Film forming apparatus, film forming method, and film forming system

Abstract

To perform the deposition and etching of ruthenium with the same depositing apparatus and embed ruthenium on a substrate in a bottom-up manner.SOLUTION: A depositing apparatus includes: a processing container; a gas supplier configured to supply gas; and a gas exhauster configured to exhaust gas, wherein the depositing apparatus embeds ruthenium in a substrate having a recess. The gas supplier includes a first supply line configured to supply a gas containing a ruthenium raw-material gas into the processing container and a second supply line configured to supply a gas containing ozone gas into the processing container. The gas exhauster includes a first exhaust line including a first exhaust apparatus and configured to exhaust a gas containing a ruthenium raw-material gas from the interior of the processing container by using the first exhaust apparatus, and a second exhaust line including a second exhaust apparatus different from the first exhaust apparatus and configured to exhaust the gas containing ozone gas by using the second exhaust apparatus.SELECTED DRAWING: Figure 5

Description

Technical Field

[0001] The present disclosure relates to a film forming apparatus, a film forming method, and a film forming system.

Background Art

[0002] Low-resistance ruthenium (Ru) has attracted attention as a material for fine shapes such as wiring and contacts that connect between transistors formed on a substrate. For example, Patent Documents 1 and 2 propose a technique for embedding ruthenium in a recess formed in a substrate. In order to realize low-resistance wiring and contacts, it is important to embed ruthenium in the recess without generating voids that increase resistance.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] The present disclosure provides a technique capable of performing ruthenium film formation and etching in the same film forming apparatus and embedding ruthenium in a bottom-up manner.

Means for Solving the Problems

[0005] According to one aspect of the present disclosure, there is provided a film forming apparatus including a processing container, a gas supply unit that supplies a gas, and a gas exhaust unit that exhausts a gas, for embedding ruthenium in a substrate having a recess, wherein the gas supply unit supplies a gas containing a ruthenium source gas into the processing container and hydrogen-containing gasA first supply line for supplying [a certain gas], and a second supply line for supplying a gas containing ozone gas. The gas exhaust section has a first exhaust device, and uses the first exhaust device to exhaust a gas containing a raw material gas of ruthenium from inside the processing container and hydrogen-containing gas A first exhaust line for exhausting, and a second exhaust device different from the first exhaust device, and has a second exhaust line for exhausting a gas containing ozone gas by using the second exhaust device Shi , The second exhaust line connects the second supply line and the second exhaust device without passing through the processing container, and has a bypass exhaust line for exhausting a gas containing ozone gas , A film forming apparatus is provided.

Advantages of the Invention

[0006] According to one aspect, ruthenium film formation and etching can be performed using the same film forming apparatus, and ruthenium can be embedded in a bottom-up manner.

Brief Description of the Drawings

[0007]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Modes for Carrying Out the Invention

[0008] Hereinafter, modes for carrying out the present disclosure will be described with reference to the drawings. In each drawing, the same reference numerals are given to the same components, and redundant descriptions may be omitted.

[0009] [Film Deposition System] First, the configuration and operation of the film deposition system 1 according to the embodiment will be described with reference to FIG. 1. FIG. 1 is a schematic plan view showing an example of the film deposition system according to the embodiment. The film deposition system 1 executes a process including a process of embedding ruthenium in a recess formed in a substrate.

[0010] The film deposition system 1 includes an atmospheric transfer chamber 11, a load lock chamber 12, a first substrate transfer chamber 13, a second substrate transfer chamber 14, and a processing chamber PM. In FIG. 1, the processing chamber PM is composed of a plurality of pre-cleaning devices 21, 22, a plurality of film deposition devices 23 to 27, and an annealing device 28. However, when the substrate is not subjected to an annealing process, the processing chamber PM may be composed of a plurality of pre-cleaning devices and a plurality of film deposition devices. The film deposition devices may include a film deposition device for ruthenium embedding for embedding ruthenium in a recess formed in a substrate, and a film deposition device for ruthenium stacking for further stacking ruthenium on the embedded ruthenium to form a flat ruthenium layer.

[0011] The number and arrangement of the pre-cleaning devices, film deposition devices, and annealing devices are not limited to the example shown in FIG. 1, and the number and arrangement of each device can be set so as to improve the overall throughput. For example, when the ruthenium embedding process takes a long time and the annealing process is not required, two pre-cleaning devices, five film deposition devices for ruthenium embedding, and one film deposition device for ruthenium stacking can be prepared and arranged at appropriate positions in eight processing chambers PM. When an annealing process is required after ruthenium stacking, two pre-cleaning devices, three film deposition devices for ruthenium embedding, one film deposition device for ruthenium stacking, and two annealing devices can be prepared and arranged at appropriate positions in eight processing chambers PM.

[0012] The first substrate transfer chamber 13 and the second substrate transfer chamber 14 are each configured in a rectangular shape in plan view, and are connected via, for example, two transfer portions 17. The interiors of the first and second substrate transfer chambers 13, 14 and the transfer portion 17 are set to a vacuum atmosphere, and their pressures are configured to be aligned with each other. The transfer portion 17 transfers the substrate between the first transfer mechanism 13a provided in the first substrate transfer chamber 13 or the second transfer mechanism 14a provided in the second substrate transfer chamber 14. The first substrate transfer chamber 13 and the second substrate transfer chamber 14 each have a turbo molecular pump (not shown) for the transfer chamber, and control the pressure in each transfer chamber to a desired pressure.

[0013] The direction in which the first substrate transfer chamber 13 and the second substrate transfer chamber 14 are arranged is defined as the length direction, with the first substrate transfer chamber 13 on the front side and the second substrate transfer chamber 14 on the back side. At this time, on the front side of the first substrate transfer chamber 13, an atmospheric transfer chamber 11 set to an atmospheric pressure atmosphere is connected via, for example, three load lock chambers 12. Between the first and second substrate transfer chambers 13, 14 and the transfer portion 17, between the load lock chamber 12 and the first substrate transfer chamber 13, and between the load lock chamber 12 and the atmospheric transfer chamber 11, there are a substrate transfer port and a gate valve for opening and closing the transfer port, respectively, but the illustration is omitted.

[0014] For example, four load ports 15 are connected to the atmospheric transfer chamber 11, and a carrier C containing a plurality of substrates is placed on each load port 15. An atmospheric transfer mechanism 11a is provided in the atmospheric transfer chamber 11, and the substrate can be transferred between the carrier C connected to the atmospheric transfer chamber 11 and the load lock chamber 12.

[0015] Two wall portions in front of the first substrate transfer chamber 13 are respectively connected with precleaning devices 21 and 22. The precleaning devices 21 and 22 perform a precleaning process of removing metal oxides as a pretreatment for the process of embedding ruthenium. For example, the precleaning devices 21 and 22 remove metal oxides that are the lower layers of the recesses of the substrate. When the lower layer of the recess of the substrate is a tungsten layer, the precleaning devices 21 and 22 remove tungsten oxide in which tungsten is oxidized. Also, for example, when the lower layer of the recess of the substrate is a ruthenium layer, the precleaning devices 21 and 22 remove ruthenium oxide in which ruthenium is oxidized. The precleaning devices 21 and 22 reduce and remove metal oxides with hydrogen plasma in which hydrogen gas is made into plasma.

[0016] Two wall portions at the back of the first substrate transfer chamber 13 are respectively connected with film forming devices 23 and 24. And a first transfer mechanism 13a provided in the first substrate transfer chamber 13 transfers a substrate among these four processing chambers PM (21 to 24), a transfer portion 17, and a load lock chamber 12. In FIG. 1, reference sign GV1 indicates a gate valve.

[0017] Two wall portions in front of the second substrate transfer chamber 14 are respectively connected with film forming devices 25 and 26. In this example, the film forming devices 25 and 26 are film forming devices for ruthenium embedding.

[0018] Two wall portions at the back of the second substrate transfer chamber 14 are respectively connected with a film forming device 27 and an annealing device 28. And a second transfer mechanism 14a transfers a substrate between these four processing chambers PM (25 to 28) and the transfer portion 17. In FIG. 1, reference signs GV2 and GV3 respectively indicate gate valves. The film forming device 27 is a film forming device for ruthenium lamination.

[0019] In this example, the film forming devices 23 to 26 use Ru3(CO) as a ruthenium raw material 12Using a source gas containing (hereinafter also referred to as DCR), ruthenium is embedded bottom-up in the recess. The film forming apparatus 27 forms a ruthenium film up to the field portion using the source gas containing DCR. This is a process of increasing the thickness of the ruthenium layer for the subsequent planarization process (CMP).

[0020] The annealing apparatus 28 anneals the substrate after forming a ruthenium film up to the field portion. The annealing apparatus 28 may not be provided. The annealing apparatus 28 is an apparatus capable of heating the substrate by heating means such as a heater.

[0021] The film forming system 1 includes a control device 100 that controls various processes in the pre-cleaning apparatuses 21 and 22, the film forming apparatuses 23 to 27, the annealing apparatus 28, and operations of each part constituting the film forming system 1 such as conveyance of the substrate. The control device 100 is composed of a computer having, for example, a CPU and a memory (storage unit) not shown, and the memory stores a control program necessary for operations of each part constituting the film forming system 1. The control program is stored in a storage medium such as a hard disk, a compact disk, a magneto-optical disk, a memory card, or a non-volatile memory, and may be installed from the storage medium into the computer. The control program may be acquired from a network connected to the control device 100 using communication means.

[0022] As described by way of example above, the film forming system 1 has at least one film forming apparatus for forming ruthenium, and executes a process of embedding ruthenium in a substrate having a recess using the film forming apparatus. In this example, the film forming apparatuses 23 to 27 have the same configuration, but the film forming apparatus 27 may not have some configurations (such as a supply line for ozone gas, a supply line for hydrogen-containing gas, an exhaust line for ozone gas, etc.) of the film forming apparatuses 23 to 26.

[0023] [Film Forming Apparatus] Next, with reference to FIG. 2, the configuration of the film forming apparatus according to the embodiment included in the film forming system 1 will be described. Here, as an example, the configuration of the film forming apparatus 23 will be described, and the description of the film forming apparatuses 24 to 27 having the same configuration will be omitted. FIG. 2 is a schematic cross-sectional view showing an example of the film forming apparatus 23 according to the embodiment. Note that the illustration of the configurations of the pre-cleaning apparatuses 21 and 22 and the annealing apparatus 28 is omitted.

[0024] The film forming apparatus 23 includes a processing container 101. The side wall of the processing container 101 is connected to the second substrate transfer chamber 14, and a transfer port 104 for loading and unloading the substrate between the processing container 101 and the second substrate transfer chamber 14 is formed. The transfer port 104 is configured to be openable and closable by a gate valve GV1.

[0025] Inside the processing container 101, a mounting table 102 for horizontally supporting the substrate W is provided in a state of being supported from the lower surface side by support columns 103. The mounting table 102 has a heater 105 and can heat the substrate W to a preset temperature.

[0026] A shower head 110 is disposed on the ceiling portion of the processing container 101 so as to face the substrate W placed on the mounting table 102. The shower head 110 has a gas diffusion space 112, and gas discharge ports 113 are dispersedly formed on the lower surface thereof.

[0027] Furthermore, the film forming apparatus 23 includes a gas supply unit 130 for supplying gas and a gas exhaust unit 180 for exhausting gas. The gas supply unit 130 includes a first supply line 131 for supplying a gas containing a raw material gas of ruthenium and a hydrogen-containing gas to the processing container 101, and a second supply line 132 for supplying a gas containing ozone gas. The first supply line 131 includes a raw material gas supply line 131a for supplying a gas containing a raw material gas of ruthenium and a hydrogen gas supply line 131b for supplying a hydrogen-containing gas.

[0028] The raw material gas supply line 131a has a supply pipe 133 for carrier gas, and supply pipes 140 and 135. The supply pipe 133 for carrier gas extends from a CO gas supply source 134 and is connected to a raw material container 161. The end of the supply pipe 133 is provided so as to be inserted into the raw material S. A valve 137a, a mass flow controller 136, and a valve 137b are provided in this order on the supply pipe 133 from the CO gas supply source 134 side. CO gas is supplied from the CO gas supply source 134 to the raw material container 161 as a carrier gas via the supply pipe 133. However, as the carrier gas, an inert gas such as argon (Ar) gas or nitrogen (N2) gas can also be used instead of CO gas.

[0029] The raw material container 161 stores the raw material S of ruthenium. In this example, DCR is stored in the raw material container 161 as the raw material S for the ruthenium film, but the raw material S for the ruthenium film is not limited to DCR and may be an organic gas. The raw material S in the raw material container 161 is heated by a heater 162 and vaporized.

[0030] The space between the raw material container 161 and the gas inlet 111 of the shower head 110 is connected by supply pipes 140 and 135. The upper end surface of the raw material container 161 is connected to the supply pipe 140, the supply pipe 140 is further connected to the supply pipe 135, and is connected to the gas inlet 111. A valve 139a, a flow meter 138, and a valve 139b are provided in this order on the supply pipe 140 from the raw material container 161 side. A valve 139c is provided on the supply pipe 140.

[0031] The raw material gas of ruthenium vaporized in the raw material container 161 flows through the supply pipes 140 and 135 using CO gas as a carrier gas and is supplied to the processing container 101 from the gas inlet 111. The flow meter 138 detects the flow rate of the raw material gas. With such a configuration, a ruthenium film is formed in the concave portions on the surface of the substrate W by the raw material gas supplied from the first supply line 131 to the processing container 101.

[0032] If ruthenium can be deposited bottom-up from the bottom of the recess formed in the substrate W, the generation of voids and seams described later can be avoided, and a ruthenium layer with low resistance can be formed. However, during the film formation process, a ruthenium film (hereinafter also referred to as a ruthenium piece) is also formed on the side wall (side surface) of the recess. When the ruthenium piece formed on the side wall is removed by etching, the side surface of the recess is in a state without a ruthenium film, and the generation of voids can be avoided. Therefore, in the film forming apparatus 23, ruthenium is grown bottom-up from the bottom of the recess by the DED method that repeatedly executes the formation (D: deposition) of the ruthenium film and the removal (E: etching) of the ruthenium piece.

[0033] When the DED method is not used, the ruthenium pieces formed on the side walls of the recesses block the opening width of the recesses, resulting in the generation of voids, or minute gaps (seams) are generated in the recesses due to the deposition of a conformal ruthenium film. In the film forming method according to the embodiment described later, the DED method enables the bottom-up embedding process of ruthenium into the recesses, and ruthenium wirings and contacts that avoid voids and seams can be realized.

[0034] Therefore, after forming a ruthenium film in the recess, a gas containing ozone is supplied into the processing container 101 from the second supply line 132, and the ruthenium pieces formed on the side walls of the recess are etched and removed by the ozone gas.

[0035] The second supply line 132 has supply pipes 170 and 175. The supply pipe 170 extends from an O2 gas supply source 174 and is connected to the supply pipe 175. The supply pipe 175 is connected to a gas introduction port 111 for introducing O2 gas. The supply pipe 170 is provided with a valve 177a, a mass flow controller 176, an ozonizer 173, and a valve 177b in order from the O2 gas supply source 174 side. The supply pipe 175 is provided with a valve 177c.

[0036] The oxygen gas supplied from the O2 gas supply source 174 is controlled in flow rate by the mass flow controller 176 and supplied to the ozonizer 173. The ozonizer 173 discharges the oxygen gas by electric energy to generate ozone gas, controls the concentration of the ozone gas with respect to the oxygen gas, and outputs a mixed gas of the ozone gas and the oxygen gas controlled to a certain concentration. The mixed gas of the ozone gas and the oxygen gas is an example of a gas containing ozone gas. The gas containing ozone gas passes through the supply pipe 175 and is supplied to the processing container 101. Thereby, the ruthenium pieces formed on the side wall of the recess are etched and removed.

[0037] The first supply line 131 further has a supply pipe 155 branched from the supply pipe 135. The supply pipe 155 extends from the H2 gas supply source 154 and is connected to the supply pipe 135. A valve 157a, a mass flow controller 156, and a valve 157b are provided in the supply pipe 155 in order from the H2 gas supply source 154 side.

[0038] The hydrogen (H2) gas supplied from the H2 gas supply source 154 is controlled in flow rate by the mass flow controller 156. The hydrogen gas is an example of a hydrogen-containing gas. The hydrogen gas passes through the supply pipes 155 and 135 and is supplied to the processing container 101. Thereby, the ruthenium layer is reformed (reduced) by the hydrogen-containing gas. In this example, hydrogen gas, which is a reducing gas, is used as the reaction gas. Also, as the reaction gas, H2 gas plasma, NH3 gas, NH3 plasma, monomethylhydrazine (MMH), hydrazine (N2H4), etc. can be used.

[0039] The gas exhaust section 180 has a first exhaust line 188 and a second exhaust line 189. The first exhaust line 188 and the second exhaust line 189 are connected to an exhaust pipe 108 provided on the bottom wall of the processing container 101 via a pressure adjustment section (APC) 181 and a turbo molecular pump (TMP) 182.

[0040] The first exhaust line 188 has an exhaust pipe. The exhaust pipe of the first exhaust line 188 extends from the dry pump (DP1) 185 and is connected to the turbo molecular pump (TMP) 182. A valve 183b, a trap device 184, and a valve 183a are provided in order on the exhaust pipe of the first exhaust line 188 from the side of the dry pump (DP1) 185. The dry pump (DP1) 185 roughly evacuates the inside of the processing vessel 101 and exhausts the residual gas of the raw material gas of ruthenium. At that time, the raw material gas is recovered by the trap device 184. The turbo molecular pump 182 evacuates the inside of the processing vessel 101 while adjusting the pressure inside the processing vessel 101 at the pressure adjustment unit 181. The first exhaust line 188 exhausts the residual gas of the raw material gas of ruthenium. Also, the first exhaust line 188 exhausts the residual gas of the hydrogen-containing gas.

[0041] The second exhaust line 189 has an exhaust pipe 190. The exhaust pipe 190 extends from the dry pump (DP2) 187 and is connected to the turbo molecular pump (TMP) 182. A valve 186a is provided in the exhaust pipe 190. The dry pump (DP2) 187 roughly evacuates the inside of the processing vessel 101 and exhausts the residual gas of the gas containing ozone gas. The turbo molecular pump 182 evacuates the inside of the processing vessel 101 while adjusting the pressure inside the processing vessel 101 at the pressure adjustment unit 181. The second exhaust line 189 exhausts the residual gas of the gas containing ozone gas.

[0042] Furthermore, the second exhaust line 189 has a bypass exhaust line 179 that connects the second supply line 132 and the second exhaust line 189 without passing through the processing vessel 101. The bypass exhaust line 179 flows the gas containing ozone gas from the second supply line 132 to the second exhaust line 189 during the film formation of ruthenium. A valve 178b is provided in the bypass exhaust line 179.

[0043] Note that the exhaust pipe 190 is an example of the second main exhaust line 190 that exhausts the gas containing ozone gas from inside the processing vessel 101.

[0044] The film forming apparatus 23 includes a control device 150 that controls the operations of the respective components constituting the film forming apparatus 23. The control device 150 is composed of a computer having, for example, a CPU (not shown) and a memory (storage unit), and the memory stores a process recipe in which a group of steps (instructions) for the control necessary for performing the film forming method described later is assembled. The process recipe may be stored in a storage medium such as a hard disk, installed in the computer from the storage medium, or acquired from a network connected to the control device 150 using communication means. The control device 150 may control the film forming apparatus 23 and the film forming system 1 in cooperation with the control device 100.

[0045] [Film Forming Method] Next, an example of the film forming method according to the embodiment executed in the film forming system 1 will be described with reference to FIGS. 3 to 6 in addition to FIG. 1. FIG. 3 is a flowchart showing an example of the film forming method according to the embodiment. FIG. 4 is a cross-sectional view of the recess of the substrate in the film forming method of FIG. 3. FIG. 6 is a diagram showing the chemical reaction occurring in the film forming method of FIG. 3.

[0046] (Substrate Preparation Step Step S1) The film forming method shown in FIG. 3 is executed by the control device 100 and / or the control device 150 in cooperation. For example, the control device 150 starts this process according to a process recipe in response to a command from the control device 100. When this process is started, in step S1, the control device 100 loads and prepares the substrate W having a recess into either the pre-cleaning devices 21 or 22.

[0047] As shown in FIG. 4(a), on the surface of the loaded substrate W, an insulating film having recesses 52, for example, a silicon oxide film (SiO x film) 51 is formed. The lower layer of the silicon oxide film 51 is a metal layer 50 such as tungsten. The metal layer 50 is exposed from the bottom of the recess 52, and the exposed metal layer 50 is oxidized to form a metal oxide film 50a.

[0048] To remove the metal oxide film 50a, the control device 100 first takes out the substrate accommodated in the carrier C by the atmospheric transfer mechanism 11a shown in FIG. 1, delivers it to the load lock chamber 12 in the atmospheric pressure atmosphere, and adjusts the load lock chamber 12 to the vacuum pressure atmosphere. Next, the control device 100 transports the substrate in the load lock chamber 12 to either the pre-cleaning devices 21 or 22 by the first transfer mechanism 13a and performs the next pre-cleaning process.

[0049] (Pre-cleaning process Step S3) Next, in step S3, it is controlled under the following process conditions, and the metal oxide film 50a at the bottom of the recess 52 shown in FIG. 4(a) is reduced and removed by hydrogen plasma in which hydrogen gas is plasmaized. In this example, the metal oxide film 50a is a tungsten oxide film.

[0050] (Pre-cleaning process conditions) Gas H2 H2 gas flow rate 2000 sccm Pressure inside the processing container 5 Torr (667 Pa)

[0051] (Ruthenium film formation (embedding) process Step S5) Next, the control device 100 transports the substrate to either the film forming devices 23 or 24 via the first transfer mechanism 13a shown in FIG. 1, or transports the substrate to either the film forming devices 25 or 26 via the first transfer mechanism 13a, the transfer unit 17, and the second transfer mechanism 14a.

[0052] In the film forming device 23, the control device 150 forms a ruthenium layer in the region including the bottom of the recess 52. Specifically, the control device 150 transports the substrate into the processing container 101 and places it on the mounting table 102, heats the substrate with the heater 105, and evacuates the inside of the processing container 101 by the gas exhaust unit 180.

[0053] In step S5 of FIG. 3, it is controlled under the following process conditions, and as shown in FIG. 4(b), ruthenium is embedded in the region including the bottom of the recess 52 with the vaporized ruthenium source gas to form a ruthenium layer 55.

[0054] <Ruthenium implantation process conditions> Raw material gas for gas DCR, CO gas CO gas flow rate 100 sccm Pressure inside the processing chamber 16.6 mTorr (2.21 Pa) Temperature of the mounting stage 100 °C to 200 °C

[0055] In the raw material container 161 shown in FIG. 2, the DCR which is the raw material of ruthenium is heated by the heater 162. The valves 137a and 137b provided in the supply pipe 133 for the carrier gas of the first supply line 131 are opened, and CO gas of the carrier gas whose flow rate is controlled by the mass flow controller 136 is supplied to the raw material container 161. The raw material gas of ruthenium is vaporized by the heating by the heater 162. At this time, the valves 139a, 139b, and 139c provided in the supply pipes 140 and 135 are open. Thereby, the vaporized raw material gas is supplied into the processing chamber 101, and a ruthenium layer 55 is formed in the recess 52.

[0056] FIG. 5(a) shows the operations of gas supply and gas exhaust in the ruthenium implantation process (during film formation). The valve 139c of the first supply line 131 is open, and the valve 177c of the second supply line 132 is closed. Thereby, the gas containing the raw material gas of ruthenium is supplied into the processing chamber 101, and the ruthenium layer 55 is formed. During film formation, a ruthenium film (hereinafter also referred to as ruthenium piece 55a) is partially formed on the side wall inside the recess 52.

[0057] During the formation of the ruthenium film in step S5, the first exhaust line 188 exhausts the gas containing the raw material gas of ruthenium in the processing vessel 101. Specifically, as shown in FIG. 5(a), the valves 183a and 183b of the first exhaust line 188 are opened, and the valve 186a of the second exhaust line 189 is closed. After roughly evacuating the inside of the processing vessel 101 using the dry pump (DP1) 185, the first exhaust line 188 evacuates the inside of the processing vessel 101 to a vacuum using the pressure adjustment unit 181 and the turbo molecular pump 182, and exhausts the gas containing the raw material gas of ruthenium from the processing vessel 101. After a predetermined time has elapsed since the start of the process in step S5, the control device 150 closes the valve 139c and stops the supply of the gas containing the raw material gas of ruthenium.

[0058] (Bypass Exhaust Step Step S7) Step S7 in FIG. 3 is executed in parallel with step S5. During the formation of the ruthenium layer in step S5, in step S7, the control device 150 exhausts the gas containing ozone from the bypass exhaust line 179. At this time, the valves 177a and 177b of the second supply line 132 are opened. Also, as shown in FIG. 5(a), the valve 178b of the bypass exhaust line 179 is opened, the valve 177c of the supply pipe 175 is closed, and the gas containing ozone gas is made to flow into the bypass exhaust line 179 without passing through the processing vessel 101, and is exhausted using the dry pump (DP2) 187. At this time, the valve 186a of the second exhaust line 189 is closed. Also, the valves 157a and 157b of the hydrogen gas supply line 131b shown in FIG. 1 are closed.

[0059] (Vacuum Evacuation Step Step S9) Next, in step S9 of FIG. 3, the inside of the processing vessel 101 is evacuated using the exhaust device of the first exhaust line 188. As a result, the gas containing the raw material gas of ruthenium is exhausted. In step S9, purging may be performed together with the above-mentioned vacuum evacuation. In the purging process, an inert gas such as Ar gas or N2 gas is supplied into the processing vessel 101, and the gas containing the raw material gas of ruthenium in the processing vessel 101 is replaced with the inert gas.

[0060] (Ruthenium Etching Process, Step S11) Next, in step S11 of FIG. 3, control is performed under the following process conditions to etch and remove the ruthenium piece 55a adhering to the side wall of the recess 52.

[0061] <Etching Process Conditions> Mixed gas of gas O3 and O2 O3 gas flow rate 300 g / m 3 Pressure inside the processing chamber 3 Torr (400 Pa) Temperature of the mounting table 100°C to 200°C

[0062] As shown in FIGS. 2 and 5(b), in step S11, the valve 139c of the first supply line 131 is closed. Also, the valve 178b of the bypass exhaust line 179 is closed. The valve 177c of the second supply line 132 is open. The valves 177a and 177b of the second supply line 132 remain open. In the second supply line 132, a mixed gas of O3 and O2 with a predetermined concentration output from the ozonizer 173 is supplied into the processing chamber 101. As a result, a gas containing ozone gas is supplied into the processing chamber 101, the ruthenium layer 55 and the ruthenium piece 55a shown in FIG. 4(b) are etched, and the ruthenium piece 55a is removed from the side wall of the recess 52 as shown in FIG. 4(c). Also, the valves 183a and 183b of the first exhaust line 188 are closed, and the valve 186a of the second exhaust line 189 is open. As a result, the residual gas of the gas containing ozone gas is exhausted from the second exhaust line 189.

[0063] In step S11, as shown in FIG. 5(a), starting from the state where valve 178b is opened and valves 177c and 186a are closed, it is switched to the state where valve 178b is closed and valves 177c and 186a are opened as shown in FIG. 5(b). Thereby, the gas containing ozone gas can be stably supplied from the second supply line 132 into the processing container 101. Also, the residual gas of the gas containing ozone gas in the processing container 101 is exhausted from the second exhaust line 189. After a predetermined time has elapsed since the start of the process of step S11, the control device 150 closes valve 177c and stops the supply of the gas containing ozone gas to the processing container 101.

[0064] (Vacuum evacuation step Step S13) In step S13, the inside of the processing container 101 is evacuated using the exhaust device of the second exhaust line 189. Thereby, the gas containing ozone gas is exhausted. Purging may be performed together with the above-mentioned vacuum evacuation. In the purging process, an inert gas is supplied into the processing container 101, and the gas containing ozone gas in the processing container 101 is replaced with the inert gas.

[0065] (Ruthenium reduction step Step S15) Next, in step S15 of FIG. 3, valves 157a, 157b, and 139c of the first supply line 131 (hydrogen gas supply line 131b) are opened. In the first supply line 131 (hydrogen gas supply line 131b), hydrogen gas output from the H2 gas supply source 154 and having its flow rate controlled by the mass flow controller 156 is supplied into the processing container 101.

[0066] In step S15, control is performed under the following process conditions, a hydrogen-containing gas is supplied from the hydrogen gas supply line 131b into the processing container 101, and the ruthenium layer 55 is reformed (reduced).

[0067] <Reforming (reduction) process conditions> Gas H2 gas H2 gas flow rate 2000 sccm Pressure inside the processing container 5 Torr Temperature of the mounting table 100°C to 200°C

[0068] Thereby, the ruthenium oxide layer formed on the surface layer of the ruthenium layer 55 can be reduced and returned to the ruthenium layer 55. When supplying H2 gas, as shown in FIG. 5(c), the valve 186a is closed, the valves 183a and 183b are opened, and the hydrogen-containing gas in the processing container 101 is exhausted from the first exhaust line 188. Further, the control device 150 opens the valve 178b, closes the valves 177c and 186a, and exhausts the gas containing ozone gas from the bypass exhaust line 179. By switching the exhaust line from the second exhaust line 189 to the first exhaust line 188, it is possible to avoid exhausting ozone gas and hydrogen gas from the same exhaust line, avoid the risk of explosion due to the reaction between ozone gas and hydrogen gas, and ensure safety.

[0069] At this time, the valve 139b of the raw material gas supply line 131a is closed. Also, as shown in FIG. 5(c), the valves 183a and 183b of the first exhaust line 188 are opened to exhaust the residual gas of hydrogen gas from the first exhaust line 188. Also, the valve 178b of the bypass exhaust line 179 is opened, and the valve 186a is closed. Thereby, the gas containing ozone gas flows through the bypass exhaust line 179 and is exhausted by the dry pump (DP2) 187. After a predetermined time has elapsed since the process of step S15 was started, the valve 139c is closed to stop the supply of hydrogen gas.

[0070] (Vacuum pumping step Step S17) Next, in step S17 of FIG. 3, the inside of the processing container 101 is evacuated from the first exhaust line 188. Thereby, the hydrogen-containing gas is exhausted. In step S17, purging may be performed together with the above-mentioned vacuum pumping. In the purging step, an inert gas is supplied into the processing container 101 to replace the hydrogen-containing gas in the processing container 101 with the inert gas.

[0071] (Judgment step Step S19) Next, the control device 150 determines whether the ruthenium implantation process (steps S5 to S17) has been executed the predetermined number of set times. When the control device 150 determines that the ruthenium implantation process has not been executed the set number of times, it returns to step S5 and executes steps S5 to S17. As a result, the film formation shown in FIG. 4(b) and the etching shown in FIG. 4(c) are repeated the set number of times. Thereby, ruthenium film formation and etching can be executed in the same film formation apparatus.

[0072] When the control device 150 determines that the ruthenium implantation process has been executed the set number of times, it unloads the substrate W, and the control device 100 transports the substrate to the film formation apparatus 27 via the first transport mechanism 13a, the transfer unit 17, and the second transport mechanism 14a.

[0073] (Ruthenium Film Formation (Lamination) Step S21) Next, in step S21 of FIG. 3, the following process conditions are controlled, and a ruthenium layer 56 is laminated on the field portion of the upper layer of the ruthenium layer 55 formed at the bottom of the recess 52 by the vaporized ruthenium source gas. As a result, as shown in FIG. 4(d), a ruthenium layer 56 is formed on the ruthenium layer 55 embedded in the recess of the substrate W. The opening and closing of each valve are the same as when implanting ruthenium in step S5. However, the process conditions may be different from those in step S5. The temperature of the mounting table may be higher than that in step S5.

[0074] <Ruthenium Lamination Process Conditions> Source gas for gas DCR, CO gas CO gas flow rate 100 sccm Pressure inside the processing chamber 16.6 mTorr (2.21 Pa) Temperature of the mounting table 100°C to 250°C

[0075] (Annealing Step S23) Next, when annealing the formed ruthenium layer, the control device 100 conveys the substrate to the annealing device 28 via the second conveyance mechanism 14a, and the annealing device 28 controls to the following process conditions and heats the conveyed substrate W at a predetermined temperature. Then, this process is terminated.

[0076] <Annealing Process Conditions> Gas N2 gas CO gas flow rate 100 sccm Pressure inside the processing chamber 5 Torr Temperature of the mounting table 300°C to 500°C

[0077] The operation of the film formation method described above will be described with reference to FIG. 6. FIG. 6 is a schematic diagram showing chemical reactions occurring in steps S5 to S17 of the film formation method of FIG. 3. FIG. 6(a) shows the case where a gas containing ozone gas is supplied to the ruthenium layer 55 formed in the recess of the substrate in step S5 of FIG. 3 in step S11 of FIG. 3. One of the chemical reactions (1) of the reaction between the ruthenium layer 55 and the ozone gas in this case is represented by Ru + 2 / 3O3 → RuO2. In this chemical reaction (1), the Gibbs free energy is -345 kJ / mol, and the chemical reaction (1) proceeds. As shown in FIG. 6(b), the surface of the ruthenium layer 55 is oxidized, and a ruthenium oxide layer 55b of RuO2 is formed.

[0078] Also, one of the chemical reactions (2) of the reaction between the ruthenium layer 55 and the ozone gas is represented by Ru + 4 / 3O3 → RuO4. In this chemical reaction (2), the Gibbs free energy is -350 kJ / mol, and the chemical reaction (2) proceeds.

[0079] Also, the chemical reaction (3) between the ruthenium oxide layer (RuO2) 55b and ozone gas is represented by RuO2 + 2 / 3O3 → RuO4. In this chemical reaction (3), the Gibbs free energy is -5.36 kJ / mol, and although the reaction is unlikely to occur, chemical reaction (2) occurs. Due to these chemical reactions (2) and (3), RuO4 volatilizes. As a result, as shown in FIGS. 6(a) and (b), the surface of the ruthenium layer 55 and the ruthenium piece 55a (see FIG. 4(b)) are etched and removed.

[0080] The chemical reaction (4) for reducing the remaining ruthenium oxide layer 55b with hydrogen gas is represented by RuO2 + 2H2 → Ru + H2O. In this chemical reaction (4), the Gibbs free energy is -215 kJ / mol, and the chemical reaction (4) proceeds. As a result, as shown in FIG. 6(c), the ruthenium oxide layer 55b is reduced with hydrogen gas and returns to the ruthenium layer 55. H2O volatilizes.

[0081] From the above, in the film formation method according to this embodiment, after forming the ruthenium layer, a gas containing ozone gas is supplied in the same film formation apparatus, and Ru film formation and etching are repeated, and the ruthenium layer can be formed bottom-up in the concave portion of the substrate without generating voids. Further, in addition to Ru film formation and etching, a hydrogen-containing gas is supplied in the same film formation apparatus, and RuO x A ruthenium layer with lower resistance can be formed by reducing the film.

[0082] In the film formation method of FIG. 3, the lines for supplying and exhausting the gas containing ozone gas (the second supply line 132 and the second exhaust line 189) and the lines for supplying and exhausting the hydrogen-containing gas (the first supply line 131 and the first exhaust line 188) are separate lines. This is because if ozone gas and hydrogen gas are supplied to the same supply line and exhaust line, there is a risk of explosion due to the reaction between ozone gas and hydrogen gas. Note that the supply line for the hydrogen-containing gas is the same as the supply line for supplying the gas containing the raw material gas of ruthenium.

[0083] During the step of supplying a gas containing a raw material gas of ruthenium (step S5), the gas containing ozone gas is exhausted by a dry pump (DP2) 187 through a bypass exhaust line 179. Since ozone gas is generated by discharging oxygen gas, it is necessary to keep flowing ozone gas even during the film formation of ruthenium for the stability of the discharge, and to stabilize the flow rate and concentration of ozone gas. For this reason, in the film formation method according to the present embodiment, when ozone gas is not used for the treatment in the processing container 101, such as during the film formation of ruthenium, the gas containing ozone gas is continuously flowed through the bypass exhaust line 179. Thereby, the flow rate and concentration of ozone gas can be stabilized. It is necessary to keep flowing.

[0084] In the film formation method of FIG. 3, the ruthenium film formation step (step S5), the step of supplying a gas containing ozone gas (ruthenium etching step: step S11), and the step of supplying a hydrogen-containing gas (ruthenium reduction step: step S15) were repeatedly executed in this order.

[0085] However, each step is not limited to being repeated in this order. For example, after executing the ruthenium film formation step, the ruthenium etching step and the ruthenium reduction step may be repeatedly executed a plurality of times and then return to the ruthenium film formation step.

[0086] When repeatedly executing the ruthenium etching step and the ruthenium reduction step a plurality of times after executing the ruthenium film formation step, the ruthenium etching step may be divided into a plurality of times and the gas containing ozone gas may be intermittently supplied a plurality of times. According to this, since the gas containing ozone gas with a certain flow rate is stored in a separate chamber and then supplied in a plurality of divided times, the ozone gas with a high pressure can be injected into the processing container 101, and the ozone gas easily reaches the bottom of the concave portion. Thereby, it becomes possible to form a ruthenium film with higher embedding performance.

[0087] In addition, in the film formation method of FIG. 3, the purge processes in steps S9, S13, and S17 may be omitted, and only the evacuation process may be performed. The configurations of the film formation apparatuses shown in FIGS. 2 and 5 correspond to the configuration of the film formation apparatus according to the first embodiment.

[0088] (Second Embodiment) Hereinafter, with reference to FIG. 7, the configuration and operation of the film forming apparatus according to the second embodiment will be described. FIG. 7 is a diagram showing the configuration and operation of the film forming apparatus according to the second embodiment.

[0089] The configuration different from the first embodiment is that a new exhaust line is provided in the second exhaust line 189. The exhaust pipe 190 is also referred to as the second main exhaust line 190. The second exhaust line 189 is a line separate from the second main exhaust line 190 and has an exhaust pipe 289 that connects the processing vessel 101 and the dry pump (DP2) 187 and exhausts the gas containing ozone gas from the processing vessel 101. The exhaust pipe 289 is also referred to as the second sub-exhaust line 289. That is, the film forming apparatus according to the second embodiment is different in that the second exhaust line 189 further includes the second sub-exhaust line 289. Other configurations are the same as those of the film forming apparatus according to the first embodiment. Note that in the film forming apparatus according to the second embodiment, the second main exhaust line 190 may not be provided. The bypass exhaust line 179 is connected to the exhaust pipe 289 of the second sub-exhaust line.

[0090] Hereinafter, the configuration of the second sub-exhaust line 289 will be mainly described. The second sub-exhaust line 289 has a pressure adjustment unit 281 between the processing vessel 101 and the dry pump (DP2) 187 and does not have a vacuum exhaust device capable of evacuation such as a turbo molecular pump. The pressure adjustment unit 281 is connected to an exhaust pipe (not shown) formed on the side wall or bottom wall of the processing vessel 101.

[0091] During ruthenium film formation (embedding) in FIG. 7(a) and during hydrogen supply in FIG. 7(c), the opening and closing states of each valve are the same. That is, the valve 139c of the first supply line 131 is open, and the valve 177c of the second supply line 132 is closed. Thereby, during ruthenium film formation in FIG. 7(a), a gas containing a raw material gas of ruthenium is supplied into the processing vessel 101 from the first supply line 131, and during hydrogen supply in FIG. 7(c), a hydrogen-containing gas is supplied into the processing vessel 101 from the first supply line 131.

[0092] Also, the valves 183a and 183b of the first exhaust line 188 are open, and the valve 178b of the bypass exhaust line 179 of the second exhaust line 189 is open. The valves 186b of the second main exhaust line 190 and 283a of the second sub-exhaust line 289 of the second exhaust line 189 are closed. Thus, during ruthenium film formation in Fig. 7(a), the gas containing the ruthenium source gas is exhausted from the first exhaust line 188, and during hydrogen supply in Fig. 7(c), the hydrogen-containing gas is exhausted from the first exhaust line 188. Also, during this period, the gas containing ozone gas is exhausted through the bypass exhaust line 179 without passing through the processing container 101.

[0093] During ozone gas supply in Fig. 7(b), the valve 177c of the second supply line 132 and the valve 283a of the second sub-exhaust line 289 are open, and the other valves (139c, 178b, 183a, 183b, 186a) are closed. Thus, during ozone gas supply, that is, during ruthenium etching, the gas containing ozone gas is supplied from the second supply line 132, and the gas containing ozone gas is exhausted from the second sub-exhaust line 289.

[0094] According to the film forming apparatus according to the second embodiment, similar to the film forming apparatus according to the first embodiment, after forming a ruthenium layer in the same film forming apparatus, the gas containing ozone gas is supplied, and further the hydrogen-containing gas is supplied repeatedly. Thereby, the film formation and etching of Ru are repeated, and the ruthenium layer can be formed bottom-up in the concave portion of the substrate without generating voids.

[0095] Furthermore, according to the film forming apparatus according to the second embodiment, during ozone gas supply, the gas containing ozone gas can be passed from the pressure adjustment unit 381 to the dry pump (DP2) 187 without passing through the turbo molecular pump 182. The flow rate of the gas that can pass through the turbo molecular pump 182 is limited, and is less than the flow rate of the gas that can pass through the dry pump (DP2) 187. Therefore, according to the film forming apparatus according to the second embodiment, a relatively large flow rate of ozone gas can be used.

[0096] (Third Embodiment) Next, with reference to FIG. 8, the configuration and operation of the film forming apparatus according to the third embodiment will be described. FIG. 8 is a diagram showing the configuration and operation of the film forming apparatus according to the third embodiment.

[0097] A configuration different from the second embodiment is that a new exhaust line is provided in the first exhaust line 188. The exhaust pipe 195 of the first exhaust line 188 is also referred to as the first main exhaust line 195. The first exhaust line 188, as a line separate from the first main exhaust line 195, connects the processing container 101 and the dry pump (DP1) 185 and has an exhaust pipe 389 for exhausting the gas containing the raw material gas and the hydrogen-containing gas from the processing container 101. The exhaust pipe 389 is also referred to as the first sub-exhaust line 389. That is, the film forming apparatus according to the second embodiment is different in that the first exhaust line 188 further includes the first sub-exhaust line 389. Other configurations are the same as those of the film forming apparatus according to the second embodiment. Note that in the film forming apparatus according to the third embodiment, the second main exhaust line 190 may not be provided.

[0098] Hereinafter, the configuration of the first sub-exhaust line 389 will be mainly described. The second sub-exhaust line 289 has a pressure adjustment unit 381 between the processing container 101 and the dry pump (DP1) 185 and does not have a vacuum exhaust device capable of evacuation such as a turbo molecular pump. The pressure adjustment unit 381 is connected to an exhaust pipe (not shown) formed on the side wall or bottom wall of the processing container 101.

[0099] In the film forming apparatus according to the third embodiment, when ruthenium film formation (embedding) in FIG. 8(a), the valve 139c of the first supply line 131 is open, and the valve 177c of the second supply line 132 is closed. Thereby, during film formation, the gas containing the raw material gas of ruthenium is supplied into the processing container 101. When ruthenium film formation in FIG. 8(a), the valves 183a and 183b of the first main exhaust line 195 are open, and the valve 383a of the first sub-exhaust line 389 is closed. Therefore, the gas containing the raw material gas of ruthenium is exhausted from the first main exhaust line 195.

[0100] At this time, the valve 178b of the bypass exhaust line 179 is open, and the valves 186a of the second main exhaust line 190 and 283a of the second sub-exhaust line 289 are closed. Therefore, the gas containing ozone gas is exhausted through the bypass exhaust line 179.

[0101] When supplying ozone gas in Fig. 8(b), the valve 139c of the first supply line 131 is closed, and the valve 177c of the second supply line 132 is open. As a result, the supply of the gas containing the raw material gas of ruthenium is stopped, and the gas containing ozone gas is supplied into the processing container 101. The valves 183a and 183b of the first main exhaust line 195 are closed, and the valve 383a of the first sub-exhaust line 389 is closed. Also, the valve 186a of the second main exhaust line 190 is closed, and the valve 283a of the second sub-exhaust line 289 is open. The valve 178b of the bypass exhaust line 179 is closed. Therefore, the gas containing ozone gas is exhausted from the second sub-exhaust line 289.

[0102] When supplying hydrogen in Fig. 8(c), the valve 139c of the first supply line 131 is open, and the valve 177c of the second supply line 132 is closed. As a result, the supply of the gas containing ozone gas is stopped, and the hydrogen-containing gas is supplied into the processing container 101. The valves 183a and 183b of the first main exhaust line 195 are closed, and the valve 383a of the first sub-exhaust line 389 is open. Therefore, the hydrogen-containing gas is exhausted from the first sub-exhaust line 389.

[0103] At this time, the valve 178b of the bypass exhaust line 179 is open, and the valves 186a of the second main exhaust line 190 and 283a of the second sub-exhaust line 289 are closed. Therefore, the gas containing ozone gas is exhausted through the bypass exhaust line 179.

[0104] According to the film forming apparatus according to the third embodiment, similar to the film forming apparatuses according to the first and second embodiments, after forming a ruthenium layer in the same film forming apparatus, a gas containing ozone gas is supplied, and further, supplying a hydrogen-containing gas is repeated. Thereby, film formation and etching of Ru are repeated, and a ruthenium layer can be formed bottom-up in the recess of the substrate without generating voids.

[0105] Furthermore, according to the film forming apparatus according to the third embodiment, when supplying a gas containing ozone gas, the gas containing ozone gas is exhausted from the second sub-exhaust line 289, and when supplying a hydrogen-containing gas, the hydrogen-containing gas is exhausted from the first sub-exhaust line 389. Therefore, according to the film forming apparatus according to the third embodiment, when supplying ozone gas, the gas containing ozone gas can be passed from the pressure adjustment unit 381 to the dry pump (DP2) 187 without passing through the turbo molecular pump 182. Also, when supplying hydrogen gas, the hydrogen gas can be passed from the pressure adjustment unit 381 to the dry pump (DP1) 185 without passing through the turbo molecular pump 182. The flow rate of the gas that can pass through the turbo molecular pump 182 is limited, and is less than the flow rate of the gas that can pass through the dry pump (DP1) 185 and the dry pump (DP2) 187. Therefore, according to the film forming apparatus according to the third embodiment, a relatively large flow rate of ozone gas can be used, and a relatively large flow rate of hydrogen gas can be used.

[0106] Also, according to the film forming apparatus according to the third embodiment, in a film forming method of repeating the gas supply of ozone gas and hydrogen-containing gas one or more times during the film formation of ruthenium, the gas supply of ozone gas and hydrogen-containing gas can be switched at high speed, and the throughput can be improved. The reason is that the exhaust volume is different between the dry pumps (DP1, DP2) and the turbo molecular pump (TMP). For this reason, when using the exhaust line passing through the turbo molecular pump for the supply of the gas containing ozone gas and the hydrogen-containing gas, it takes time to reach pressure stability. Since the dry pump (DP1) and the dry pump (DP2) have the same or similar exhaust volume, when repeating the gas supply of the gas containing ozone gas and the hydrogen-containing gas, the pressure change in the processing vessel 101 is small at the time of switching, and it can be controlled in the same order of pressure. Therefore, according to the film forming method using the film forming apparatus according to the third embodiment, it does not take time to reach pressure stability in the processing vessel 101 only by switching the opening and closing of the valve 283a and the valve 383a. As a result, the film forming time of the ruthenium layer can be shortened, and the throughput can be improved.

[0107] As described above, according to the film forming apparatus, film forming method, and film forming system of the present embodiment, ruthenium film formation and etching can be performed in the same film forming apparatus, and ruthenium can be embedded in a bottom-up manner.

[0108] The film forming apparatus, film forming method, and film forming system according to the embodiment disclosed this time should be considered to be illustrative and not restrictive in all respects. The embodiment can be deformed and improved in various forms without departing from the scope and gist of the appended claims. The matters described in the above plurality of embodiments can also adopt other configurations and can be combined within a non-contradictory range.

[0109] For example, in the film forming apparatus of the present disclosure, it is also possible to clean the processing container 101 when supplying a gas containing ozone gas. By the ozone gas supplied from the ozonizer 173 to the processing container 101, not only the etching of ruthenium attached to the side wall of the recess, but also the cleaning of ruthenium deposited on the wall surface of the processing container 101 and the like can be performed.

Explanation of Signs

[0110] 1 Film forming system 100, 150 Control device 101 Processing container 130 Gas supply unit 131 First supply line 131a Raw material gas supply line 131b Hydrogen gas supply line 132 Second supply line 179 Bypass exhaust line 180 Gas exhaust unit 188 First exhaust line 189 Second exhaust line 190 Second main exhaust line 195 First main exhaust line 289 Second sub-exhaust line 389 First sub-exhaust line

Claims

1. A film forming apparatus for embedding ruthenium in a substrate having a concave portion, the apparatus comprising a processing container, a gas supply unit for supplying gas, and a gas exhaust unit for exhausting gas, The gas supply unit has a first supply line for supplying a gas containing a raw material gas of ruthenium and a hydrogen-containing gas into the processing container, and a second supply line for supplying a gas containing ozone gas. The gas exhaust unit has a first exhaust device, a first exhaust line for exhausting a gas containing a raw material gas of ruthenium and a hydrogen-containing gas from the processing container using the first exhaust device, and a second exhaust device different from the first exhaust device, and a second exhaust line for exhausting a gas containing ozone gas using the second exhaust device. The second exhaust line connects the second supply line and the second exhaust device without passing through the processing container, and has a bypass exhaust line for exhausting a gas containing ozone gas. Film forming apparatus.

2. The second exhaust line connects the processing container and the second exhaust device, and has a second main exhaust line for exhausting a gas containing ozone gas from the processing container. The film forming apparatus according to claim 1.

3. The second main exhaust line has a pressure adjustment unit and a vacuum exhaust device between the processing container and the second exhaust device. The film forming apparatus according to claim 2.

4. The second exhaust line is a separate line from the second main exhaust line, connects the processing container and the second exhaust device, and has a second sub-exhaust line for exhausting a gas containing ozone gas from the processing container. The film forming apparatus according to claim 2 or 3.

5. The second sub-exhaust line has a pressure adjustment unit between the processing container and the second exhaust device, and does not have a vacuum exhaust device. The film forming apparatus according to claim 4.

6. The first exhaust line has a first main exhaust line connecting the processing vessel and the first exhaust device, and a first sub-exhaust line that is a separate line from the first main exhaust line and connects the processing vessel and the first exhaust device. While the first supply line supplies a hydrogen-containing gas into the processing vessel, the first sub-exhaust line exhausts the hydrogen-containing gas from the processing vessel. The film forming apparatus according to any one of claims 1 to 5.

7. The first main exhaust line has a pressure adjustment unit and a vacuum exhaust device between the processing vessel and the first exhaust device. The first sub-exhaust line has a pressure adjustment unit between the processing vessel and the first exhaust device and does not have a vacuum exhaust device. The film forming apparatus according to claim 6.

8. A film forming method of embedding ruthenium in a substrate having a concave portion, which is executed by the film forming apparatus according to any one of claims 1 to 7. (a) A step of preparing the substrate in the processing vessel. (b) A step of supplying a gas containing a raw material gas of ruthenium into the processing vessel from the first supply line to form a ruthenium layer, and exhausting the gas containing the raw material gas of ruthenium in the processing vessel from the first exhaust line. (c) A step of supplying a gas containing ozone gas into the processing vessel from the second supply line to etch the ruthenium layer, and exhausting the gas containing ozone gas in the processing vessel from a second exhaust line different from the first exhaust line. (d) A step of supplying a hydrogen-containing gas into the processing vessel from the first supply line to modify the ruthenium layer, and exhausting the hydrogen-containing gas in the processing vessel from the first exhaust line. A film forming method including the above steps.

9. During the step (b), a gas containing ozone gas is supplied from the second supply line, and exhausted from the bypass exhaust line without passing through the processing vessel. The film forming method according to claim 8.

10. The second exhaust line has a second main exhaust line connecting the processing container and the second exhaust device, and the second main exhaust line has a pressure adjustment unit and a vacuum exhaust device between the processing container and the second exhaust device. During (c), it includes a step of switching from the bypass exhaust line to the second main exhaust line to exhaust the gas containing ozone gas from the processing container. The film forming method according to claim 9.

11. The second exhaust line has a second sub-exhaust line connecting the processing container and the second exhaust device, and the second sub-exhaust line has a pressure adjustment unit between the processing container and the second exhaust device and does not have a vacuum exhaust device. During (c), it includes a step of switching from the bypass exhaust line to the second sub-exhaust line to exhaust the gas containing ozone gas from the processing container. The film forming method according to claim 9.

12. The first exhaust line has a first main exhaust line connecting the processing container and the first exhaust device, and a first sub-exhaust line which is a separate line from the first main exhaust line and connects the processing container and the first exhaust device. The first main exhaust line has a pressure adjustment unit and a vacuum exhaust device between the processing container and the first exhaust device. The first sub-exhaust line has a pressure adjustment unit between the processing container and the first exhaust device and does not have a vacuum exhaust device. When predetermined conditions are satisfied, switch the first main exhaust line and the first sub-exhaust line to exhaust the gas containing the raw material gas of ruthenium or the hydrogen-containing gas. The film forming method according to any one of claims 8 to 11.

13. When switching from the bypass exhaust line to the second sub-exhaust line to exhaust the gas containing ozone gas, it is determined that the predetermined conditions are satisfied, the gas containing the raw material gas of ruthenium is exhausted from the first main exhaust line, and the hydrogen-containing gas is exhausted from the first sub-exhaust line. The film forming method according to claim 12.

14. Repeatedly execute the steps (b), (c), and (d). The film forming method according to any one of claims 8 to 13.

15. Execute the steps (b), (c), and (d) in the same film forming apparatus. The film forming method according to any one of claims 8 to 14.

16. A film forming system having at least one film forming apparatus according to any one of claims 1 to 7, and performing a process including a process of embedding ruthenium in a substrate having a concave portion using the film forming apparatus.

17. The film forming system has a pre-cleaning apparatus that performs a process of removing an oxide on the substrate, and removes a metal oxide on the substrate before the process of embedding the ruthenium using the pre-cleaning apparatus. The film forming system according to claim 16.

18. The film forming system further laminates a ruthenium layer on the ruthenium embedded in the concave portion of the substrate after performing the process of embedding the ruthenium using the film forming apparatus. The film forming system according to claim 16 or 17.

19. The film forming system has an annealing apparatus that performs a process of annealing the substrate, and anneals the substrate after performing the process of embedding the ruthenium using the annealing apparatus or the substrate after further laminating a ruthenium layer. The film forming system according to claim 18.

Images