet lines with empty-fill cycles and final pressurization in the gas lines.
    [3]
    3. - Procedure for obtaining a solid material with gaseous aggregates according to any of claims 1 or 2, characterized in that it further comprises an additional step of cleaning the target after step (c) and prior to step (d).
    [4]
    4. - Procedure for obtaining a solid material with gaseous aggregates according to any of claims 1 to 3, where two mobile shutters are used between white and substrate, one in front of the magnetron and the other on the substrate.
    [5]
    5. - Procedure for obtaining a solid material with gaseous aggregates according to any of claims 1 to 4, where the working gas is 3He.
    [6]
    6. - Procedure for obtaining a solid material with gaseous aggregates according to any of claims 1 to 5, wherein the solid element used as the target of step (a) is selected from Si, Cu, Co, Ti, Au, Al, W, Pt, Ta, B and C.
    [7]
    7. - Procedure for obtaining a solid material with gaseous aggregates according to claim 6, where the solid element used as the target of step (a) is Si.
    [8]
    8. - Procedure for obtaining a solid material with gaseous aggregates according to claim 6, wherein the solid element used as the target of step (a) is W.
    [9]
    9. - Procedure for obtaining a solid material with gaseous aggregates according to any of claims 1 to 8, where the distance between the target and the sample holder is 10 cm.
    [10]
    10. - Procedure for obtaining a solid material with gaseous aggregates according to any of claims 1 to 9, wherein the substrate located on the sample holder of step (a) is NaCl.
    [11]
    11. - Procedure for obtaining a solid material with gaseous aggregates according to any of claims 1 to 10, where in step (d) the working gas is introduced into the deposition chamber from a tank located between the gas bullet of working and deposition chamber and this tank has been previously filled with working gas.
    [12]
    12. - Procedure for obtaining a solid material with gaseous aggregates according to any of claims 1 to 11, where in step (d) the working gas is introduced into the deposition chamber by automatic control of the working pressure, combining the signal from a pressure sensor and through automatic valve control.
    [13]
    13. - Procedure for obtaining a solid material with gaseous aggregates according to any of claims 1 to 12, where the final solid material with gaseous aggregates is more than 1 pm thick, the process can be carried out by repeating steps (d) a (f) during successive depositions by turning off the magnetron discharge potential at the end of each deposition.
    [14]
    14. - Procedure for obtaining a solid material with gaseous aggregates according to claim 13, where a white cleaning is applied prior to each stage of filling of the working gas (d) for the start of each deposition.
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    同族专利:
    公开号 | 公开日
    ES2761148B2|2020-10-28|
    WO2020099695A1|2020-05-22|
    EP3882372A1|2021-09-22|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2002058858A1|2000-11-08|2002-08-01|Advanced Technology Materials, Inc.|Non-plasma $mi$min situ$m/i$m cleaning of processing chambers using static flow methods|
    WO2017207848A1|2016-05-31|2017-12-07|Consejo Superior De Investigaciones Científicas |Solid target of noble gases for nuclear reactions|
    ES2347123B1|2009-04-22|2011-09-22|Consejo Superior De Investigaciones Cientificas 50%|PROCEDURE FOR OBTAINING COATINGS THROUGH CATHODIC SPRAYING AND COVERING OBTAINABLE THROUGH SUCH PROCEDURE.|
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    ES201831107A|ES2761148B2|2018-11-15|2018-11-15|PROCEDURE FOR OBTAINING A SOLID MATERIAL WITH GASEOUS AGGREGATES BY CATHODIC SPRAYING BY MAGNETRON UNDER STATIC OR QUASISTATIC CONDITIONS TO REDUCE GAS CONSUMPTION|ES201831107A| ES2761148B2|2018-11-15|2018-11-15|PROCEDURE FOR OBTAINING A SOLID MATERIAL WITH GASEOUS AGGREGATES BY CATHODIC SPRAYING BY MAGNETRON UNDER STATIC OR QUASISTATIC CONDITIONS TO REDUCE GAS CONSUMPTION|
    EP19884840.0A| EP3882372A1|2018-11-15|2019-10-28|Method for obtaining a solid material with gaseous aggregates by means of magnetron cathode sputtering in static or quasistatic conditions to reduce the use of gas|
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