Substrate processing method, method for manufacturing semiconductor device, substrate processing device, and program

Abstract

Provided is a technique comprising: a preparation step for preparing a substrate in a state in which a resist removal process has been performed on the substrate, the substrate having an organic interlayer insulating film, a first metal-containing film that contains a first metal, a first diffusion prevention film that is provided between the first metal-containing film and the organic interlayer insulating film, and a resist that is formed on the side of the first metal-containing film; and a diffusion prevention film formation step for forming a second diffusion prevention film in a space between the organic interlayer insulating film and the first metal-containing film, the space being formed by removing a portion of the first diffusion prevention film in the resist removal process.

Description

Substrate processing method, semiconductor device manufacturing method, substrate processing apparatus and program

[0001] This disclosure relates to a substrate processing method, a semiconductor device manufacturing method, a substrate processing apparatus, and a program.

[0002] One manufacturing process for semiconductor devices involves supplying a processing gas to a substrate having metal-containing wiring (for example, Patent Document 1).

[0003] Japanese Patent Publication No. 2017-220642

[0004] When processing a circuit board, not only the wiring being processed but also the film surrounding it may be processed.

[0005] This disclosure provides a technology capable of improving the quality of wiring and the film formed around it.

[0006] According to one aspect of the present disclosure, a technique is provided comprising: a preparation step of preparing a substrate having an organic interlayer insulating film, a first metal-containing film containing a first metal, a first diffusion-blocking film provided between the first metal-containing film and the organic interlayer insulating film, and a resist formed on the side of the first metal-containing film, to which a resist removal treatment has been performed; and a diffusion-blocking film formation step of forming a second diffusion-blocking film in the space between the first metal-containing film and the organic interlayer insulating film, which is formed when a part of the first diffusion-blocking film is removed in the resist removal treatment.

[0007] According to this disclosure, it is possible to improve the quality of the wiring and the film formed around it.

[0008] Figure 1 is a diagram illustrating the state of the substrate, specifically the state after a resist has been applied. Figure 2 is a diagram illustrating the state of the substrate, specifically the state after a removal process to remove the resist described in Figure 1. Figure 3 is a diagram illustrating the state of the substrate, specifically the state after a barrier metal film has been formed on the substrate described in Figure 2. Figure 4 is a diagram illustrating the state of the substrate, specifically the state after an interlayer insulating film has been formed on the substrate described in Figure 3. Figure 5 is a diagram illustrating the state of the substrate, specifically the state after a seed film has been formed on the substrate described in Figure 4. Figure 6 is a diagram illustrating the state of the substrate, specifically the state after a wiring film has been formed on the substrate described in Figure 5. Figure 7 is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus preferably used in one embodiment of this disclosure, showing the processing furnace 202 portion in a vertical cross-sectional view. Figure 8 is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus preferably used in one embodiment of this disclosure, showing the processing furnace 202 portion in a cross-sectional view along line A-A in Figure 7. Figure 9 is a schematic configuration diagram of a controller 121 of a substrate processing apparatus preferably used in one embodiment of the present disclosure, and is a block diagram showing the control system of the controller 121. Figure 10(a) is a schematic cross-sectional view showing the surface portion of a wafer having a first surface and a second surface. Figure 10(b) is a schematic cross-sectional view showing the surface portion of a wafer after a modification step has been performed from the state in Figure 10(a) to selectively form an inhibitor layer on the first surface. Figure 10(c) is a schematic cross-sectional view showing the surface portion of a wafer after a first film formation step of a second diffusion prevention film has been performed from the state in Figure 10(b) to selectively form a first film on the second surface.

[0009] Embodiments of this disclosure are described below.

[0010] (1) Description of the processing substrate First, a first aspect of the present disclosure will be described with reference to the drawings.

[0011] The first aspect of this disclosure will be described below with reference to the drawings. Note that the drawings used in the following description are schematic, and the dimensional relationships and proportions of the elements shown in the drawings do not necessarily correspond to reality. Furthermore, the dimensional relationships and proportions of the elements do not necessarily correspond between multiple drawings.

[0012] The state of the substrate S processed according to the first embodiment of this disclosure will be explained with reference to Figures 1 to 6.

[0013] As shown in Figure 1, a pad terminal 101, a passivation film 102, an organic interlayer insulating film 103, a barrier metal film 104, a wiring film 105, and a resist 106 are formed on the substrate S. Before reaching the state shown in Figure 1, the resist 106 is applied without the wiring film 105, and then a masking process is performed before the wiring film 105 is formed. Here, the layer having the wiring film 105 is referred to as the Nth layer.

[0014] The pad terminal 101 and the wiring film 105 are electrically connected. The wiring film 105 is a metal-containing film containing, for example, copper (Cu) as a first metal. The wiring film 105 is also referred to as a metal-containing film. Furthermore, the wiring film 105 is also referred to as a first metal-containing film to distinguish it from the wiring film 113 described later. Multiple wiring films 105 are provided according to the circuit structure, and an organic interlayer insulating film 103 is provided between the multiple wiring films 105 to electrically insulate the wiring 105. The organic interlayer insulating film 103 is an organic insulating film containing organic matter. Furthermore, the organic interlayer insulating film 103 contains impurities such as oxygen components that are mixed in during the formation process. The organic interlayer insulating film 103 electrically insulates the multiple wiring films 103 and is also referred to as an interlayer insulating film. The organic interlayer insulating film 103 is also referred to as a first interlayer insulating film or a first organic interlayer insulating film to distinguish it from the organic interlayer insulating film 109 described later.

[0015] A passivation film 102 is provided below the organic interlayer insulating film 103 to suppress the penetration of components in the organic interlayer insulating film 103 downwards. In addition, a barrier metal film 104 is formed above and to the sides of the organic interlayer insulating film 103 to suppress the penetration of components in the wiring film 105, such as copper components, into the organic interlayer insulating film 103. The barrier metal film 104 is also called a diffusion prevention film because it suppresses the diffusion of components in the wiring film 105. The barrier metal film 104 is also called a first barrier metal film or a first diffusion prevention film to distinguish it from the barrier metal film 108 described later.

[0016] Figure 2 shows the substrate S in the state shown in Figure 1, with the resist 106 and the barrier metal film 104 located below the resist 106 removed. After removing the resist 106, the barrier metal film 104 located below the resist 106 is removed by the existing wet etching process. However, as a result of the disclosed research, it was found that after the wet etching process, a portion of the barrier metal film 104 located between the wiring film 105 and the organic interlayer insulating film 103 is removed, and a space 107 is formed between the wiring film 105 and the organic interlayer insulating film 103. This is presumed to be because a portion of the barrier metal film 104 was removed by the wet etching process.

[0017] After the state of FIG. 2, in order to form the (N + 1)-th layer on the N-th layer, an interlayer insulating film and a wiring film as a second metal-containing film are formed. Here, the substrate S is processed while being heated to a predetermined temperature. However, when forming the (N + 1)-th layer in the state where the space 107 exists as described above, it is conceivable that components in the wiring film 105, such as copper, move from the wiring film 105 to the organic interlayer insulating film 103. In that case, the resistance value may vary in the organic interlayer insulating film 103, which may affect the quality of the organic interlayer insulating film 103. Further, for example, components in the organic interlayer insulating film 103, such as oxygen, may move to the wiring film 105, which may cause oxidation, corrosion, etc. of the wiring film 105 and may affect the quality of the wiring film 105. Further, due to these actions, there is a risk that the organic interlayer insulating film 103 may peel off. Furthermore, there is a possibility that the wiring film 105 and the organic interlayer insulating film 103 may be electrically connected through the space 107. When the distance between the wiring films 105 is reduced in the future to achieve a narrow pitch, it is conceivable that the adjacent wiring films 105 may be electrically connected through the organic interlayer insulating film 103 between the adjacent wiring films 105. As a result, it is conceivable that the adjacent pads 101 may be electrically connected unintentionally. These are considered to have a greater impact on device characteristics as miniaturization progresses in the future.

[0018] Therefore, in this aspect, as shown in FIG. 3, a barrier metal film 108 is formed around the wiring film 105, and in the space 107, the barrier metal film 108 containing a second metal described later is formed. The barrier metal film 108 is also referred to as a second barrier metal film or a second diffusion prevention film.

[0019] Here, among the barrier metal film 108, the film formed in the space 107 is referred to as a barrier metal film 108a, the film formed on the side surface of the wiring film 105 is referred to as a barrier metal film 108b, and the film formed on the upper surface of the wiring film 105 is referred to as a barrier metal film 108c. The barrier metal film 108a is also referred to as the first film of the second barrier metal film, the barrier metal film 108b is also referred to as the second film of the second barrier metal film, and the barrier metal film 108c is also referred to as the third film of the second barrier metal film. The method for forming the barrier metal film 108 will be described later.

[0020] The barrier metal film 108a can suppress the movement of components in the wiring film 105 into the organic interlayer insulating film 103, and can also suppress the movement of components in the organic interlayer insulating film 103 into the first metal-containing film.

[0021] After forming the barrier metal film 108, the (N + 1)th layer is formed. For example, as shown in FIG. 4, a second interlayer insulating film 109 is formed on the barrier metal film 108 (108a, 108b, 108c), and then a pattern is formed according to the circuit configuration.

[0022] After forming the second interlayer insulating film 109, as shown in FIG. 5, a seed layer 111 is formed. After forming the seed layer 111, a contact 110 is formed. A recess 112 is formed between the second interlayer insulating films 109, and a wiring film 113 is formed as shown in FIG. 6 so as to fill the recess 112. Similar to the wiring film 105, the wiring film 113 is configured as a metal-containing film containing, for example, copper. The wiring film 113 is also referred to as a second metal-containing film.

[0023] Here, since the barrier metal film 108 has a metal component, the wiring film 105 and the wiring film 113 can be electrically connected. Here, the metal component in the barrier metal film 108 is also called a second metal and is composed of a component different from the first metal. Also, the barrier metal film 108 is a copper-free film. By making it copper-free, the diffusion of copper components from the barrier metal film 108 to the surrounding films is suppressed. Therefore, by using the barrier metal film 108 as a metal-containing film as in this embodiment, electrical conduction can be ensured between the wiring film 105 and the wiring film 113 without performing the step of removing the barrier metal film 108.

[0024] The barrier metal film 108 may be composed of an inorganic metal film that does not contain an organic substance rather than a metal containing an organic substance. Since the inorganic metal film has a higher density than the metal film containing an organic substance, it is possible to more reliably suppress the movement of components in the wiring film 105 into the organic interlayer insulating film 103.

[0025] Next, a substrate processing apparatus and a forming method for forming the barrier metal film 108 will be described with reference to FIGS. 7 to 9.

[0026] (2) As shown in the configuration diagram 7 of the substrate processing apparatus, the processing furnace 202 has a heater 207 as a temperature controller (heating unit). The heater 207 is cylindrical and is mounted vertically by being supported by a holding plate. The heater 207 functions as an energy supply unit that provides energy to the gas, and also functions as an activation mechanism (excitation unit) when the gas is activated (excited) by heat.

[0027] Inside the heater 207, a reaction tube 203 is arranged concentrically with the heater 207. The reaction tube 203 is made of, for example, quartz (SiO₂ ２ The reaction tube 203 is made of a heat-resistant material such as silicon carbide (SiC) and is formed in a cylindrical shape with a closed upper end and an open lower end. Below the reaction tube 203, a manifold 209 is arranged concentrically with the reaction tube 203. The manifold 209 is made of a metal material such as stainless steel (SUS) and is formed in a cylindrical shape with open upper and lower ends. The upper end of the manifold 209 engages with the lower end of the reaction tube 203 and is configured to support the reaction tube 203. An O-ring 220a is provided between the manifold 209 and the reaction tube 203 as a sealing member. The reaction tube 203 is installed vertically, similar to the heater 207. The reaction tube 203 and the manifold 209 mainly constitute the processing vessel (reaction vessel). A processing chamber 201 is formed in the hollow cylindrical part of the processing vessel. The processing chamber 201 is configured to accommodate the substrate S. Processing of the substrate S is performed in this processing chamber 201.

[0028] Within the processing chamber 201, nozzles 249a to 249c, which serve as the first to third supply units, are provided so as to penetrate the side walls of the manifold 209. Nozzles 249a to 249c are also referred to as the first to third nozzles. Nozzles 249a to 249c are made of a heat-resistant material such as quartz or SiC. Gas supply pipes 232a to 232c are connected to nozzles 249a to 249c, respectively. Nozzles 249a to 249c are all different nozzles, and nozzles 249a and 249c are each provided adjacent to nozzle 249b.

[0029] Gas supply pipes 232a to 232c are equipped with, in order from the upstream side of the gas flow, mass flow controllers (MFCs) 241a to 241c and valves 243a to 243c, which are flow control devices (flow control units). Downstream of valve 243a of gas supply pipe 232a, gas supply pipes 232d and 232f are connected, respectively. Downstream of valve 243b of gas supply pipe 232b, gas supply pipes 232e and 232g are connected, respectively. Downstream of valve 243c of gas supply pipe 232c, gas supply pipe 232h is connected. Downstream of the connection between gas supply pipe 232c and gas supply pipe 232h, a remote plasma unit (RPU) 270, which is a plasma excitation unit (plasma generation unit, plasma generator) for exciting the gas into a plasma state, is provided. Gas supply pipes 232d to 232h are equipped with MFCs 241d to 241h and valves 243d to 243h, respectively, in order from the upstream side of the gas flow. Gas supply pipes 232a to 232h are made of a metal material such as SUS.

[0030] As shown in Figure 8, nozzles 249a to 249c are each provided in an annular space in plan view between the inner wall of the reaction tube 203 and the substrate S, extending upward from the lower part of the inner wall of the reaction tube 203 towards the direction of arrangement of the substrate S. That is, nozzles 249a to 249c are each provided in a region that horizontally surrounds the substrate arrangement region, on the side of the substrate arrangement region where the substrate S are arranged, and along the substrate arrangement region. In plan view, nozzle 249b is positioned to be directly opposite the exhaust port 231a, described later, with the center of the substrate S being transported into the processing chamber 201 in between. Nozzles 249a and 249c are positioned to sandwich a straight line L passing through the center of nozzle 249b and the center of exhaust port 231a from both sides along the inner wall of the reaction tube 203 (outer periphery of the substrate S). Straight line L is also the straight line passing through the center of nozzle 249b and the center of the substrate S. In other words, nozzle 249c is located on the opposite side of nozzle 249a across the straight line L. Nozzles 249a and 249c are arranged symmetrically with respect to the straight line L as the axis of symmetry. Gas supply holes 250a to 250c are provided on the sides of nozzles 249a to 249c, respectively, for supplying gas. Each of the gas supply holes 250a to 250c opens so as to face (oppose) the exhaust port 231a in a plan view, making it possible to supply gas toward the substrate S. Multiple gas supply holes 250a to 250c are provided extending from the bottom to the top of the reaction tube 203.

[0031] From the gas supply pipe 232a, the reforming agent is supplied into the processing chamber 201 via the MFC 241a, valve 243a, and nozzle 249a.

[0032] From the gas supply pipe 232b, the first raw material is supplied into the processing chamber 201 via the MFC 241b, valve 243b, and nozzle 249b. The first raw material is used as one of the first film-forming agents.

[0033] From the gas supply pipe 232c, the first reactant and the second reactant are supplied into the processing chamber 201 via the MFC 241c, valve 243c, and nozzle 249c. The first reactant is used as one of the first film-forming agents. The second reactant is used as one of the second film-forming agents.

[0034] From the gas supply pipe 232d, the second raw material is supplied into the processing chamber 201 via the MFC 241d, valve 243d, gas supply pipe 232a, and nozzle 249a. The second raw material is used as one of the second film-forming agents.

[0035] From the gas supply pipe 232e, the cleaning agent is supplied into the processing chamber 201 via the MFC 241e, valve 243e, gas supply pipe 232b, and nozzle 249b.

[0036] Inert gas is supplied from gas supply pipes 232f to 232h into the processing chamber 201 via MFCs 241f to 241h, valves 243f to 243h, gas supply pipes 232a to 232c, and nozzles 249a to 249c, respectively. The inert gas acts as a purge gas, carrier gas, diluent gas, etc.

[0037] The reformer supply system is mainly composed of gas supply pipe 232a, MFC 241a, and valve 243a. The first raw material supply system is mainly composed of gas supply pipe 232b, MFC 241b, and valve 243b. The first and second reactant supply systems are mainly composed of gas supply pipe 232c, MFC 241c, and valve 243c. The second raw material supply system is mainly composed of gas supply pipe 232d, MFC 241d, and valve 243d. The cleaning agent supply system is mainly composed of gas supply pipe 232e, MFC 241e, and valve 243e. The inert gas supply system is mainly composed of gas supply pipes 232f to 232h, MFCs 241f to 241h, and valves 243f to 243h. The first raw material supply system and the first reactant supply system, or all of them, may also be referred to as the first film-forming agent supply system. The second raw material supply system and the second reactant supply system, or all of them, may also be referred to as the second film-forming agent supply system. Either the first film-forming agent supply system or the second film-forming agent supply system, or both, may be collectively referred to as the supply system. Furthermore, the supply system may include a cleaning agent supply system. Furthermore, the supply system may include an inert gas supply system.

[0038] Of the various supply systems described above, one or all of them may be configured as an integrated supply system 248, which is comprised of valves 243a to 243h and MFCs 241a to 241h. The integrated supply system 248 is connected to each of the gas supply pipes 232a to 232h, and the supply operation of various substances (various gases) into the gas supply pipes 232a to 232h, i.e., the opening and closing operation of valves 243a to 243h and the flow rate adjustment operation by MFCs 241a to 241h, is controlled by a controller 121, which will be described later. The integrated supply system 248 is configured as an integrated or segmented integrated unit, and can be attached to and detached from the gas supply pipes 232a to 232h, etc., in units of the integrated unit, and is configured so that maintenance, replacement, and expansion of the integrated supply system 248 can be performed in units of the integrated unit.

[0039] An exhaust port 231a for exhausting the atmosphere inside the processing chamber 201 is provided at the lower part of the side wall of the reaction tube 203. As shown in Figure 8, the exhaust port 231a is located in a position opposite (facing) the nozzles 249a to 249c (gas supply holes 250a to 250c) with the substrate S in between, in a plan view. The exhaust port 231a may also be provided along the upper part of the side wall of the reaction tube 203, that is, along the substrate arrangement area. An exhaust pipe 231 is connected to the exhaust port 231a. A vacuum pump 246, which is a vacuum evacuation device, is connected to the exhaust pipe 231 via a pressure sensor 245, which is a pressure detector (pressure detection unit) for detecting the pressure inside the processing chamber 201, and an APC (Auto Pressure Controller) valve 244, which is a pressure regulator (pressure adjustment unit). The APC valve 244 can be opened and closed while the vacuum pump 246 is operating to evacuate and stop the vacuum evacuation from the processing chamber 201. Furthermore, while the vacuum pump 246 is operating, the valve opening can be adjusted based on the pressure information detected by the pressure sensor 245 to adjust the pressure inside the processing chamber 201. The exhaust system mainly consists of the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. The vacuum pump 246 may also be included in the exhaust system.

[0040] Below the manifold 209, a seal cap 219 is provided as a furnace opening cover capable of airtightly closing the lower end opening of the manifold 209. The seal cap 219 is made of a metal material such as SUS and is formed in a disc shape. An O-ring 220b is provided on the upper surface of the seal cap 219 as a sealing member that contacts the lower end of the manifold 209. Below the seal cap 219, a rotating mechanism 267 for rotating the boat 217, which will be described later, is installed. The rotating shaft 255 of the rotating mechanism 267 passes through the seal cap 219 and is connected to the boat 217. The rotating mechanism 267 is configured to rotate the substrate S by rotating the boat 217. The seal cap 219 is configured to be raised and lowered vertically by a boat elevator 115, which is installed outside the reaction tube 203 as a lifting mechanism. The boat elevator 115 is configured as a transport device (transport mechanism) that moves the substrate S into and out of the processing chamber 201 by raising and lowering the seal cap 219.

[0041] Below the manifold 209, a shutter 219s is provided as a furnace opening cover that can airtightly close the lower end opening of the manifold 209 when the seal cap 219 is lowered and the boat 217 is removed from the processing chamber 201. The shutter 219s is made of a metal material such as SUS and is formed in a disc shape. An O-ring 220c is provided on the upper surface of the shutter 219s as a sealing member that contacts the lower end of the manifold 209. The opening and closing operation of the shutter 219s (such as lifting and lowering or rotating) is controlled by the shutter opening and closing mechanism 115s.

[0042] The boat 217, which serves as a substrate support, is configured to support multiple substrates S, for example 25 to 200 substrates S, in a horizontal position and aligned vertically with their centers aligned, in multiple layers, that is, arranged with spacing between them. The boat 217 is made of a heat-resistant material such as quartz or SiC. At the bottom of the boat 217, multiple layers of heat-insulating plates 218, also made of a heat-resistant material such as quartz or SiC, are supported.

[0043] A temperature sensor 263 is installed inside the reaction tube 203 as a temperature detector. By adjusting the amount of power supplied to the heater 207 based on the temperature information detected by the temperature sensor 263, the temperature inside the processing chamber 201 is adjusted to the desired temperature distribution. The temperature sensor 263 is installed along the inner wall of the reaction tube 203.

[0044] As shown in Figure 9, the controller 121, which is the control unit (control means), is configured as a computer equipped with a CPU (Central Processing Unit) 121a, RAM (Random Access Memory) 121b, storage device 121c, and I / O port 121d. The RAM 121b, storage device 121c, and I / O port 121d are configured to exchange data with the CPU 121a via an internal bus 121e. An input / output device 122, configured as, for example, a touch panel, is connected to the controller 121. Furthermore, an external storage device 123 can be connected to the controller 121.

[0045] The storage device 121c is composed of, for example, flash memory, HDD (Hard Disk Drive), SSD (Solid State Drive), etc. The storage device 121c contains, in a readable format, control programs that control the operation of the substrate processing device, and process recipes that describe the procedures and conditions for substrate processing, as described later. The process recipe functions as a program, combining the procedures in the substrate processing described later so that the controller 121 causes the substrate processing device to execute them and obtain a predetermined result. Hereinafter, process recipes and control programs will be collectively referred to simply as "programs." Similarly, process recipes will be simply referred to as "recipes." In this specification, the term "program" may include only a recipe, only a control program, or both. The RAM 121b is configured as a memory area (work area) where programs and data read by the CPU 121a are temporarily held.

[0046] The I / O port 121d is connected to the MFCs 241a to 241h, valves 243a to 243h, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, rotating mechanism 267, boat elevator 115, shutter opening / closing mechanism 115s, etc.

[0047] The CPU 121a is configured to read and execute a control program from the storage device 121c, and to read a recipe from the storage device 121c in response to input of operation commands from the input / output device 122. The CPU 121a is configured to control the flow rate adjustment operation of various substances (various gases) by the MFCs 241a to 241h, the opening and closing operation of valves 243a to 243h, the opening and closing operation of the APC valve 244 and the pressure adjustment operation of the APC valve 244 based on the pressure sensor 245, the starting and stopping of the vacuum pump 246, the temperature adjustment operation of the heater 207 based on the temperature sensor 263, the rotation and rotation speed adjustment operation of the boat 217 by the rotation mechanism 267, the raising and lowering operation of the boat 217 by the boat elevator 115, and the opening and closing operation of the shutter 219s by the shutter opening and closing mechanism 115s, in accordance with the contents of the read recipe.

[0048] The controller 121 can be configured by installing the above-mentioned program stored in the external storage device 123 onto a computer. The external storage device 123 includes, for example, magnetic disks such as HDDs, optical disks such as CDs, magneto-optical disks such as MOs, and semiconductor memory such as USB memory and SSDs. The storage device 121c and the external storage device 123 are configured as computer-readable recording media. Hereinafter, these will be collectively referred to simply as recording media. In this specification, the term recording media may include only the storage device 121c, only the external storage device 123, or both. Note that the program may be provided to the computer using communication means such as the Internet or a dedicated line, without using the external storage device 123.

[0049] (3) Substrate Processing Process Using the substrate processing apparatus described above, an example of a processing sequence for processing a substrate as one step in the manufacturing process of a semiconductor device, that is, for selectively forming a barrier metal film 108 on the second surface of the substrate S, out of the first and second surfaces of the substrate S, will be described. In the following description, the operation of each part constituting the substrate processing apparatus is controlled by the controller 121.

[0050] Furthermore, as shown in Figure 2, the substrate S processed by the substrate processing apparatus is in a state in which a space 107 has been formed after etching. In this embodiment, a first surface is formed on the surface of the organic interlayer insulating film 103, and a second surface is formed on the surface of the wiring film 105.

[0051] Furthermore, the following example describes a case in which, during the barrier metal film formation step, the first raw material and the first reactant are alternately supplied to the substrate S as the first film-forming agent.

[0052] In this specification, the processing sequence described above may also be shown as follows for convenience. The same notation will be used in the following descriptions of modifications and other embodiments.

[0053] Modifier → (First raw material → First reactant) × m

[0054] Furthermore, as shown in the processing sequence below, a cleaning step may be performed before the modification step, in which a cleaning agent is supplied to the substrate S to remove the native oxide film formed on the surface of the substrate S.

[0055] Detergent → Modifier → (First raw material → First reactant) × m Modifier → (First raw material → First reactant) × m Detergent → Modifier → (First raw material → First reactant) × m

[0056] In this specification, the term "substrate" may refer to the substrate itself or to a laminate of a substrate and a predetermined layer or film formed on its surface. In this specification, the term "surface of the substrate" may refer to the surface of the substrate itself or to the surface of a predetermined layer formed on the substrate. In this specification, when it is stated that "a predetermined layer is formed on the substrate," it may refer to directly forming the predetermined layer on the surface of the substrate itself or to forming the predetermined layer on top of a layer already formed on the substrate.

[0057] As used herein, the term "agent" includes at least one of gaseous substances and liquid substances. Liquid substances include mist-like substances. That is, each of the modifier, the first film-forming agent (first raw material, first reactant), and the second film-forming agent (second raw material, second reactant) may contain a gaseous substance, a liquid substance such as a mist-like substance, or both.

[0058] As used herein, the term "layer" includes at least one of a continuous layer and a discontinuous layer. For example, an inhibitor layer may include a continuous layer, a discontinuous layer, or both, as long as it is capable of causing a film formation inhibitory effect.

[0059] (Substrate charging and boat loading) Once multiple substrates S are loaded into the boat 217 (substrate charging), the shutter 219s is moved by the shutter opening / closing mechanism 115s, opening the lower end opening of the manifold 209 (shutter opening). Then, as shown in Figure 7, the boat 217 supporting the multiple substrates S is lifted by the boat elevator 115 and carried into the processing chamber 201 (boat loading). In this state, the seal cap 219 seals the lower end of the manifold 209 via the O-ring 220b. In this way, the substrates S are prepared in the processing chamber 201.

[0060] The substrate S loaded into the boat 217 has a first surface and a second surface, as shown in Figure 10(a). The first surface is the surface of the first substrate, and the second surface is the surface of the second substrate. As described above, here we will explain, for example, the case in which the first surface is the surface of the organic interlayer insulating film as the first substrate, and the second surface is the surface of the wiring film as the second substrate.

[0061] (Pressure and Temperature Adjustment) After the boat loading is complete, the processing chamber 201, i.e., the space where the substrate S is located, is evacuated (reduced pressure exhaust) by the vacuum pump 246 so that it reaches the desired pressure (vacuum level). At this time, the pressure inside the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 244 is feedback controlled based on this measured pressure information. The substrate S inside the processing chamber 201 is also heated by the heater 207 so that it reaches the desired processing temperature. At this time, the amount of power supplied to the heater 207 is feedback controlled based on the temperature information detected by the temperature sensor 263 so that the processing chamber 201 has the desired temperature distribution. The rotation of the substrate S by the rotation mechanism 267 is also started. The exhaust of the processing chamber 201, the heating of the substrate S, and the rotation are all carried out continuously at least until the processing of the substrate S is completed. Here, the desired temperature refers to a temperature below the glass transition temperature of the film surrounding the diffusion prevention film 108, for example, the organic interlayer insulating film 103. By processing at a temperature below the glass transition temperature, a diffusion-blocking film 108 can be formed while maintaining the quality of the surrounding film, such as the organic interlayer insulating film 103.

[0062] (Cleaning step) After that, a cleaning agent is supplied to the substrate S.

[0063] Specifically, valve 243e is opened to allow the cleaning agent to flow into the gas supply pipe 232e. The flow rate of the cleaning agent is adjusted by MFC 241e and supplied into the processing chamber 201 via gas supply pipe 232b and nozzle 249b, and exhausted from exhaust port 231a. At this time, the cleaning agent is supplied to the substrate S from the side of the substrate S (cleaning agent supply). At this time, valves 243f to 243h may be opened to supply inert gas into the processing chamber 201 via nozzles 249a to 249c, respectively.

[0064] By supplying a cleaning agent to the substrate S under the processing conditions described later, the native oxide film formed on the second surface of the substrate S can be removed (etched), exposing the second surface. At this time, the surfaces of the first and second substrates of the substrate S, i.e., the first surface and the second surface, are exposed as shown in Figure 10(a).

[0065] Examples of processing conditions when supplying the cleaning agent in the washing step include: Processing temperature: 50 to 200°C, preferably 70 to 150°C; Processing pressure: 10 to 2000 Pa, preferably 100 to 1500 Pa; Processing time: 10 to 60 minutes, preferably 30 to 60 minutes; Cleaning agent supply flow rate: 0.05 to 1 slm, preferably 0.1 to 0.5 slm; Inert gas supply flow rate (per gas supply pipe): 1 to 10 slm, preferably 2 to 10 slm.

[0066] In this specification, numerical ranges such as "50 to 200°C" mean that the lower and upper limits are included within that range. For example, "50 to 200°C" means "50°C or more and 200°C or less." The same applies to other numerical ranges. In this specification, processing temperature means the temperature of the substrate S or the temperature inside the processing chamber 201, and processing pressure means the pressure inside the processing chamber 201. Processing time means the time during which the processing is continued. When the supply flow rate includes 0, 0 slm means that the substance (gas) is not supplied. These same rules apply in the following explanations.

[0067] After removing the native oxide film from the second surface and exposing the second surface, valve 243e is closed to stop the supply of cleaning agent into the processing chamber 201. Then, the processing chamber 201 is evacuated to remove any remaining gaseous substances from the processing chamber 201. At this time, valves 243f to 243h are opened to supply inert gas into the processing chamber 201 via nozzles 249a to 249c. The inert gas supplied from nozzles 249a to 249c acts as a purge gas, thereby purging the processing chamber 201.

[0068] Examples of processing conditions when purging in the washing step include: processing pressure: 1 to 30 Pa; processing time: 1 to 120 seconds, preferably 1 to 60 seconds; inert gas supply flow rate (per gas supply pipe): 0.5 to 20 slm. It is preferable that the processing temperature when purging in this step is the same as the processing temperature when supplying the cleaning agent.

[0069] As a cleaning agent, for example, a fluorine (F)-containing gas can be used. Examples of F-containing gases include chlorine trifluoride (ClF). ３ ) gas, chlorine fluoride (ClF) gas, nitrogen fluoride (NF ３ ) gas, hydrogen fluoride (HF) gas, fluorine (F ２ Gases and the like can be used. Various cleaning solutions can also be used as cleaning agents. For example, an aqueous HF solution can be used as a cleaning agent to perform DHF cleaning. For example, a cleaning solution containing ammonia water, hydrogen peroxide, and pure water can be used as a cleaning agent to perform SC-1 cleaning (APM cleaning). For example, a cleaning solution containing hydrochloric acid, hydrogen peroxide, and pure water can be used as a cleaning agent to perform SC-2 cleaning (HPM cleaning). For example, a cleaning solution containing sulfuric acid and hydrogen peroxide can be used as a cleaning agent to perform SPM cleaning. In other words, the cleaning agent may be a gaseous substance or a liquid substance. The cleaning agent may also be a liquid substance such as a mist. One or more of these can be used as cleaning agents.

[0070] As an inert gas, nitrogen (N ２ Other gases such as argon (Ar), helium (He), neon (Ne), and xenon (Xe) can be used. One or more of these can be used as the inert gas. This also applies to each of the steps described later.

[0071] If the native oxide film formed on the surface of the substrate S is removed beforehand and the substrate S is used in that state, the cleaning step can be omitted. In that case, the modification step described later will be performed after pressure adjustment and temperature adjustment.

[0072] (Modification step) After the cleaning step, a modifier that reacts with the first surface is supplied to the substrate S.

[0073] Specifically, valve 243a is opened, and the reforming agent is allowed to flow into the gas supply pipe 232a. The flow rate of the reforming agent is adjusted by MFC 241a, supplied into the processing chamber 201 via nozzle 249a, and exhausted from exhaust port 231a. At this time, the reforming agent is supplied to the substrate S from the side of the substrate S (reforming agent supply). At this time, valves 243f to 243h may be opened to supply inert gas into the processing chamber 201 via nozzles 249a to 249c, respectively.

[0074] By supplying a modifier that reacts with the first surface to the substrate S under the processing conditions described later, inhibitor molecules, which are at least a part of the molecular structure of the molecules constituting the modifier, can be chemically adsorbed onto the first surface of the substrate S, thereby forming an inhibitor layer on the first surface as shown in Figure 10(b). In other words, in this step, by supplying a modifier that reacts with the first surface to the substrate S, inhibitor molecules contained in the modifier can be adsorbed onto the first surface, thereby forming an inhibitor layer on the first surface. To put it another way, in this step, the first surface can be modified to form an inhibitor layer on the first surface. This makes it possible to terminate the first surface, which is the outermost surface of the first substrate, with inhibitor molecules, which are at least a part of the molecular structure of the molecules constituting the modifier. Inhibitor molecules are also called film formation inhibiting molecules (adsorption inhibiting molecules, reaction inhibiting molecules). The inhibitor layer is also called a film formation inhibiting layer (adsorption inhibiting layer, reaction inhibiting layer).

[0075] The inhibitor layer formed in this step contains residues derived from the modifier, which are at least a portion of the molecular structure of the molecules constituting the modifier. In the first film formation step described later, the inhibitor layer prevents the adsorption of the first raw material (first film-forming agent) onto the first surface and inhibits (suppresses) the progress of the film formation reaction on the first surface.

[0076] In this step, at least a portion of the molecular structure of the molecules constituting the modifier may be adsorbed onto a part of the second surface of the substrate S, but the amount of adsorption is small, and the amount adsorbed onto the first surface of the substrate S is overwhelmingly larger. This selective (preferential) adsorption is possible because the processing conditions in this step are set so that the modifier does not undergo gas phase decomposition in the processing chamber 201.

[0077] After selectively forming an inhibitor layer on the first surface of the substrate S, the valve 243a is closed to stop the supply of the modifier into the processing chamber 201. Then, using the same processing procedure and conditions as the purging in the washing step, any remaining gaseous substances in the processing chamber 201 are removed from the processing chamber 201 (purging). It is preferable that the processing temperature when purging in this step is the same as the processing temperature when supplying the modifier.

[0078] (First film formation step) After the modification step, the first film-forming agent is supplied to the substrate S, and the first film is formed on the second surface of the substrate S. That is, the first film-forming agent is supplied to the substrate S so as to react with the second surface, and a film is formed selectively (preferentially) on the second surface. Specifically, the following first raw material supply step and first reactant supply step are performed in order.

[0079] [First Raw Material Supply Step] In this step, the first raw material (first raw material gas) is supplied as a first film-forming agent to the substrate S after the modification step, that is, the substrate S after an inhibitor layer has been selectively formed on the first surface, at a first temperature.

[0080] Specifically, valve 243b is opened and the first raw material flows into the gas supply pipe 232b. The flow rate of the first raw material is adjusted by MFC 241b and supplied into the processing chamber 201 via nozzle 249b, and exhausted from exhaust port 231a. At this time, the first raw material is supplied to the substrate S from the side of the substrate S (first raw material supply). At this time, valves 243f to 243h may be opened and inert gas may be supplied into the processing chamber 201 via nozzles 249a to 249c, respectively.

[0081] By supplying the first raw material to the substrate S under the processing conditions described later, it becomes possible to selectively chemically adsorb at least a portion of the molecular structure of the molecules constituting the first raw material onto the second surface while suppressing the chemical adsorption of at least a portion of the molecular structure of the molecules constituting the first raw material onto the first surface. As a result, the first layer is selectively formed on the second surface. The first layer contains at least a portion of the molecular structure of the molecules constituting the first raw material, which are residues of the first raw material. That is, the first layer contains at least a portion of the atoms constituting the first raw material.

[0082] In this step, the formation of the first layer can be carried out under low temperature conditions, as described later, that is, at a first temperature. By forming the first layer at a first temperature in this way, it becomes possible to maintain the molecules and atoms constituting the inhibitor layer formed on the first surface without them disappearing (desorbing) from the first surface.

[0083] Furthermore, by forming the first layer under low temperature conditions as described later, i.e., at a first temperature, the first raw material can be prevented from thermally decomposing (gas phase decomposition), i.e., from self-decomposing, within the processing chamber 201. This suppresses the layering of at least a portion of the molecular structure of the molecules constituting the first raw material on the first and second surfaces, and makes it possible to selectively adsorb at least a portion of the molecular structure of the molecules constituting the first raw material onto the second surface of the first and second surfaces.

[0084] In this step, at least a portion of the molecular structure of the molecules constituting the first raw material may be adsorbed onto a part of the first surface of the substrate S, but the amount of adsorption is small, and the amount of adsorption onto the second surface of the substrate S is overwhelmingly larger. This selective (preferential) adsorption is possible because the processing conditions in this step are low temperature conditions, as described later, namely the first temperature, and conditions under which the raw material does not undergo gas phase decomposition in the processing chamber 201. Furthermore, an inhibitor layer is formed over the entire first surface, whereas an inhibitor layer is not formed over many areas of the second surface.

[0085] After selectively forming the first layer on the second surface of the substrate S, the valve 243b is closed and the supply of the first raw material into the processing chamber 201 is stopped. Then, in the same processing procedure and under the same processing conditions as the purge in the cleaning step, gaseous substances and the like remaining in the processing chamber 201 are removed from the processing chamber 201 (purge). Note that when performing the purge in this step, the processing temperature is preferably the same as the processing temperature when supplying the first raw material.

[0086] As the first raw material, for example, when forming the first film containing atom X in the first film formation step, a gas (substance) containing one or more atoms X in one molecule can be used. Further, as the first raw material, a gas (substance) that does not contain a chemical bond between atoms X can be used. Atom X includes titanium (Ti), tantalum (Ta), tungsten (W), molybdenum (Mo), ruthenium (Ru), vanadium (V), and the like.

[0087] As the first raw material, for example, titanium tetrafluoride (TiF ４ ), titanium tetrachloride (TiCl ４ ), tungsten hexafluoride (WF ６ ), tungsten hexachloride (WCl ６ ), tantalum pentafluoride (TaF ５ ), molybdenum pentafluoride (MoF ５ ), molybdenum pentachloride (MoCl ５ ), molybdenum dichloride dioxide (MoO ２ Cl ２ ), molybdenum oxychloride tetrachloride (MoOCl ４ ), tantalum pentachloride (TaCl ５ ), ruthenium trifluoride (RuF ３ ), ruthenium trichloride (RuCl ２ ), bis(ethylcyclopentadienyl)ruthenium (Ru(EtCp)2), bis(cyclopentadienyl)ruthenium (RuCp) ２At least one of the following can be used: ), etc. Also, when using V, at least one of the following can be used: tetrakisdiethylaminovanadium (V(Net2)4), tetrakisethyldimethylaminovanadium (V(NETMe2)4), tetrakisdimethylaminovanadium (V(NMe2)4), etc. Here, N represents an amino group, Me represents a methyl group, and Et represents an ethyl group.

[0088] [First Reactant Supply Step] After the first raw material supply step is completed, the first reactant (first reaction gas) is supplied to the substrate S, that is, the substrate S after the first layer has been selectively formed on the second surface, at a first temperature, as the first film-forming agent. Here, an example in which a nitrogen (N)-containing gas (N-containing substance) is used as the first reactant (first reaction gas) will be described.

[0089] Specifically, valve 243c is opened, and the first reactant is allowed to flow into the gas supply pipe 232c. The flow rate of the first reactant is adjusted by MFC 241c and supplied into the processing chamber 201 via nozzle 249c, and exhausted from exhaust port 231a. At this time, the first reactant is supplied to the substrate S from the side of the substrate S (first reactant supply). At this time, valves 243f to 243h may be opened to supply inert gas into the processing chamber 201 via nozzles 249a to 249c, respectively.

[0090] By supplying the first reactant to the substrate S under the processing conditions described later, it becomes possible to nitride at least a portion of the first layer formed on the second surface of the substrate S in the first raw material supply step. As a result, a second layer is formed on the second surface, which is the nitrided first layer.

[0091] In this step, the formation of the second layer can be carried out under low temperature conditions, as described later, i.e., at the first temperature. By forming the second layer under these low temperature conditions, i.e., at the first temperature, it becomes possible to maintain the molecules and atoms constituting the inhibitor layer formed on the first surface without them disappearing (detaching) from the first surface.

[0092] After nitriding the first layer formed on the second surface of the substrate S to transform it into a second layer, the valve 243c is closed to stop the supply of the first reactant into the processing chamber 201. Then, using the same processing procedure and conditions as the purging in the washing step, any gaseous substances remaining in the processing chamber 201 are removed from the processing chamber 201 (purging). It is preferable that the processing temperature when purging in this step is the same as the processing temperature when supplying the first reactant.

[0093] As the first reactant, for example, an N-containing gas (N-containing substance) can be used. As the N-containing gas (N-containing substance), for example, a gas containing N and hydrogen (H), or a gas containing C and N can be used. As the N and H-containing gas, for example, a hydrogen nitride-based gas containing N-H bonds can be used. As the C and N-containing gas, an amine-based gas or an organic hydrazine-based gas can be used. The first reactant may be supplied to the substrate S in a plasma state.

[0094] For example, the first reactant is ammonia (NH₄). ３ ), hydrazine (N ２ H ４ ), diazene (N ２ H ２ ), N ３ H ８ The following can be used. In addition, as the first reactant, for example, monoethylamine (C) ２ H ５ NH ２ (Abbreviation: MEA), diethylamine ((C) ２ H ５ ) ２ NH, abbreviation: DEA), triethylamine ((C ２ H ５ ) ３ N, abbreviation: TEA), monomethylamine (CH ３ NH ２ (Abbreviation: MMA), dimethylamine ((CH ３ ) ２ NH, abbreviation: DMA), trimethylamine ((CH ３ ) ３N (abbreviated as TMA), etc. can be used as the first reactant. ３ ) HN ２ H ２ (Abbreviation: MMH), dimethylhydrazine ((CH ３ ) ２ N ２ H ２ (Abbreviation: DMH), trimethylhydrazine ((CH ３ ) ２ N ２ (CH ３ )H (abbreviated as TMH), etc., can be used. One or more of these can be used as the first reactant.

[0095] [Performed a predetermined number of times] By performing the above-described first raw material supply step and first reactant supply step alternately, without synchronization, a predetermined number of times (m times, where m is an integer of 1 or more), the first film can be selectively (preferentially) formed on the second surface of the substrate S, as shown in Figure 10(c). For example, when using the above-described first raw material and first reactant, a titanium nitride (TiN) film can be selectively grown on the second surface as a barrier metal film 108. It is preferable to repeat the above cycle multiple times. That is, it is preferable to make the thickness of the second layer formed per cycle thinner than the desired thickness of the first film, and to repeat the above cycle multiple times until the thickness of the first film formed by stacking the second layer reaches the desired thickness.

[0096] As described above, by performing the above cycle a predetermined number of times, the first film can be selectively grown on the second surface of the substrate S. At this time, since an inhibitor layer is formed on the first surface of the substrate S, the growth of the first film on the first surface can be suppressed. In other words, by performing the above cycle a predetermined number of times, the growth of the first film on the second surface can be promoted while suppressing the growth of the first film on the first surface.

[0097] In the above-described embodiment, a TiN film was used as an example of the second barrier metal film, but it is not limited to that. For example, it may be composed of at least one of the following: tungsten nitride (WN) film, titanium carbide (TiC) film, ruthenium (Ru) film, tungsten carbonitride (WCN) film, RuSiN film containing ruthenium and silicon nitride, tantalum carbide (TaC) film, molybdenum nitride (MoN) film, vanadium nitride (VN) film, Ti / TiN film which is a laminated film of titanium and titanium nitride, and tantalum nitride (TaN) film. In particular, TiN films, WN films, TaC films, MoN films, and VN films can be formed using plasma at a low temperature below a predetermined temperature, for example, 250°C or below, taking into consideration the overheating of the surrounding film. Overheating refers to heating to a temperature that affects the properties of the surrounding film, for example.

[0098] As described above, when the first raw material supply step and the first reactant supply step are carried out, the inhibitor layer formed on the first surface is maintained on the first surface as described above, thereby suppressing the growth of the first film on the first surface. However, in cases where the formation of the inhibitor layer on the first surface is insufficient due to some factor, the formation and growth of the first film on the first surface may occur to a very small extent. However, even in this case, the thickness of the first film formed on the first surface will be much thinner than the thickness of the first film formed on the second surface. In this specification, "high selectivity in selective growth" includes not only the case in which no first film is formed on the first surface and the first film is formed only on the second surface, but also the case in which a very thin first film is formed on the first surface, but a much thicker first film is formed on the second surface.

[0099] (After-purging and return to atmospheric pressure) After the heat treatment step is completed, inert gas is supplied as a purge gas into the treatment chamber 201 from nozzles 249a to 249c and exhausted from exhaust port 231a. This purges the treatment chamber 201, removing any remaining gases and reaction by-products (after-purging). Subsequently, the atmosphere inside the treatment chamber 201 is replaced with inert gas (inert gas replacement), and the pressure inside the treatment chamber 201 is returned to normal pressure (return to atmospheric pressure).

[0100] (Boat Unloading and Substrate Discharge) Subsequently, the seal cap 219 is lowered by the boat elevator 115, and the lower end of the manifold 209 is opened. Then, the processed substrate S, supported by the boat 217, is unloaded from the lower end of the manifold 209 to the outside of the reaction tube 203 (boat unloading). After boat unloading, the shutter 219s is moved, and the lower end opening of the manifold 209 is sealed by the shutter 219s via the O-ring 220c (shutter close). After the processed substrate S has been unloaded from the reaction tube 203, it is removed from the boat 217 (substrate discharge).

[0101] As described above, it is preferable to perform the cleaning step, modification step, and first film formation step in the same processing room (in-situ). This allows the modification step and first film formation step to be performed without exposing the substrate S to the atmosphere, i.e., while keeping the surface of the substrate S clean, after cleaning the surface of the substrate S in the cleaning step (after removing the native oxide film), thereby enabling appropriate selective growth. In other words, performing these steps in the same processing room makes it possible to perform selective growth with high selectivity. If the cleaning step can be omitted as described above, it is preferable to perform the modification step and the first film formation step in the same processing room.

[0102] (4) Effects of this embodiment This embodiment produces one or more of the following effects:

[0103] By forming a second diffusion-blocking film in the space between the first metal-containing film, which is formed by removing a portion of the first diffusion-blocking film during the resist removal process, and the organic interlayer insulating film, the migration of components in the first metal film to the organic interlayer insulating film can be suppressed.

[0104] When the first metal film is a film containing copper, forming a second diffusion-blocking film between the first metal-containing film and the organic interlayer insulating film can suppress the migration of copper from the first metal film to the organic interlayer insulating film.

[0105] When the second diffusion-blocking film is made of a second metal different from the first metal, forming the second diffusion-blocking film between the first metal-containing film and the organic interlayer insulating film can suppress the influence of the first metal on the organic interlayer insulating film.

[0106] When the second diffusion-blocking film is a non-copper-containing film, forming the second diffusion-blocking film between the first metal-containing film and the organic interlayer insulating film can suppress the influence of copper on the organic interlayer insulating film.

[0107] By configuring the second diffusion-blocking film to include at least one of TiN, WN, TiC, Ru, WCN, RuSiN, TaC, MoN, VN, Ti / TiN, and TaN, it is possible to suppress the movement of components of the first metal-containing film between the organic interlayer insulating film and the first metal-containing film.

[0108] By configuring the second diffusion barrier to include at least one of TiN, WN, TaC, MoN, and VN, plasma treatment at a relatively lower temperature becomes possible compared to the treatment temperature in the case of heat treatment alone. Therefore, the second diffusion barrier can be formed without affecting the quality of the surrounding film.

[0109] In the diffusion-blocking film formation process, by forming the first layer of the second diffusion-blocking film in the space between the first metal-containing film and the organic interlayer insulating film, the second layer of the second diffusion-blocking film on the side surface of the first metal-containing film, and the third layer of the second diffusion-blocking film on the upper surface of the first metal-containing film, the throughput for film formation can be increased compared to forming each film individually.

[0110] By enabling the first film to suppress the migration of components from the organic interlayer insulating film into the first metal-containing film, it is possible to suppress the influence of components from the organic interlayer insulating film on the quality of the first metal film.

[0111] By enabling the first film to suppress the migration of oxygen components from the organic interlayer insulating film into the first metal-containing film, it is possible to suppress the effect of oxygen components on the quality of the first metal film.

[0112] By constructing the second diffusion-blocking film from inorganic materials, the migration of components from the first metal-containing film to the surrounding film can be more reliably suppressed.

[0113] By keeping the substrate temperature below the glass transition temperature of the organic interlayer insulating film during the diffusion prevention film formation process, a second diffusion prevention film can be formed while maintaining the quality of the organic interlayer insulating film.

[0114] In the diffusion prevention film formation process, a plasma-state gas is supplied to the substrate, allowing for processing at a lower temperature than that achieved with heat treatment alone. Therefore, the second diffusion prevention film can be formed while maintaining the quality of the surrounding film.

[0115] If a second metal-containing film is formed on the second diffusion-blocking film after the diffusion-blocking film formation process, the second diffusion-blocking film can electrically connect the first metal-containing film and the second metal-containing film.

[0116] <Other Aspects of the Disclosure> The aspects of the Disclosure have been described in detail above. However, the Disclosure is not limited to the aspects described above and can be modified in various ways without departing from its essence.

[0117] It is preferable that the recipes used for each process are prepared individually according to the processing content and stored in the storage device 121c via a telecommunications line or external storage device 123. When starting each process, it is preferable that the CPU 121a appropriately selects the appropriate recipe from among the multiple recipes stored in the storage device 121c according to the processing content. This makes it possible to form films of various film types, composition ratios, film quality, and film thickness with good reproducibility using a single substrate processing device. Furthermore, it reduces the burden on the operator and allows each process to be started quickly while avoiding operational errors.

[0118] The above-mentioned recipes are not limited to newly created ones; they may also be prepared, for example, by modifying existing recipes already installed in the board processing device. When modifying a recipe, the modified recipe may be installed in the board processing device via a telecommunications line or a recording medium on which the recipe is stored. Alternatively, existing recipes already installed in the board processing device may be directly modified by operating the input / output device 122 provided in the existing board processing device.

[0119] The above-described embodiments illustrate an example of forming a film using a batch-type substrate processing apparatus that processes multiple substrates at once. This disclosure is not limited to the above-described embodiments and can be suitably applied, for example, to forming a film using a single-wafer substrate processing apparatus that processes one or several substrates at once. Furthermore, the above-described embodiments illustrate an example of forming a film using a substrate processing apparatus having a hot-wall type processing furnace. This disclosure is not limited to the above-described embodiments and can be suitably applied to forming a film using a substrate processing apparatus having a cold-wall type processing furnace.

[0120] Even when using these substrate processing devices, each process can be carried out using the same processing procedures and conditions as described above, and the same effects as described above can be obtained.

[0121] The above-described embodiments and modifications can be used in combination as appropriate. The processing procedure and processing conditions in this case can be the same as, for example, the processing procedure and processing conditions of the above-described embodiments and modifications.

[0122] S board

Claims

1. A substrate processing method comprising: a preparation step of preparing a substrate having been subjected to a resist removal treatment, the substrate having an organic interlayer insulating film, a first metal-containing film containing a first metal, a first diffusion-blocking film provided between the first metal-containing film and the organic interlayer insulating film, and a resist formed on the side of the first metal-containing film; and a diffusion-blocking film formation step of forming a second diffusion-blocking film in the space between the first metal-containing film and the organic interlayer insulating film, which is formed when a part of the first diffusion-blocking film is removed in the resist removal treatment.

2. The substrate processing method according to claim 1, wherein the first metal-containing film is a film containing copper.

3. The substrate processing method according to claim 1, wherein the second diffusion-blocking film is a film containing a second metal different from the first metal.

4. The substrate processing method according to claim 1, wherein the second diffusion-blocking film is a copper-free film.

5. The substrate processing method according to claim 1, wherein the second diffusion-blocking film is configured to include at least one of TiN, WN, TiC, Ru, WCN, RuSiN, TaC, MoN, VN, Ti / TiN, and TaN.

6. The substrate processing method according to claim 1, wherein the second diffusion-blocking film is formed at a predetermined temperature or below and is configured to contain at least one of TiN, WN, TaC, MoN, and VN.

7. The substrate processing method according to claim 1, wherein in the diffusion-blocking film formation step, a first film of the second diffusion-blocking film is formed in the space between the first metal-containing film and the organic interlayer insulating film, a second film of the second diffusion-blocking film is formed on the side surface of the first metal-containing film, and a third film of the second diffusion-blocking film is formed on the upper surface of the first metal-containing film.

8. The substrate processing method according to claim 1, wherein the first film is capable of suppressing the migration of components in the organic interlayer insulating film into the first metal-containing film.

9. The substrate processing method according to claim 1, wherein the first film is configured to suppress the migration of oxygen components in the organic interlayer insulating film into the first metal-containing film.

10. The substrate processing method according to claim 1, wherein the second diffusion-blocking film is composed of an inorganic material.

11. The substrate processing method according to claim 1, wherein the diffusion prevention film formation step is performed at a temperature of the substrate that is below the glass transition temperature of the organic interlayer insulating film.

12. The substrate processing method according to claim 1, wherein in the diffusion prevention film formation step, a plasma gas is supplied to the substrate.

13. The substrate processing method according to claim 1, wherein a cleaning step is performed to clean the surface of the first metal-containing film before the diffusion prevention film formation step.

14. The substrate processing method according to claim 7, wherein a second metal-containing film is formed on the third film after the diffusion-preventing film formation step.

15. The substrate processing method according to claim 14, wherein the second metal-containing film is a film containing copper.

16. The substrate processing method according to claim 7, wherein the third film is electrically conductive with the second metal-containing film.

17. The substrate processing method according to claim 1, wherein in the diffusion prevention film formation step, a first film of the second diffusion prevention film is formed in the space between the first metal-containing film and the organic interlayer insulating film, a second film of the second diffusion prevention film is formed on the side surface of the first metal-containing film, and a third film of the second diffusion prevention film is formed on the upper surface of the first metal-containing film, and after the diffusion prevention film formation step, the second metal-containing film is formed so as to be in contact with the third film.

18. A method for manufacturing a semiconductor device, comprising: a preparation step of preparing a substrate having an organic interlayer insulating film, a first metal-containing film, a first diffusion-blocking film provided between the first metal-containing film and the organic interlayer insulating film, and a resist formed on the side of the first metal-containing film, and having been subjected to a resist removal treatment; and a diffusion-blocking film formation step of forming a second diffusion-blocking film in the space between the first metal-containing film and the organic interlayer insulating film, which is formed when a part of the first diffusion-blocking film is removed by the resist removal treatment.

19. A substrate processing apparatus comprising: a supply system for supplying gas to a substrate having been subjected to a resist removal treatment, the substrate having an organic interlayer insulating film, a first metal-containing film, a first diffusion-blocking film provided between the first metal-containing film and the organic interlayer insulating film, and a resist formed on the side of the first metal-containing film; and a control unit configured to control the supply system so as to form a second diffusion-blocking film in the space between the first metal-containing film and the organic interlayer insulating film, which is formed when a part of the first diffusion-blocking film is removed in the resist removal treatment.

20. A program that causes a substrate processing device to perform the following steps by computer: a procedure for preparing a substrate having an organic interlayer insulating film, a first metal-containing film, a first diffusion-blocking film provided between the first metal-containing film and the organic interlayer insulating film, and a resist formed on the side of the first metal-containing film, and a procedure for forming a second diffusion-blocking film in the space between the first metal-containing film and the organic interlayer insulating film, formed by removing a portion of the first diffusion-blocking film in the resist-removal procedure.

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