CN114981473A - Platinum group metal recovery method, method for producing platinum group metal-containing film, and film forming apparatus - Google Patents

Platinum group metal recovery method, method for producing platinum group metal-containing film, and film forming apparatus Download PDF

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CN114981473A
CN114981473A CN202180010030.9A CN202180010030A CN114981473A CN 114981473 A CN114981473 A CN 114981473A CN 202180010030 A CN202180010030 A CN 202180010030A CN 114981473 A CN114981473 A CN 114981473A
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film
platinum group
gas
group metal
film forming
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CN114981473B (en
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真锅俊树
泉浩一
荘所正
永山谅太郎
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Iwatani Corp
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    • C22B11/00—Obtaining noble metals
    • C—CHEMISTRY; METALLURGY
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    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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    • C23C16/4401—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber
    • C23C16/4405—Cleaning of reactor or parts inside the reactor by using reactive gases
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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    • C23C16/4412—Details relating to the exhausts, e.g. pumps, filters, scrubbers, particle traps
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Abstract

Provided are a platinum group metal recovery method, a method for producing a platinum group metal-containing film, and a film forming apparatus. A method for recovering a platinum group metal, which is a method for introducing a raw material gas containing a platinum group metal into a film forming chamber, forming a platinum group metal-containing film on the surface of a substrate accommodated in the film forming chamber, and then recovering the platinum group metal present in the film forming chamber, the method comprising: (i) introducing a cleaning gas containing fluorine into the film forming chamber from which the substrate is taken out; and (ii) introducing the cleaning gas discharged from the film forming chamber into a trap container holding a trapping agent composed of at least one selected from the group consisting of soda lime, slaked lime, and CaO.

Description

Platinum group metal recovery method, method for producing platinum group metal-containing film, and film forming apparatus
Technical Field
The present invention relates to a method for recovering platinum group metals, a method for producing a platinum group metal-containing film, and a film forming apparatus. The present invention is based on and claims the benefit of priority from Japanese application No. 2020-095296, filed on 6/1/2020, which is hereby incorporated by reference in its entirety.
Background
A method of forming a metal-containing film such as ruthenium on a surface of a substrate by a Chemical Vapor Deposition (CVD) method is known. In forming the metal-containing film, a source gas of an organic metal compound is introduced into a film forming chamber, and the metal-containing film is formed on the surface of the substrate accommodated in the film forming chamber. In this process, it is considered that about 10% of the organometallic compound introduced into the chamber forms a metal film on the surface of the substrate. The excess organometallic compound is discharged from an exhaust pipe of the film forming chamber and is deposited in the film forming chamber.
In order to improve the recovery efficiency of noble metals such as ruthenium during film formation, it has been proposed to trap metal compounds discharged from an exhaust pipe during the film formation step. Patent document 1 describes a CVD film forming process including: a step of recovering an organic metal compound by bringing an exhaust gas containing a reaction product generated in the film formation step and an unreacted raw material gas into contact with a solvent and an adsorbent; next, the organometallic compound is separated and purified.
In addition, a dry cleaning method is known in which deposits in a film forming chamber are removed by using a chlorine-based or fluorine-based cleaning gas. However, for safety reasons, the cleaning gas discharged from the film formation chamber cannot be introduced into the trap for trapping the metal compound in the source gas during cleaning. Therefore, the metal compounds contained in the cleaning gas are not recovered. Therefore, patent document 2 proposes to suppress the number of times of dry cleaning or to omit the dry cleaning process itself by making the inside of the film formation chamber a specific structure.
[ Prior art documents ]
[ patent document ]
Patent document 1: japanese patent laid-open No. 2001 and 342566.
Patent document 2: japanese patent laid-open publication No. 2011-192661.
Disclosure of Invention
Problems to be solved by the invention
However, there is no method of performing dry cleaning in a film forming chamber and recovering the noble metal contained in the cleaning gas by using a film forming chamber of the related art, and there is a limit to the recovery efficiency of the noble metal used in film formation.
The object of the present invention is to provide a method for safely recovering precious metals contained in a clean gas. Another object of the present invention is to provide a method for producing a metal film and a film-forming apparatus, which have high recovery efficiency of precious metals.
Means for solving the problems
A method for recovering a platinum group metal according to the present invention is a method for recovering a platinum group metal present in a film forming chamber after introducing a raw material gas containing a platinum group metal into the film forming chamber and forming a platinum group metal-containing film on a surface of a substrate accommodated in the film forming chamber, the method comprising:
(i) introducing a cleaning gas containing fluorine into the film forming chamber from which the substrate is taken out; and
(ii) and introducing the cleaning gas discharged from the film forming chamber into a trap container holding a trapping agent containing at least one selected from the group consisting of soda lime, slaked lime, and CaO.
The method for producing a platinum group metal-containing film according to the present invention includes:
(I) introducing a raw material gas containing a platinum group metal into a film forming chamber, and forming a platinum group metal-containing film on a surface of a substrate accommodated in the film forming chamber;
(II) taking out the substrate on which the platinum group metal-containing film is formed from the film formation chamber; and
(III) a step of recovering the platinum group metal present in the film-forming chamber,
the step (III) of recovering the platinum group metal present in the film forming chamber is carried out by the above-mentioned method of recovering the platinum group metal.
Further, a film forming apparatus according to the present invention includes:
a film formation chamber for forming a thin film on a surface of a substrate;
a gas supply mechanism connected to the film formation chamber;
a gas exhaust mechanism connected to the film forming chamber; and
a control unit that controls the film formation chamber, the gas supply mechanism, and the gas discharge mechanism,
the gas supply mechanism includes:
a first supply pipe that supplies a raw material gas containing a platinum group metal to the film formation chamber; and
a second supply pipe that supplies a cleaning gas containing fluorine to the film formation chamber,
the gas discharge mechanism includes:
a first exhaust pipe connecting the film formation chamber and a first trap device capable of trapping platinum group metals contained in the raw material gas discharged from the film formation chamber; and
and a second exhaust pipe connecting the film formation chamber and a second trap device holding a trapping agent capable of trapping a platinum group metal contained in the cleaning gas discharged from the film formation chamber.
Effects of the invention
According to the method for recovering platinum group metals of the present invention, the platinum group metals contained in the clean gas can be recovered. In addition, according to the method for producing a platinum group metal-containing film and the film forming apparatus of the present invention, the platinum group metal in the clean gas can be recovered, and the recovery efficiency of the platinum group metal is high.
Drawings
Fig. 1 is a schematic diagram illustrating a connection state of pipes in an example of an embodiment of a film formation apparatus.
Fig. 2 is a schematic diagram illustrating a connection state in control in an example of the embodiment of the film formation apparatus.
FIG. 3 is a flowchart showing an example of an embodiment of a method for producing a platinum group metal-containing film.
Fig. 4 is a schematic diagram showing a connection state of pipes in an example of the embodiment of the film formation apparatus.
Detailed Description
In the present specification, "platinum group metal" does not refer to only the simple substance of the platinum group metal, but refers to a chemical species containing the platinum group metal including ions, compounds and complexes. For example, "ruthenium" does not refer to only the simple substance of metallic ruthenium, but refers to a chemical species containing ruthenium that contains ruthenium ions, ruthenium compounds, and ruthenium complexes. However, when a specific compound name (for example, ruthenium fluoride, ruthenium oxide, or the like) is described, the name is not limited thereto.
[ summary of embodiments ]
A method for recovering a platinum group metal according to the present invention is a method for recovering a platinum group metal present in a film forming chamber after introducing a raw material gas containing a platinum group metal into the film forming chamber and forming a platinum group metal-containing film on a surface of a substrate accommodated in the film forming chamber, the method comprising:
(i) introducing a cleaning gas containing fluorine into the film forming chamber from which the substrate is taken out; and
(ii) and introducing the cleaning gas discharged from the film forming chamber into a trap container holding a trapping agent composed of at least one selected from the group consisting of soda lime, slaked lime, and CaO.
In the prior art, a method of safely recovering the noble metals contained in the cleaning gas is not known, and the noble metals contained in the cleaning gas are not recovered. In addition, a method and a film forming apparatus for producing a metal film having excellent recovery efficiency of precious metals are required. The inventors have studied this problem repeatedly, and have conceived that, when forming a platinum group metal film, an exhaust pipe for discharging a cleaning gas during cleaning is provided in addition to an exhaust pipe for discharging a raw material gas during film formation. Further, it was confirmed that the platinum group metals contained in the cleaning gas discarded in the prior art can be recovered by connecting a trap device housing a trapping agent capable of trapping the platinum group metals (platinum group metal fluorides) fluorinated by the cleaning gas containing fluorine to the pipe, and the recovery efficiency of the platinum group metals in the method for producing a platinum group metal film can be improved.
The method for recovering a platinum group metal according to the present invention comprises: (i) introducing a cleaning gas containing fluorine into the film forming chamber from which the substrate is taken out; and (ii) introducing the cleaning gas discharged from the film forming chamber into a second trap container holding a trapping agent composed of at least one selected from the group consisting of soda lime, slaked lime, and CaO. With this configuration, the platinum group metals contained in the clean gas can be captured without the clean gas passing through the first capturing device that can capture the platinum group metals contained in the raw material gas. With this configuration, the platinum group metals contained in the clean gas can be recovered without safety problems.
In the above method for recovering platinum group metals, soda lime may be used as a capturing agent. When the trapping agent is soda lime, the recovery efficiency of the platinum group metal fluorinated by the cleaning gas is excellent, and the cleaning gas containing fluorine can be reliably rendered harmless, and the safety is excellent.
In the above method for recovering a platinum group metal, the platinum group metal may be ruthenium or osmium. In the case where the platinum group metal is ruthenium or osmium, a high-quality thin film with less defects can be obtained, and dry cleaning can be performed at a relatively low temperature in the recovery step.
In the above method for recovering platinum group metals, ClF can be used 3 As a cleaning gas. ClF 3 As a dry cleaning gas for film formation of platinum group metals, many practical results have been obtained, and dry cleaning can be reliably performed under mild conditions.
The method for recovering a platinum group metal may further comprise (iii) a step of removing a platinum group metal from the capturing agent after the steps (i) and (ii). In step (iii), the platinum group metal is separated from the capturing agent into a metal compound, and can be reused as a film forming raw material after further purification or other treatment.
The method for recovering platinum group metals may include a step of removing the trapping vessel from the film forming apparatus, and then introducing a strong acid into the trapping agent to extract the platinum group metal fluoride adsorbed on the trapping agent as an aqueous platinum group metal solution. By this step, the platinum group metal can be recovered from the capturing agent by a simple procedure using a general-purpose material, and the practical applicability is excellent.
The method for producing a platinum group metal-containing film according to the present invention comprises:
(I) introducing a raw material gas containing a platinum group metal into a film forming chamber, and forming a platinum group metal-containing film on the surface of a substrate accommodated in the film forming chamber;
(II) a step of taking out the substrate on which the platinum group metal-containing film is formed from the film formation chamber; and
(III) a step of recovering the platinum group metal present in the film-forming chamber,
the step (III) of recovering the platinum group metal present in the film forming chamber can be carried out by a recovery method of the platinum group metal.
According to the above production method, the film formation step of the platinum group metal-containing film, the substrate removal step, and the step of collecting the platinum group metal present in the film formation chamber can be continuously performed as a series of steps. Further, the platinum group metal can be recovered without changing the configuration of the film forming chamber of the conventional art. Therefore, the recovery efficiency of the platinum group metal as the whole production method can be improved without changing or readjusting the film forming step rule.
In the above manufacturing method, the structure may be such that: the step (I) of forming the platinum group metal-containing film and the step (II) of taking out the substrate from the film formation chamber are sequentially repeated a plurality of times, and thereafter the step (III) of recovering the platinum group metal present in the film formation chamber is performed. With this configuration, excessive dry cleaning is not required, the number of steps can be reduced, and the amount of raw materials such as dry cleaning gas can be reduced.
The film forming apparatus according to the present invention includes: a film formation chamber for forming a thin film on a surface of a substrate; a gas supply mechanism connected to the film formation chamber; a gas discharge mechanism connected to the film forming chamber; and a control unit that controls the film formation chamber, the gas supply mechanism, and the gas discharge mechanism. The gas supply mechanism includes: a first supply pipe that supplies a raw material gas containing a platinum group metal to the film formation chamber; and a second supply pipe that supplies a cleaning gas containing fluorine to the film formation chamber. The gas discharge mechanism is provided with a first exhaust pipe and a second exhaust pipe. The first exhaust gas pipe connects the film formation chamber and a first trap device capable of trapping platinum group metals contained in the raw material gas exhausted from the film formation chamber. The second exhaust pipe connects the film formation chamber and a second trap device that holds a trapping agent capable of trapping a platinum group metal contained in the cleaning gas discharged from the film formation chamber. The film forming apparatus of the present invention can suitably perform the above-described platinum group metal recovery method and the above-described platinum group metal-containing film production method.
In the above manufacturing method, the second trap device may be detachable from the second exhaust pipe. By making the second trap device detachable, the platinum group metal can be taken out at a time independent of the film forming step at a place different from the place where the film forming chamber and the gas supply mechanism are installed. In addition, the second capturing means can be easily replaced. For example, by using a plurality of trap apparatuses while replacing them, it is possible to recover platinum group metals without affecting the time management of the film formation step.
[ specific examples of embodiments ]
Hereinafter, embodiments of the present invention will be described with reference to the drawings. In the drawings, the same or corresponding portions are denoted by the same reference characters, and description thereof will not be repeated.
[ film Forming apparatus ]
Fig. 1 is a diagram schematically showing a connection state of pipes in one embodiment of a film deposition apparatus according to the present invention. The film forming apparatus of the present invention can form a film containing a platinum group metal such as a ruthenium-containing film and an osmium-containing film, and the film forming apparatus of the present invention uses Ru as an example 3 (CO) 12 Gas as ruthenium raw material gas, ClF was used 3 Gas is taken as an example of a cleaning gas containing fluorine.
The film forming apparatus 1 is a film forming apparatus for forming a ruthenium-containing film by a CVD method. Referring to fig. 1, a film deposition apparatus 1 includes: a film forming chamber 10; a gas supply mechanism 20 for supplying a source gas and a cleaning gas to the film formation chamber 10; and a gas exhaust mechanism 50 for exhausting the raw material gas and the cleaning gas from the film formation chamber 10. Referring to fig. 2, the film formation chamber 10, the gas supply mechanism 20, and the gas exhaust mechanism 50 are controlled by the controller 100.
The film forming chamber 10 may be a single-wafer type film forming chamber or a batch type film forming chamber as long as it has a function of forming a ruthenium-containing film by a CVD method. The film formation chamber 10 includes a door (not shown) for carrying in and out substrates to be processed, and a heater (not shown) for setting the temperature in the chamber to a predetermined temperature.
Referring to fig. 1, the film formation chamber 10 is connected to the gas supply mechanism 20 via a first supply pipe 91 and a second supply pipe 92 of the gas supply mechanism 20. The first supply pipe 91 is configured to supply a source gas containing ruthenium for forming a ruthenium-containing film by CVD to the film formation chamber 10. The second supply pipe 92 is configured to supply a cleaning gas containing fluorine to the film formation chamber 10.
In the embodiment shown in fig. 1, the first supply pipe 91 and the second supply pipe 92 are connected to the film formation chamber 10, respectively, but the first supply pipe 91 and the second supply pipe 92 may be joined at a position upstream of the film formation chamber 10 and may be provided at one gas supply port of the film formation chamber 10. When the first supply pipe 91 and the second supply pipe 92 are merged at the upstream side of the film formation chamber 10, valves may be provided in the first supply pipe 91 and the second supply pipe 92, respectively, to switch from which of the first supply pipe 91 and the second supply pipe 92 the gas is supplied.
The film formation chamber 10 is connected to the gas exhaust mechanism 50 via the first exhaust pipe 75 and the second exhaust pipe 76 of the gas exhaust mechanism 50. The first exhaust pipe 75 is provided to exhaust gas exhausted from the film forming chamber 10 in the film forming step. The second exhaust pipe 76 is provided to exhaust the gas exhausted from the film forming chamber 10 in the cleaning step.
In the embodiment shown in fig. 1, the first exhaust pipe 75 and the second exhaust pipe 76 are connected to the film formation chamber 10, respectively, or the first exhaust pipe 75 and the second exhaust pipe 76 may be branched downstream of the gas discharge port of the film formation chamber 10 as one portion.
The gas supply mechanism 20 will be explained.
The gas supply mechanism 20 is a mechanism for supplying a raw material gas for forming a ruthenium-containing film by the CVD method and a cleaning gas for cleaning the film formation chamber 10 to the film formation chamber 10. The gas supply mechanism 20 has a storage Ru 3 (CO) 12 As a solidA film forming raw material container 45 for containing the film forming raw material P in a body form. A heater 46 is provided around the film forming material container 45. Ru contained in film-forming material container 45 3 (CO) 12 Heated by the heater 46 and gasified into Ru 3 (CO) 12 Gas (ruthenium carbonyl gas). A carrier gas supply pipe 25 for supplying CO gas as a carrier gas is inserted from above into the film forming material container 45. A carrier gas supply source 24 for supplying CO gas is connected to the carrier gas supply pipe 25. Further, a source gas supply pipe 26 is inserted into the film formation source container 45. The carrier gas supply pipe 25 is provided with a mass flow controller 31 for flow control and valves 44a and 44b in front of and behind the mass flow controller. In addition, the raw material gas supply pipe 26 is provided with a device for detecting Ru 3 (CO) 12 A flow meter 35 for the gas amount, and a valve 44c capable of adjusting the opening and closing based on the measurement value of the flow meter 35.
The gas supply mechanism 20 includes an additional gas supply source 23 for supplying Ar as a diluent gas and an additional gas supply pipe 27. The additional gas supply pipe 27 connects the additional gas supply source 23 to the raw material gas supply pipe 26 and the first supply pipe 91. The additional gas supply source 23 side of the additional gas supply pipe 27 is provided with a mass flow controller 32 for flow rate control and valves 43a and 43b in front of and behind the mass flow controller.
With the above-described configuration, the film-forming material container 45 is supplied with Ru 3 (CO) 12 The source gas (2) can be supplied to CO gas as a carrier gas, mixed with Ar gas, and supplied into the film forming chamber 10 through the first supply pipe 91. The carrier gas supply pipe 25 may be branched to introduce the CO gas as a reverse gas into the film forming chamber 10 separately from the raw material gas.
The gas supply mechanism 20 has a function of supplying a ClF used as a cleaning gas 3 A clean gas supply source 22 for gas and a clean gas supply pipe 28. The cleaning gas supply pipe 28 connects the cleaning gas supply source 22 to the carrier gas supply pipe 29 and the second supply pipe 92. A mass flow controller 33 for flow rate control and valves 42a and 42b before and after the mass flow controller are provided on the cleaning gas supply source 22 side of the cleaning gas supply pipe 28.
ClF as cleaning gas 3 The gas is delivered by Ar gas supplied as a carrier gas from the carrier gas supply source 21. One end of the carrier gas supply pipe 29 is connected to the carrier gas supply source 21, and the other end of the carrier gas supply pipe 29 is connected to the cleaning gas supply pipe 28 and the second supply pipe 92. A mass flow controller 34 for flow rate control and valves 41a and 41b before and after the mass flow controller are provided on the carrier gas supply source 21 side of the carrier gas supply pipe 29.
With the above-described configuration, the ClF supplied from the clean gas supply source 22 3 The gas can be carried by the Ar gas and supplied into the film forming chamber 10 through the second supply pipe 92.
The gas discharge mechanism 50 will be explained.
The gas exhaust mechanism 50 is a mechanism for exhausting the raw material gas and the cleaning gas after the dry cleaning, which are supplied after the film formation, from the film formation chamber 10. The gas discharge mechanism 50 includes a first trap device 51 connected to the film formation chamber 10 via a first exhaust pipe 75. The first trap device 51 can trap ruthenium contained in the raw material gas discharged from the film formation chamber 10. The first trap 51 is specifically configured as a cold trap, for example. When the first trap 51 is a cold trap, water can be used as the refrigerant. Instead of using the refrigerant, a vacuum trap having a cooling surface may be used as the first trap 51.
A dry pump 61 is connected to the first trap 51 via a pipe. The dry pump 61 exhausts the gas from the film formation chamber 10 based on a measurement value of a pressure gauge (not shown), and maintains the inside of the film formation chamber 10 at a predetermined pressure.
The dry pump 61 is connected to a detoxifying device 80 via a pipe. The detoxifying device 80 detoxifies the raw material gas containing CO gas and ruthenium that cannot be captured by the first capture device 51. The specific form of the harmful means 80 is, for example, a combustion type harmful means. The CO gas supplied to the detoxifying device 80 is incinerated in the detoxifying device 80 as CO 2 The gas is vented to the atmosphere. As the harm removing device, a heating type harm removing device such as a plasma type harm removing device or a heater type harm removing device can be used in addition to the combustion type harm removing device.
In the embodiment of fig. 1, the first exhaust pipe 75 is connected to the first trap device 51, but an auxiliary trap device may be provided in the middle of the first exhaust pipe 75. Further, a dry pump may be disposed upstream of the first trap device 51, and the first trap device 51 may be set at atmospheric pressure.
The gas exhaust mechanism 50 includes a second trap 52 connected to the film formation chamber 10 via a second exhaust pipe 76. The second trap 52 is, for example, a dry-type detoxifying device that holds the individual granular trapping agent 53 in a container made of stainless steel. The trapping agent 53 is a trapping agent capable of trapping ruthenium contained in the cleaning gas discharged from the film formation chamber 10 at the time of cleaning the film formation chamber 10.
The capturing agent 53 is preferably at least one selected from the group consisting of soda lime, slaked lime, and CaO (calcium oxide), and is more preferably soda lime. By using these substances as the trapping agent 53, ruthenium (ruthenium fluoride) contained in the cleaning gas and fluorinated by the fluorine-based cleaning gas can be trapped as ruthenium oxide. In addition, ClF can be captured by the capturing agent 53 3 And (5) removing the harm.
The second trap 52 includes a clean gas introduction pipe 77. The cleaning gas introduction pipe 77 is connected to the second exhaust pipe 76 via the flange 54a, and is inserted into the trapping agent 53. The second capturing device 52 is provided with an outlet pipe 78. The outlet pipe 78 discharges the detoxified gas having passed through the trapping agent 53. The outlet pipe 78 is provided with a flange 54 b. At the position of the flanges 54a, 54b, the second capture device 52 is detachable from the second exhaust pipe 76. Since the second trap device 52 can be detached from the second exhaust pipe 76, the ruthenium can be taken out from the trapping agent 53 in a state where the second trap device 52 is separated from the film formation apparatus 1. That is, the ruthenium can be separated and purified from the trapping agent 53 at a place different from the place where the film forming apparatus is installed, and at a time independent of the film forming step.
In the embodiment of fig. 1, when the second capturing device 52 has not only the capturing function of ruthenium but also the detoxifying function of fluorine compounds, the second capturing device 52 does not need to be connected to the detoxifying device 80, and expensive stainless piping does not need to be used. As a result, the fluorine compound is not mixed into the poisoning device 80, and therefore, corrosion is not caused, and the maintenance frequency can be reduced.
Next, the connection of control in the embodiment shown in fig. 1 will be described with reference to fig. 1 and 2.
Referring to fig. 2, the film formation apparatus 1 includes a film formation chamber 10, a gas supply mechanism 20, a gas exhaust mechanism 50, and a control unit 100.
The control unit 100 functions as a flow path control device of the film forming apparatus, and controls the entire film forming apparatus from the plurality of gas supply sources and the film forming material containers to the abatement device through the film forming chamber. The control unit 100 controls the open/close states of the valves 41a to 44a, 41b to 44b, and 44c included in the gas supply mechanism 20, thereby adjusting the types, mixing ratios, and flow rates of the raw gas and the clean gas supplied from the gas supply mechanism 20. The control unit 100 receives the measurement value signal from the flowmeter 35 and adjusts the open/close state of the valve 44c based on the measurement value. The controller 100 controls the heater 46 included in the gas supply mechanism 20 to adjust the temperature in the film formation material container 45.
The control unit 100 also controls the operation of a heater, a susceptor, a door, and the like provided in the film formation chamber 10 to perform film formation according to a predetermined protocol. In these operations, the control unit 100 can receive measurement value signals from a temperature sensor, a pressure sensor, and the like provided in the film formation chamber 10, and adjust the on/off, degree, and timing of the operations based on the measurement values.
The control unit 100 also controls the open/close states of the plurality of valves 71, 72, 73 included in the gas discharge mechanism 50. The controller 100 controls the output of the pumps 61 and 62 included in the gas discharge mechanism 50. The control unit 100 adjusts and maintains the pressure in the film forming chamber 10 and the pipe connected thereto to a predetermined value by adjusting the output of the pumps 61 and 62. The flow rates and pressures of the raw material gas and the cleaning gas supplied to the film formation chamber 10 and the flow rates and pressures of the raw material gas after film formation and the cleaning gas after film formation discharged from the film formation chamber 10 are adjusted by controlling the outputs of the pumps 61 and 62.
[ Material for use in film Forming method ]
[ Material for use in film formation ]
The metal film formed in the film forming apparatus of the present invention is a film containing a platinum group metal, and examples of the platinum group metal include ruthenium, osmium, iridium, and platinum. Ruthenium-containing films or osmium-containing films are particularly preferred.
In the case of forming a ruthenium-containing film, various organic and inorganic gases can be used as the ruthenium source gas. For example, ruthenium carbonyl (Ru) can be used more preferably 3 (CO) 12 )。Ru 3 (CO) 12 The gas is thermally decomposed into Ru. In this case, it is more preferable to use CO gas as Ru 3 (CO) 12 A carrier gas for the gas. By using CO as a carrier gas, Ru in the processing container can be suppressed 3 (CO) 12 Decomposition reaction of gas, and Ru can be maintained as much as possible 3 (CO) 12 The film is formed by supplying the film to the substrate to be processed. Also can be made of Ru 3 (CO) 12 The gas reacts with the reaction gas to form a ruthenium-containing film other than the ruthenium film.
As the ruthenium raw material gas, in addition to Ru 3 (CO) 12 Besides, RuO can be mentioned 2 、Ru(EtCp) 2 、Ru(DMDB)(CO) 3 、RuO 4 (HFE)、Ru(HDAC)、Ru(PF 3 )、Ru(AMD) 2 CO, RuCOT, etc., Ru-containing can be used 3 (CO) 12 At least one of these raw materials.
The reaction gas for forming a ruthenium-containing film other than ruthenium film is appropriately selected depending on the ruthenium raw material gas and the ruthenium-containing film to be obtained. The reaction gas may be, for example, CO 2 、O 2 、H 2 、SiH 4 、Si 2 H 6 、Si 3 H 8 、Si 4 H 10 、NH 3 、CH 3 (NH)NH 2 、C 2 H 8 N 2 、N 2 H 4 Etc., at least one of them can be used.
In the use of CO 2 、O 2 、H 2 In the case of using the ruthenium oxide film as a reaction gas, a ruthenium film or a ruthenium oxide film can be formed. In the use of SiH 4 、Si 2 H 6 、Si 3 H 8 、Si 4 H 10 In the case of using as the reaction gas, a ruthenium film containing Si can be formed. In the use of NH 3 、CH 3 (NH)NH 2 、C 2 H 8 N 2 、N 2 H 4 In the case of using the ruthenium compound as a reactive gas, a ruthenium film containing N can be formed. In addition, a doped ruthenium film can also be formed using a gas containing a dopant.
In the case of forming a ruthenium simple film, no reaction gas is used. In the case of forming a ruthenium single-layer film, N can be used as a carrier gas for diluting and transporting a raw material gas 2 Inert gases such as gas and noble gas. Examples of the rare gas include Ar, He, Ne, Xe, and Kr.
[ Material for use in cleaning ]
In the recovery method and the production method of the present invention, a cleaning gas containing fluorine is used as the cleaning gas. As the cleaning gas containing fluorine, ClF can be preferably used 3 . As ClF 3 Other cleaning gases include F 2 、F 2 /N 2 Mixed gas, NF excited in plasma state 3 、CF 4 、C 2 F 6 、C 3 F 8 、SF 6 And the like. These fluorine-containing cleaning gases may be used alone or in combination of two or more.
In the cleaning, a carrier gas that transports the above-described cleaning gas may also be used. As the carrier gas, N can be used 2 Inert gases such as gases and noble gases. Examples of the rare gas include Ar, He, Ne, Xe, and Kr.
[ film Forming method ]
A method for producing a ruthenium-containing film according to an embodiment of the present invention will be described with reference to fig. 1 to 3.
Fig. 3 is a flowchart showing a method for manufacturing a ruthenium-containing film as one embodiment of the present invention. As shown in fig. 3, the manufacturing method according to the present embodiment includes: a step S10 of forming a ruthenium-containing film on a substrate; a step S20 of taking out the substrate from the film formation chamber; a step S30 of introducing a cleaning gas into the film formation chamber; and a step S40 of introducing the cleaning gas into the trapping vessel.
The step S10 of forming a ruthenium-containing film on a substrate will be explained. In the film forming step S10, the control unit 100 executes the following operation.
In the film forming step S10, the substrate is transported into the film forming chamber 10 of the film forming apparatus 1, and the dry pump 61 of the heater and the gas exhaust mechanism 50 provided in the film forming chamber 10 is operated to set the inside of the film forming chamber 10 to a predetermined temperature and pressure. At this time, Ar, which is a carrier gas of the purge gas, may be introduced into the film forming chamber 10 by opening the valves 43a and 43 b. The pressure in the film forming chamber 10 in the film forming step S10 can be, for example, 10 to 100Pa, and the temperature can be, for example, 120 to 250 ℃.
At the same time or subsequently, the heater 46 of the film forming material container 45 is operated to heat the film forming material P (Ru) 3 (CO) 12 ) So as to gasify the mixture. Further, the valves 44a and 44b are opened, and CO gas is blown into the film forming material container 45 through the carrier gas supply pipe 25. Ru in film Forming Material Container 45 3 (CO) 12 The gas is supplied into the film forming chamber 10 through the source gas supply pipe 26 and the first supply pipe 91 while being carried by the CO gas. Ru 3 (CO) 12 The flow rate of the gas is measured by the flow meter 35, and the control unit 100 can change the open/close state of the valve 44c based on the measured value. The control unit 100 can supply the additional gas (diluent gas) from the additional gas supply source 23 by adjusting the open/close state of the valves 43a and 43 b. The flow rate of the raw material gas and the mixing ratio of the raw material gas and the diluent gas can be appropriately set according to the target ruthenium-containing film thickness, the type of the substrate, and the like.
By the above-described operation, a ruthenium-containing film having a predetermined film thickness is formed on the surface of the substrate placed in the film formation chamber 10.
In the film forming step S10, the valves 41a, 41b, 42a, and 42b of the gas supply mechanism 20 are closed, and the gas from the second supply pipe 92 to the film forming chamber 10 is cut off.
While the film forming step S10 is being performed, the valve 71 is opened and the valve 72 is closed. That is, in the film forming step S10, the gas discharged from the film forming chamber 10 is discharged through the first exhaust pipe 75. The gas discharged from the film formation chamber in the film formation step S10 includes a source gas and a diluent gas. When a reaction gas is used as the additional gas, the exhaust gas also contains a reaction product of ruthenium and the reaction gas.
The exhaust gas in the film forming step S10 passes through the first trap device 51, and ruthenium contained in the exhaust gas is trapped in the first trap device 51. The ruthenium trapped in the first trap 51 is generally considered to be about 70% of the ruthenium used as a film forming raw material. The exhaust gas after passing through the first capturing device 51 mainly contains CO gas.
The exhaust gas having passed through the first trap device 51 reaches the detoxifying device 80 via the dry pump 61. In the detoxifying device 80, the exhaust gas is detoxified by, for example, incineration and precipitation separation, and is discharged into the atmosphere.
In the film forming step S10, the valves 72 and 73 of the gas discharge mechanism 50 are closed, and the dry pump 62 is stopped. That is, the off gas in the film forming step S10 is not discharged to the second exhaust pipe 76.
The step S20 of taking out the substrate from the film formation chamber will be described.
After the film formation step S10, the substrate having the ruthenium-containing film formed on the surface thereof is taken out of the film formation chamber 10. This step can be performed by a known method, and is not particularly limited, and for example, the raw material gas may be supplied into the film formation chamber 10 in the film formation step S10, and after a predetermined time (for example, 1 to 600 seconds) has elapsed, the substrate may be taken out from the film formation chamber 10, and a state in which no substrate is present in the film formation chamber 10 may be obtained.
After repeating the film formation step S10 and the removal step S20 one or more times, it is determined whether or not cleaning in the film formation chamber is performed. Specifically, for example, it is determined whether or not the deposition amount of ruthenium in the film formation chamber 10 exceeds an allowable amount (step Q10). The judgment criterion may be, for example, the number of repetitions of film formation (the number of film formations), or the elapsed time from the start of film formation. If it is determined that the deposition amount of ruthenium in the film formation chamber 10 is within the allowable range (no in step Q10), the film formation step S10 and the removal step S20 are performed again.
On the other hand, if it is determined that the deposition amount of ruthenium in the film formation chamber 10 exceeds the allowable range (yes in step Q10), the method of recovering ruthenium present in the film formation chamber is performed. Specifically, step S30 of introducing the cleaning gas into the film formation chamber and step S40 of introducing the cleaning gas into the trapping vessel are performed.
The cleaning gas introduction step S30 is performed after the step S20 of taking out the substrate from the film formation chamber, in a state where no substrate is present in the film formation chamber 10. The inside of the film forming chamber 10 is heated to a predetermined temperature, for example, 150 to 250 ℃, by a heater of the film forming chamber 10.
In the cleaning gas introduction step S30, the valves 43a, 43b, 44a, 44b, and 44c of the gas supply mechanism 20 are closed, and the gas from the first supply pipe 91 to the film formation chamber 10 is cut off.
In the clean gas introduction step S30, the valve 71 of the gas discharge mechanism 50 is closed, and the clean gas is not discharged from the first exhaust pipe 75. If a clean gas is introduced into the first trap device 51 that traps ruthenium or the like, there is a risk of explosion, and therefore, introduction of the clean gas into the first exhaust pipe 75 is avoided.
In the cleaning gas introduction step S30, the dry pump 62 is operated to open the valves 41a and 41b first, and a carrier gas (for example, Ar gas) is supplied from the carrier gas supply source 21 to purge the inside of the film formation chamber 10. The pressure in the film forming chamber 10 is adjusted to 10 to 1000Pa, for example. In this state, ClF as a cleaning gas is used 3 Introduced into the film forming chamber 10, and dry cleaned.
Although not bound by any particular theory, it is believed that the following chemical reaction occurs during the dry cleaning, and ruthenium present in the film formation chamber 10 is discharged as ruthenium fluoride gas.
Ru+5/3ClF 3 →RuF 5 ↑+5/6Cl 2 ↑
In dry cleaning, the valves 41a and 41b are opened to flow Ar gas as a carrier gas, and the valves 42a and 42b are further opened to supply ClF 3 A gas. ClF 3 The gas flow rate can be appropriately set in accordance with the internal volume of the film formation chamber, the film thickness of the ruthenium film accumulated in the film formation chamber, and the like. ClF 3 The gas supply time is preferably 1 toThe number of repetitions is preferably in the range of 60sec about 1 to 100.
After the cleaning gas introduction step S30, or simultaneously with the cleaning gas introduction step S30, the valves 73, 79a, 79b are opened to introduce the cleaning gas into the second trap 52 (step S40). The second capture device 52 is disposed downstream of the dry pump 62, i.e., at atmospheric pressure. The cleaning gas introduced into the second capturing device 52 is introduced into the capturing agent 53 through the cleaning gas introduction pipe 77 and contacts the capturing agent 53.
The cleaning gas introduced into the capturing agent 53 contains ClF 3 And RuF 5 (ruthenium fluoride). The capturing agent 53 is at least one selected from the group consisting of soda lime, slaked lime, and CaO (calcium oxide), and captures ClF 3 And ruthenium fluoride, thereby detoxifying the cleaning gas.
Soda lime, also called soda lime, is a strongly basic solid particulate substance containing calcium hydroxide as a main component and water, potassium hydroxide, and sodium hydroxide. The composition of soda lime includes, for example, soda lime containing 75 to 85 wt% of calcium hydroxide, 10 to 20 wt% of water, 1 to 5 wt% of potassium hydroxide, and 1 to 5 wt% of sodium hydroxide.
Although not bound by any particular theory, it is believed that the following chemical reaction occurs when ruthenium fluoride is brought into contact with the capturing agent, and ruthenium fluoride becomes ruthenium oxide and is immobilized in the capturing agent.
Ca(OH) 2 +RuF 5 →CaF 2 +RuO 2 +CaCl 2
The clean gas removed in the second trap 52 is released to the atmosphere through the outlet pipe 78 of the second trap 52.
After repeating the cleaning gas introducing step S30 to the film forming chamber 10 and the cleaning gas introducing step S40 to the second trap device 52 one or more times, it is determined whether or not the trap device should be replaced. Specifically, it is determined whether or not the replacement timing of the second capturing device 52 has reached (step Q20). The determination criterion may be, for example, the number of repetitions of dry cleaning or the elapsed time from the start of use of the trap device. In addition, can also be based onFrom a gas detector (e.g. Cl) arranged in the second trap 52 2 Sensor) to determine the replacement time. If it is determined that the container replacement timing has not been reached (no in step Q20), the cleaning gas introduction step S30 into the film formation chamber 10 and the cleaning gas introduction step S40 into the second trap device 52 are performed again.
On the other hand, when it is determined that the container replacement timing has come (yes in step Q20), the valves 79a and 79b are closed, the pipes are cut at the flanges 54a and 54b, and the second trap device 52 is detached from the second exhaust pipe 76 (step S50). In order to easily move the detached capturing device, the second capturing device 52 is preferably provided with casters or the like.
After the second capture device 52 is detached from the second exhaust pipe 76, ruthenium is taken out from the capture agent 53 housed in the second capture device 52 (step S60). The ruthenium takeout step S60 can be performed independently of the ruthenium film production at a location different from the installation location of the film formation apparatus.
Specifically, the ruthenium removal step S60 can be performed by, for example, introducing a strong acid such as hydrochloric acid or sulfuric acid into the trapping agent 53 and flowing out the ruthenium oxide immobilized on the trapping agent as an aqueous ruthenium chloride solution.
The ruthenium chloride taken out can be reused as a ruthenium precursor for film formation after a predetermined treatment.
[ other embodiments ]
Fig. 4 shows a film deposition apparatus 100 according to another embodiment of the present invention. In the film forming apparatus 100, the film forming chamber 10 and the gas supply mechanism 20 are the same as those of the film forming apparatus 1 shown in fig. 1, and the description thereof is omitted.
The gas exhaust mechanism 500 in the film formation apparatus 100 includes a first exhaust pipe 75 and a second exhaust pipe 76. The downstream of the first exhaust pipe 75 is the same as the film forming apparatus 1, and the description thereof is omitted.
The second exhaust pipe 76 connects the film formation chamber 10 to the second trap device 520. The second trap 520 includes a clean gas introduction pipe 770. The cleaning gas introduction pipe 770 is connected to the second exhaust pipe 76 via a flange 540a, and is inserted into the trapping agent 530. The second trap 520 includes an outlet pipe 780. The outlet pipe 780 discharges the gas after the detoxification by the capturing agent 530. The outlet pipe 780 is provided with a flange 540 b. In the flange 540a, the second trap 520 is detachable from the second exhaust pipe 76. A pipe 731 is connected downstream of the flange 540 b. That is, the second trap 520 can be detached from the second exhaust pipe 76 and the pipe 731 at the positions of the flanges 540a and 540 b.
The second trap 520 is connected to the dry pump 620 via a pipe 731. That is, when the dry pump 620 is operated to perform dry cleaning, the second trap 520 is in a reduced pressure atmosphere. The downstream of the dry pump 620 is connected to the detoxifying device 800, and the gas discharged from the dry pump 620 is detoxified by the detoxifying device 800 and released into the atmosphere.
In the embodiment of fig. 4, the second capturing device 520 is connected to the poisoning device 800, and thus the poisoning function of the fluorine compound is not required and only ruthenium may be captured. In this case, since the alkali agent in the second trap 520 reacts with the fluorine compound, the amount of the fluorine compound mixed into the poisoning device 800 is reduced, thereby suppressing corrosion of the poisoning device 800.
[ examples ]
Hereinafter, examples will be described.
Using the film forming apparatus shown in FIG. 1, Ru was formed by the above-described film forming method 3 (CO) 12 The ruthenium film was formed by the gas and the CO gas. ClF for ruthenium film deposited on the wall of film forming chamber 3 Dry cleaning was performed as the cleaning gas. In the present example, ClF was used for each film formation process 3 The cleaning is performed, but whether or not the cleaning is performed may be determined based on the thickness of the ruthenium film deposited on the wall of the film forming chamber. In the dry cleaning, ruthenium was captured by using a capturing device containing soda lime in a stainless outer cylinder container.
After the dry cleaning, the trap apparatus was detached from the exhaust pipe for the cleaning gas, and the appearance of the trapping agent in the trap apparatus was observed. The color of the capturing agent changed to blackish brown, and it was confirmed that ruthenium fluoride was immobilized. Hydrochloric acid was added to the trapping agent, and ruthenium was recovered as an aqueous ruthenium chloride solution.
The ruthenium recovered in the dry cleaning was calculated to be about 10% of the ruthenium raw material used in the film formation. In the film forming method according to the related art, since ruthenium removed by dry cleaning is not recovered, the recovery efficiency of ruthenium was improved by about 10% in the present example as compared with the related art.
It should be understood that the embodiments disclosed herein are illustrative in all respects and not restrictive in any respect. The scope of the present invention is defined not by the above description but by the claims, and is intended to include all modifications within the meaning and scope equivalent to the claims.
[ industrial applicability ]
The method for recovering a platinum group metal, the method for producing a platinum group metal-containing film, and the film forming apparatus according to the present invention can be particularly advantageously applied to the production of a semiconductor by the CVD method.
Description of the symbols
1. 100, a film forming apparatus; 10. a film forming chamber; 20. a gas supply mechanism; 21. a carrier gas supply source; 22. a cleaning gas supply source; 23. an additional gas supply source; 24. a carrier gas supply source; 25. a carrier gas supply pipe; 26. a raw material gas supply pipe; 27. an additional gas supply pipe; 28. a clean gas supply pipe; 29. a carrier gas supply pipe; 31. 32, 33, 34, a mass flow controller; 35. a flow meter; 41a, 41b, 42a, 42b, 43a, 43b, 44a, 44b, 44c, 71, 72, 73, 79a, 79b, valves; 45. a film forming raw material container; 46. a heater; 50. 500, a gas discharge mechanism; 51. 52, 520, capture device; 53. 530, a capture agent; 54a, 54b, 540a, 540b, flange; 61. 62, 620, dry pump; 731. piping; 75. 76, an exhaust pipe; 77. 770, a clean gas introduction pipe; 78. 780, outlet piping; 80. 800, a pest eliminating device; 91. 92, supply piping.

Claims (11)

1. A method for recovering a platinum group metal, which is a method for introducing a raw material gas containing a platinum group metal into a film forming chamber, forming a platinum group metal-containing film on a surface of a substrate accommodated in the film forming chamber, and then recovering the platinum group metal present in the film forming chamber, the method comprising the steps of:
(i) introducing a cleaning gas containing fluorine into the film forming chamber from which the substrate is taken out; and
(ii) and introducing the cleaning gas discharged from the film forming chamber into a trap container holding a trapping agent composed of at least one selected from the group consisting of soda lime, slaked lime, and CaO.
2. The method for recovering platinum group metals according to claim 1, wherein the capturing agent is soda lime.
3. The method for recovering a platinum group metal according to claim 1 or 2, wherein the platinum group metal is ruthenium or osmium.
4. The recovery method of a platinum group metal according to any one of claims 1 to 3, wherein the cleaning gas is ClF 3 。
5. The method according to any one of claims 1 to 4, wherein, after (i) the step of introducing the cleaning gas into the film-forming chamber and (ii) the step of introducing the cleaning gas discharged from the film-forming chamber into the capturing vessel,
further comprising (iii) a step of removing the platinum group metal from the capturing agent.
6. The platinum group metal recovery process of claim 5, wherein said (iii) removing platinum group metals from said capture agent comprises: and a step of introducing a strong acid into the trapping agent after the trapping vessel is detached from the film forming apparatus, and thereby taking out the platinum group metal fluoride adsorbed to the trapping agent as a platinum group metal salt solution.
7. A method for producing a platinum group metal-containing film, comprising the steps of:
(I) introducing a raw material gas containing a platinum group metal into a film forming chamber, and forming a platinum group metal-containing film on a surface of a substrate accommodated in the film forming chamber;
(II) taking out the substrate on which the platinum group metal-containing film is formed from the film formation chamber; and
(III) a step of recovering platinum group metals present in the film-forming chamber,
the step of (III) recovering the platinum group metals present in the film-forming chamber is carried out by the method for recovering platinum group metals according to any one of claims 1 to 6.
8. The method according to claim 7, wherein (I) the step of forming the platinum group metal-containing film and (II) the step of removing the substrate from the film-forming chamber are performed repeatedly in this order,
thereafter, (III) a step of recovering platinum group metals present in the film forming chamber is carried out.
9. A film forming apparatus includes:
a film formation chamber for forming a thin film on a surface of a substrate;
a gas supply mechanism connected to the film formation chamber;
a gas exhaust mechanism connected to the film forming chamber; and
a control unit that controls the film formation chamber, the gas supply mechanism, and the gas discharge mechanism,
the gas supply mechanism includes:
a first supply pipe that supplies a raw material gas containing a platinum group metal to the film formation chamber; and
a second supply pipe that supplies a cleaning gas containing fluorine to the film formation chamber,
the gas discharge mechanism includes:
a first exhaust pipe connecting the film formation chamber and a first trap device capable of trapping platinum group metals contained in the raw material gas discharged from the film formation chamber; and
and a second exhaust pipe connecting the film formation chamber and a second trap device holding a trapping agent capable of trapping a platinum group metal contained in the cleaning gas discharged from the film formation chamber.
10. The film forming apparatus according to claim 9, wherein the scavenger is at least one selected from the group consisting of soda lime, slaked lime, and CaO.
11. The film formation apparatus according to claim 9 or 10, wherein the second trap apparatus is detachable from the second exhaust pipe.
CN202180010030.9A 2020-06-01 2021-05-28 Platinum group metal recovery method, method for producing platinum group metal-containing film, and film forming apparatus Active CN114981473B (en)

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JPS62238337A (en) * 1986-04-09 1987-10-19 Nichibi:Kk Method for recovering noble metal
JPS62273038A (en) * 1986-05-21 1987-11-27 Kanto Denka Kogyo Kk Treatment of chemical vapor deposition exhaust gas
JPH01142036A (en) * 1987-11-30 1989-06-02 Tanaka Kikinzoku Kogyo Kk Method for recovering platinum metal
JPH04311570A (en) * 1991-04-10 1992-11-04 Central Glass Co Ltd Film forming device provided with deposit recovering device
JPH10279317A (en) * 1997-03-31 1998-10-20 Korea Atom Energ Res Inst Method for removing ruthenium compound in industrial waste gas, and collecting material
JP2001342566A (en) * 2000-03-31 2001-12-14 Tanaka Kikinzoku Kogyo Kk Manufacturing process and apparatus of cvd thin film
US20020072211A1 (en) * 2000-12-13 2002-06-13 Hideharu Itatani Method of manufacturing semiconductor devices
CN1410589A (en) * 2001-09-28 2003-04-16 田中贵金属工业株式会社 Technique and equipment for making film by chemical vapour deposition process
JP2004190092A (en) * 2002-12-11 2004-07-08 Toyota Motor Corp Method and apparatus for recovering noble metal from waste
JP2006002174A (en) * 2004-06-15 2006-01-05 Hitachi Kokusai Electric Inc Substrate treatment apparatus
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