Film deposition method and film deposition apparatus

Abstract

To provide a technology for improving block performance of a SAM.SOLUTION: A film deposition method includes following (A)-(C). (A) To prepare a substrate having a first film and a second film made of a material different from that of the first film on two different regions of the surface. (B) To supply a gas of a carboxylic acid or phosphonic acid to the surface of the substrate to form a self-assembled monolayer on the surface of the second film selectively against the surface of the first film. (C) To form an object film on the surface of the first film, while inhibiting formation of the object film on the surface of the second film using the self-assembled monolayer after the (B). The (C) includes (Ca) supplying a precursor gas of the object film to the surface of the substrate and (Cb) supplying the gas of a carboxylic acid or phosphonic acid as an oxidation gas to the surface of the substrate.SELECTED DRAWING: Figure 1

Description

Technical Field

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

Background Art

[0002] Patent Document 1 describes a film forming method in which a target film is formed on a part of a substrate surface while inhibiting the formation of a target film on a part of the substrate surface using a self-assembled monolayer (SAM). It is described that a thiol-based compound or a silane-based compound is used as a precursor of the SAM.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] One aspect of the present disclosure provides a technique for improving the blocking performance of the SAM.

Means for Solving the Problems

[0005] A film forming method according to one aspect of the present disclosure includes the following (A) to (D) . (A) insulating film and a insulating film formed of a material different from the above-mentioned conductive film are provided on different regions of the surface of a substrate. (B) By supplying a gas of carboxylic acid or phosphonic acid to the surface of the substrate, a self-assembled monolayer is selectively formed on the surface of the insulating film with respect to the surface of the conductive film . (C) After (B), while inhibiting the formation of a target film on the surface of the conductive film using the self-assembled monolayer, the insulating filmThe target film is formed on the surface of the substrate. (C) includes (Ca) supplying a precursor gas of the target film to the surface of the substrate, and (Cb) supplying a carboxylic acid or phosphonic acid gas to the surface of the substrate as an oxidizing gas. (D) After (C), a plasma-generated hydrogen-containing gas is supplied to the surface of the substrate to remove any residue of carboxylic acid or phosphonic acid attached to the target film in (Ca). The cycle comprising (B), (Ca), (Cb), and (D) is repeatedly executed. [Effects of the Invention]

[0006] According to one aspect of this disclosure, the blocking performance of SAM can be improved. [Brief explanation of the drawing]

[0007] [Figure 1] Figure 1 is a flowchart showing a film deposition method according to one embodiment. [Figure 2] Figure 2(A) shows an example of step S1, Figure 2(B) shows an example of step S2, and Figure 2(C) shows an example of step S3. [Figure 3] Figure 3(A) shows an example of step S41, Figure 3(B) shows an example of step S42, and Figure 3(C) shows an example of step S5. [Figure 4] Figure 4 is a flowchart showing a film deposition method related to a modified example. [Figure 5] Figure 5 is a plan view showing a film deposition apparatus according to one embodiment. [Figure 6] Figure 6 is a cross-sectional view showing an example of the first processing unit shown in Figure 5. [Modes for carrying out the invention]

[0008] Embodiments of this disclosure will be described below with reference to the drawings. In each drawing, the same or corresponding components are denoted by the same reference numerals, and their descriptions may be omitted.

[0009] A film deposition method according to one embodiment will be described with reference to Figures 1 to 3. The film deposition method includes, for example, steps S1 to S6 shown in Figure 1. Note that the film deposition method only needs to include steps S1 and S3 to S4, and does not need to include, for example, steps S2 and S5 to S6. Furthermore, the film deposition method may include steps other than steps S1 to S6 shown in Figure 1.

[0010] Step S1 in Figure 1 includes preparing the substrate 1 as shown in Figure 2(A). The substrate 1 has a base substrate (not shown). The base substrate is, for example, a silicon wafer, a compound semiconductor wafer, or a glass substrate.

[0011] The substrate 1 has an insulating film 11 and a conductive film 12 in different regions of its substrate surface 1a. The substrate surface 1a is, for example, the top surface of the substrate 1. The insulating film 11 and the conductive film 12 are formed on a base substrate. Another functional film may be formed between the base substrate and the insulating film 11, or between the base substrate and the conductive film 12. The insulating film 11 is an example of a first film, and the conductive film 12 is an example of a second film. The materials of the first film and the second film are not particularly limited.

[0012] The insulating film 11 is, for example, an interlayer insulating film. The interlayer insulating film is preferably a low-dielectric constant (Low-k) film. The insulating film 11 is not particularly limited, but is, for example, an SiO film, a SiN film, a SiOC film, a SiON film, or a SiCN film. Here, an SiO film means a film containing silicon (Si) and oxygen (O). The atomic ratio of Si to O in an SiO film is usually 1:2, but the atomic ratio of Si to O in an SiO film in this application is not limited to 1:2. The same applies to SiN films, SiOC films, SiON films, and SiCN films. The insulating film 11 has recesses on the substrate surface 1a. The recesses are trenches, contact holes, or via holes.

[0013] The conductive film 12 is filled in the recess of the insulating film 11, for example. The conductive film 12 is, for example, a metal film. The metal film is, for example, a Cu film, a Co film, a Ru film, or a W film. Note that the conductive film 12 may be a cap film. That is, a second conductive film (not shown) may be embedded in the recess of the insulating film 11, and the conductive film 12 may cover the second conductive film. The second conductive film is formed of a metal different from that of the conductive film 12.

[0014] Although not shown, the substrate 1 may further have a third film on the substrate surface 1a. The third film is, for example, a barrier film. The barrier film is formed between the insulating film 11 and the conductive film 12 and suppresses metal diffusion from the conductive film 12 to the insulating film 11. The barrier film is not particularly limited, and is, for example, a TaN film or a TiN film. Here, the TaN film means a film containing tantalum (Ta) and nitrogen (N). The atomic ratio of Ta and N in the TaN film is not limited to 1:1. The same applies to the TiN film.

[0015] Although not shown, the substrate 1 may further have a fourth film on the substrate surface 1a. The fourth film is, for example, a liner film. The liner film is formed between the conductive film 12 and the barrier film. The liner film is formed on the barrier film and assists in forming the conductive film 12. The conductive film 12 is formed on the liner film. The liner film is not particularly limited, and is, for example, a Co film or a Ru film.

[0016] As shown in FIG. 2(B), step S2 in FIG. 1 includes cleaning the substrate surface 1a. Contaminants 22 (see FIG. 2(A)) present on the substrate surface 1a can be removed. The contaminants 22 include, for example, at least one of a metal oxide and an organic substance. The metal oxide is, for example, an oxide formed by the reaction of the conductive film 12 with the atmosphere, that is, a so-called natural oxide film. The organic substance is, for example, a deposit containing carbon and adheres during the process of processing the substrate 1. The cleaning of the substrate surface 1a may be either a dry process or a wet process.

[0017] For example, step S2 includes supplying a cleaning gas to the surface 1a of the substrate. The cleaning gas may be made into plasma in order to improve the removal efficiency of the contaminants 22. The cleaning gas includes, for example, a reducing gas such as H2 gas. The reducing gas removes oxides such as natural oxide films and organic substances.

[0018] An example of the processing conditions for step S2 is shown below. Flow rate of H2 gas: 200 sccm to 10,000 sccm Flow rate of Ar gas: 20 sccm to 2,000 sccm Power supply frequency for plasma generation: 400 kHz to 40 MHz Power for plasma generation: 50 W to 1,000 W Processing time: 10 sec to 600 sec Processing temperature (substrate temperature): 100°C to 250°C Processing pressure: 100 Pa to 2,000 Pa.

[0019] Step S3 in FIG. 1 includes selectively forming a SAM 17 on the surface of the conductive film 12 with respect to the surface of the insulating film 11, as shown in FIG. 2(C). Step S3 includes supplying a gas of a carboxylic acid, which is a precursor of the SAM 17.

[0020] The carboxylic acid contains a carboxy group (COOH group) and is represented by the general formula "R-COOH". R is, for example, a hydrocarbon group or a group in which at least a part of the hydrogen of the hydrocarbon group is substituted with fluorine. The carboxylic acid is more likely to chemisorb on the surface of the conductive film 12 than on the surface of the insulating film 11. Therefore, the SAM 17 is selectively formed on the surface of the conductive film 12.

[0021] The carboxylic acid includes, for example, at least one selected from the group consisting of CF3(CF2)2COOH, CF3COOH, C6H5COOH, and CH3(CH2) n COOH (n is an integer from 2 to 10). Hereinafter, CF3(CF2)2COOH is also referred to as PFBA (Perfluorobutyric acid).

[0022] Carboxylic acids are more readily chemiadsorbed onto the Ru film surface than thiol compounds. Therefore, when the conductive film 12 is a Ru film, the density of SAM17 can be improved. Furthermore, carboxylic acids can form SAM17 with superior high-temperature resistance compared to thiol compounds. Therefore, it is possible to set a higher processing temperature in step S4 (formation of the target film), which will be described later.

[0023] An example of the processing conditions for step S3 is shown below. PFBA gas flow rate: 10 sccm to 100 sccm Processing time: 30 sec to 600 sec Processing pressure: 100 Pa ~ 300 Pa Processing temperature: 100℃~250℃.

[0024] Note that phosphonic acid may be used instead of carboxylic acid. Phosphonic acid is represented by the general formula "RP(=O)(OH)2", where R is, for example, a hydrocarbon group in which at least some of the hydrogen atoms are replaced with fluorine. Like carboxylic acid, phosphonic acid is more readily chemiadsorbed onto the surface of the conductive film 12 than onto the surface of the insulating film 11. Therefore, SAM 17 is selectively formed on the surface of the conductive film 12.

[0025] Step S4 in Figure 1 includes forming the target film 18 on the surface of the insulating film 11 while inhibiting the formation of the target film 18 on the surface of the conductive film 12 using the SAM 17, as shown in Figures 3(A) and 3(B). The target film 18 is, for example, an insulating film and is formed on the insulating film 11.

[0026] The target film 18 is not particularly limited, but examples include AlO films, SiO films, ZrO films, or HfO films. Here, an AlO film means a film containing aluminum (Al) and oxygen (O). The atomic ratio of Al to O in an AlO film is usually 2:3, but the atomic ratio of Al to O in an AlO film in this application is not limited to 2:3. The same applies to SiO films, ZrO films, and HfO films.

[0027] The target film 18 is formed, for example, by the ALD (Atomoic Layer Deposition) method. When forming an oxide film as the target film 18 by the ALD method, the precursor gas for the target film 18 and the oxidizing gas are alternately supplied to the substrate surface 1a. The precursor gas for the target film 18 contains, for example, a metal element or metalloid element that is oxidized by the oxidizing gas.

[0028] The target film 18 may also be formed by the CVD (Chemical Vapor Deposition) method. When forming an oxide film as the target film 18 by the CVD method, the precursor gas for the target film 18 and the oxidizing gas are supplied simultaneously to the substrate surface 1a.

[0029] The following describes the process of forming the target film 18 using the ALD method. Step S4 includes steps S41 to S42, as shown in Figure 1.

[0030] Step S41 includes supplying the precursor gas of the target film 18 to the substrate surface 1a. As shown in Figure 3(A), since SAM 17 is formed on the surface of the conductive film 12, the precursor gas is selectively adsorbed onto the surface of the insulating film 11.

[0031] Step S42 includes supplying a carboxylic acid gas to the substrate surface 1a as an oxidizing gas. The carboxylic acid gas oxidizes the metal elements or metalloid elements contained in the precursor gas of the target film 18, thereby forming the target film 18 as shown in Figure 3(B). In addition, the carboxylic acid gas is used during the formation of the target film 18. conductive film 12 SAM17 can be added to the surface, improving the blocking performance of SAM17.

[0032] The same carboxylic acid gas may be used in both step S42 and step S3. Using the same carboxylic acid gas reduces the number of gas types used and the number of individual pipes required for each gas. However, as will be described later, different carboxylic acid gases may be used in both step S42 and step S3.

[0033] Furthermore, instead of carboxylic acid gas, phosphonic acid gas may be used as the oxidizing gas. Similar to carboxylic acid gas, phosphonic acid gas can also form the target film 18 by oxidizing the metal elements or metalloid elements contained in the precursor gas of the target film 18. Also, similar to carboxylic acid gas, during the formation of the target film 18, phosphonic acid gas... conductive film 12 SAM17 can be added to the surface, improving the blocking performance of SAM17.

[0034] The same phosphonic acid gas may be used in both step S42 and step S3. Using the same phosphonic acid gas reduces the number of gas types used and the number of individual pipes required for each gas. However, as will be described later, different phosphonic acid gases may be used in both step S42 and step S3.

[0035] An example of the processing conditions for step S4 is shown below. In the processing conditions below, TMA (trimethylaluminum) gas is the precursor gas for the AlO film. Step S41 TMA gas flow rate: 50 sccm Processing time: 0.1 sec to 2 sec Processing temperature: 100℃~250℃ Processing pressure: 133 Pa to 1200 Pa. Step S42 PFBA gas flow rate: 50 sccm~200 sccm Processing time: 0.5 sec to 2 sec Processing temperature: 100℃~250℃ Processing pressure: 133 Pa to 1200 Pa.

[0036] The amount of carboxylic acid or phosphonic acid gas supplied in step S42 may be less than the amount of carboxylic acid or phosphonic acid gas supplied in step S3. This reduces the amount of carboxylic acid or phosphonic acid residue attached to the target film 18 in step S42. The residue consists of, for example, hydrocarbon groups or hydrocarbon groups in which at least some of the hydrogen atoms have been replaced with fluorine. The amount of gas supplied is determined by integrating the flow rate per unit time over time.

[0037] Step S5 in Figure 1, as shown in Figure 3(C), removes the residue of carboxylic acid or phosphonic acid attached to the target film 18 in step S42 by supplying a plasma-generated hydrogen-containing gas to the substrate surface 1a. This improves the film quality of the target film 18.

[0038] The hydrogen-containing gas used in step S5 is, for example, H2 gas, H2O gas, NH3 gas, or N2H4 gas. Hydrocarbon gases such as CH4 gas can also be used. Note that if there is little residue, step S5 is unnecessary.

[0039] Although not shown in the diagram, in step S42, the blocking performance of SAM17 may not be perfect, and the periphery of the target film 18 may extend laterally from the surface of the insulating film 11, covering a portion of the surface of the conductive film 12. In this case, step S5 may include etching the periphery of the target film 18, as described later. This can enlarge the opening of the target film 18 and reduce the wiring resistance of the substrate 1.

[0040] If SAM17 contains fluorine, the reaction between the plasma-generated hydrogen-containing gas and SAM17 generates active species containing fluorine and carbon. These generated active species etch the periphery of the target film 18. The periphery of the target film 18 becomes a volatile compound, which is removed by exhaust gas. The volatile compound contains either fluorine or fluorine and carbon.

[0041] As described above, the active species containing fluorine and carbon are generated by the reaction between the plasma-induced hydrogen-containing gas and SAM17. Therefore, the active species are generated only in the vicinity of SAM17. Consequently, the periphery of the target film 18 is etched, while the center of the target film 18 (the part deposited on the surface of the insulating film 11) is not etched. Only the periphery of the target film 18 can be selectively removed.

[0042] An example of the processing conditions for step S5 is shown below. H2 gas flow rate: 200 sccm to 10000 sccm Ar gas flow rate: 20 sccm to 2000 sccm Power supply frequency for plasma generation: 400kHz~40MHz Power for plasma generation: 50W~1000W Processing time: 10 sec to 600 sec Processing temperature (substrate temperature): 100℃~250℃ Processing pressure: 100 Pa to 2000 Pa.

[0043] The plasma-generated hydrogen-containing gas not only removes residue attached to the target film 18 but also removes SAM 17. Therefore, after step S5 and before repeating step S4, step S3 is repeated (see Figure 1). By repeatedly performing the cycle including steps S3, S41, S42, and S5, a target film 18 with excellent film quality and thickness can be selectively formed on the surface of the insulating film 11. The thickness of the target film 18 formed in one cycle is at the level of one atom to several atoms, and is less than 1 nm.

[0044] Steps S3, S41, S42, and S5 are repeated, for example, within the same processing container. Steps S3, S41, S42, and S5 are repeated by supplying various gases into the same processing container in a desired order. Between adjacent steps, there may be a step to discharge any remaining gases from the processing container by supplying an inert gas, such as argon gas, into the processing container.

[0045] Step S6 in Figure 1 includes checking whether steps S3, S41, S42, and S5 have been performed the set number of times. If the number of executions has not reached the set number (Step S6, NO), the film thickness of the target film 18 has not reached the target film thickness, so steps S3, S41, S42, and S5 are performed again. On the other hand, if the number of executions has reached the set number (Step S6, YES), the film thickness of the target film 18 has reached the target film thickness, so the current process is terminated. The set number of executions in Step S6 is set according to the target film thickness of the target film 18, for example, between 20 and 80 times.

[0046] Next, with reference to Figure 4, a modified film formation method will be described. If there is little residue of carboxylic acid or phosphonic acid attached to the target film 18 in step S42, the film quality of the target film 18 is good even if step S5 in Figure 1 is not performed. Furthermore, if step S5 is not performed, SAM 17 is not removed, so there is no need to repeat step S3 before repeating step S4.

[0047] As shown in Figure 4, the film deposition method of this modified example selectively forms a target film 18 having a desired thickness on the surface of the insulating film 11 by repeatedly performing a cycle including steps S41 and S42. The thickness of the target film 18 formed in one cycle is at the level of one atom to several atoms, and is less than 1 nm.

[0048] The carboxylic acid or phosphonic acid gas used in step S42 may have a shorter linear chain than the carboxylic acid or phosphonic acid gas used in step S3. A linear chain is a region where carbon atoms are connected in a straight line without branching or forming rings. The longer the linear chain, the better the blocking performance of SAM17, but the more residue adheres to the target film 18.

[0049] As described above, if the carboxylic acid or phosphonic acid gas used in step S42 has a shorter linear chain than the carboxylic acid or phosphonic acid gas used in step S3, during the formation of the target film 18 conductive film 12This allows for the replenishment of SAM17 on the surface and reduces the residue of carboxylic acid or phosphonic acid adhering to the target film 18.

[0050] Next, with reference to Figure 5, the film deposition apparatus 100 that carries out the above film deposition method will be described. As shown in Figure 5, the film deposition apparatus 100 has a first processing unit 200A, a second processing unit 200B, a transport unit 400, and a control unit 500. The first processing unit 200A carries out step S2 in Figure 1. The second processing unit 200B repeatedly carries out a cycle including steps S3 to S5 in Figure 1. The first processing unit 200A and the second processing unit 200B have similar structures. Therefore, it is also possible to carry out all of steps S2 to S5 in Figure 1 with only the first processing unit 200A. The transport unit 400 transports the substrate 1 to the first processing unit 200A and the second processing unit 200B. The control unit 500 controls the first processing unit 200A, the second processing unit 200B, and the transport unit 400.

[0051] The transport unit 400 includes a first transport chamber 401 and a first transport mechanism 402. The internal atmosphere of the first transport chamber 401 is an atmospheric atmosphere. The first transport mechanism 402 is provided inside the first transport chamber 401. The first transport mechanism 402 includes an arm 403 for holding the substrate 1 and travels along a rail 404. The rail 404 extends in the direction of the arrangement of the carriers C.

[0052] Furthermore, the transport unit 400 includes a second transport chamber 411 and a second transport mechanism 412. The internal atmosphere of the second transport chamber 411 is a vacuum atmosphere. The second transport mechanism 412 is provided inside the second transport chamber 411. The second transport mechanism 412 includes an arm 413 for holding the substrate 1, and the arm 413 is arranged to be movable in the vertical and horizontal directions and rotatable about a vertical axis. The first processing unit 200A and the second processing unit 200B are connected to the second transport chamber 411 via different gate valves G.

[0053] Furthermore, the conveying section 400 has a load lock chamber 421 between the first conveying chamber 401 and the second conveying chamber 411. The internal atmosphere of the load lock chamber 421 is switched between a vacuum atmosphere and an atmospheric atmosphere by a pressure regulating mechanism (not shown). This allows the inside of the second conveying chamber 411 to always be maintained in a vacuum atmosphere. It also prevents gas from flowing from the first conveying chamber 401 into the second conveying chamber 411. Gate valves G are provided between the first conveying chamber 401 and the load lock chamber 421, and between the second conveying chamber 411 and the load lock chamber 421.

[0054] The control unit 500 is, for example, a computer and includes a CPU (Central Processing Unit) 501 and a storage medium 502 such as memory. The storage medium 502 stores programs that control various processes performed in the film deposition apparatus 100. The control unit 500 controls the operation of the film deposition apparatus 100 by causing the CPU 501 to execute the programs stored in the storage medium 502. The control unit 500 controls the first processing unit 200A, the second processing unit 200B, and the transport unit 400 to carry out the above-described film deposition method.

[0055] Next, the operation of the film deposition apparatus 100 will be described. First, the first transport mechanism 402 removes the substrate 1 from the carrier C, transports the removed substrate 1 to the load lock chamber 421, and exits the load lock chamber 421. Next, the internal atmosphere of the load lock chamber 421 is switched from an atmospheric atmosphere to a vacuum atmosphere. After that, the second transport mechanism 412 removes the substrate 1 from the load lock chamber 421 and transports the removed substrate 1 to the first processing unit 200A.

[0056] Next, the first processing unit 200A performs step S2. After that, the second transport mechanism 412 removes the substrate 1 from the first processing unit 200A and transports the removed substrate 1 to the second processing unit 200B. During this time, the surrounding atmosphere of the substrate 1 can be maintained in a vacuum atmosphere, and oxidation of the substrate 1 can be suppressed.

[0057] Next, the second processing unit 200B repeatedly performs the cycle including steps S3 to S5. After that, the second transport mechanism 412 removes the substrate 1 from the second processing unit 200B, transports the removed substrate 1 to the load lock chamber 421, and exits the load lock chamber 421. Subsequently, the internal atmosphere of the load lock chamber 421 is switched from a vacuum atmosphere to an atmospheric atmosphere. After that, the first transport mechanism 402 removes the substrate 1 from the load lock chamber 421 and places the removed substrate 1 into the carrier C. Then, the processing of the substrate 1 is completed.

[0058] Next, the first processing unit 200A will be described with reference to Figure 6. Note that the second processing unit 200B is configured similarly to the first processing unit 200A, so its illustration and description are omitted.

[0059] The first processing unit 200A includes a substantially cylindrical, airtight processing container 210. An exhaust chamber 211 is provided in the center of the bottom wall of the processing container 210. The exhaust chamber 211 has a shape that protrudes downward, for example, a substantially cylindrical shape. An exhaust pipe 212 is connected to the exhaust chamber 211, for example, on the side of the exhaust chamber 211.

[0060] An exhaust source 272 is connected to the exhaust piping 212 via a pressure controller 271. The pressure controller 271 includes a pressure regulating valve, such as a butterfly valve. The exhaust piping 212 is configured to reduce the pressure inside the processing container 210 by the exhaust source 272. The pressure controller 271 and the exhaust source 272 constitute a gas discharge mechanism 270 that discharges gas from inside the processing container 210.

[0061] A transport port 215 is provided on the side of the processing container 210. The transport port 215 is opened and closed by a gate valve G. The substrate 1 is loaded and unloaded between the processing container 210 and the second transport chamber 411 (see Figure 5) through the transport port 215.

[0062] A stage 220, which is a holding part for holding the substrate 1, is provided inside the processing container 210. The stage 220 holds the substrate 1 horizontally with the substrate surface 1a facing upwards. The stage 220 is formed in a substantially circular shape in plan view and is supported by a support member 221. A substantially circular recess 222 is formed on the surface of the stage 220 for placing a substrate 1, for example, with a diameter of 300 mm. The recess 222 has an inner diameter slightly larger than the diameter of the substrate 1. The depth of the recess 222 is set to be approximately the same as the thickness of the substrate 1, for example. The stage 220 is formed of a ceramic material such as aluminum nitride (AlN). Alternatively, the stage 220 may be formed of a metallic material such as nickel (Ni). Instead of the recess 222, a guide ring for guiding the substrate 1 may be provided on the peripheral edge of the surface of the stage 220.

[0063] A lower electrode 223, for example, grounded, is embedded in the stage 220. A heating mechanism 224 is embedded below the lower electrode 223. The heating mechanism 224 is powered by a power supply unit (not shown) based on a control signal from the control unit 500 (see Figure 5), and heats the substrate 1 placed on the stage 220 to a set temperature. If the entire stage 220 is made of metal, the entire stage 220 functions as the lower electrode, so the lower electrode 223 does not need to be embedded in the stage 220. The stage 220 is provided with a plurality (for example, three) of lifting pins 231 for holding and raising and lowering the substrate 1 placed on the stage 220. The material of the lifting pins 231 may be, for example, ceramics such as alumina (Al2O3) or quartz. The lower ends of the lifting pins 231 are attached to a support plate 232. The support plate 232 is connected via a lifting shaft 233 to a lifting mechanism 234 located outside the processing container 210.

[0064] The lifting mechanism 234 is installed, for example, at the bottom of the exhaust chamber 211. The bellows 235 is provided between the opening 219 for the lifting shaft 233 formed on the lower surface of the exhaust chamber 211 and the lifting mechanism 234. The shape of the support plate 232 may be such that it can move up and down without interfering with the support member 221 of the stage 220. The lifting pin 231 is configured to move up and down between the upper surface of the stage 220 and the lower surface of the stage 220 by the lifting mechanism 234.

[0065] A gas supply unit 240 is provided on the top wall 217 of the processing vessel 210 via an insulating member 218. The gas supply unit 240 forms the upper electrode and faces the lower electrode 223. A high-frequency power supply 252 is connected to the gas supply unit 240 via a matching unit 251. By supplying high-frequency power of 450 kHz to 100 MHz from the high-frequency power supply 252 to the upper electrode (gas supply unit 240), a high-frequency electric field is generated between the upper electrode (gas supply unit 240) and the lower electrode 223, and a capacitively coupled plasma is generated. The plasma generation unit 250 that generates the plasma includes the matching unit 251 and the high-frequency power supply 252. Note that the plasma generation unit 250 is not limited to generating capacitively coupled plasma, but may generate other plasmas such as inductively coupled plasma.

[0066] The gas supply unit 240 includes a hollow gas supply chamber 241. On the lower surface of the gas supply chamber 241, numerous holes 242 are evenly arranged, for example, to distribute and supply the processing gas into the processing container 210. Above the gas supply chamber 241 in the gas supply unit 240, for example, a heating mechanism 243 is embedded. The heating mechanism 243 is heated to a set temperature by being powered from a power supply unit (not shown) based on a control signal from the control unit 500.

[0067] A gas supply mechanism 260 is connected to the gas supply room 241 via a gas supply passage 261. The gas supply mechanism 260 supplies the gas used in at least one of steps S2 to S5 in Figure 1 to the gas supply room 241 via the gas supply passage 261. Although not shown, the gas supply mechanism 260 includes individual piping for each type of gas, on-off valves installed in the middle of the individual piping, and flow controllers installed in the middle of the individual piping. When the on-off valve opens the individual piping, gas is supplied from the supply source to the gas supply passage 261. The amount of gas supplied is controlled by the flow controller. On the other hand, when the on-off valve closes the individual piping, the supply of gas from the supply source to the gas supply passage 261 is stopped.

[0068] While embodiments of the film deposition method and film deposition apparatus relating to this disclosure have been described above, this disclosure is not limited to the above embodiments. Various changes, modifications, substitutions, additions, deletions, and combinations are possible within the scope of the claims. These, too, naturally fall within the technical scope of this disclosure. [Explanation of Symbols]

[0069] 1 circuit board 1a Substrate surface 11. Insulating film (first layer) 12. Conductive film (second film) 17 SAM (Self-assembled monolayer)

Claims

1. (A) Prepare a substrate having an insulating film and a conductive film formed of a different material from the insulating film in different regions of its surface, (B) By supplying a carboxylic acid or phosphonic acid gas to the surface of the substrate, a self-assembled monolayer is selectively formed on the surface of the conductive film relative to the surface of the insulating film, (C) After (B) above, the self-assembled monolayer is used to inhibit the formation of the target film on the surface of the conductive film while forming the target film on the surface of the insulating film, It has, The above (C) includes (Ca) supplying a precursor gas of the target film to the surface of the substrate, and (Cb) supplying a carboxylic acid or phosphonic acid gas to the surface of the substrate as an oxidizing gas. (D) After (C), the residue of carboxylic acid or phosphonic acid attached to the target film in (Ca) is removed by supplying a plasma-formed hydrogen-containing gas to the surface of the substrate. A film deposition method comprising repeatedly executing a cycle including (B), (Ca), (Cb), and (D).

2. (A) Prepare a substrate having an insulating film and a conductive film formed of a different material from the insulating film in different regions of its surface, (B) By supplying a carboxylic acid or phosphonic acid gas to the surface of the substrate, a self-assembled monolayer is selectively formed on the surface of the conductive film relative to the surface of the insulating film, (C) After (B) above, the self-assembled monolayer is used to inhibit the formation of the target film on the surface of the conductive film while forming the target film on the surface of the insulating film, It has, The above (C) includes (Ca) supplying a precursor gas of the target film to the surface of the substrate, and (Cb) supplying a carboxylic acid or phosphonic acid gas to the surface of the substrate as an oxidizing gas. A film formation method in which the same carboxylic acid or the same phosphonic acid gas is used in (B) and (Cb).

3. (A) Prepare a substrate having an insulating film and a conductive film formed of a different material from the insulating film in different regions of its surface, (B) By supplying a carboxylic acid or phosphonic acid gas to the surface of the substrate, a self-assembled monolayer is selectively formed on the surface of the conductive film relative to the surface of the insulating film, (C) After (B) above, the self-assembled monolayer is used to inhibit the formation of the target film on the surface of the conductive film while forming the target film on the surface of the insulating film, It has, The above (C) includes (Ca) supplying a precursor gas of the target film to the surface of the substrate, and (Cb) supplying a carboxylic acid or phosphonic acid gas to the surface of the substrate as an oxidizing gas. A film formation method wherein the carboxylic acid used in (B) above comprises at least one selected from the group consisting of CF3(CF2)2COOH, CF3COOH, C6H5COOH, and CH3(CH2)nCOOH (where n is an integer from 2 to 10).

4. The method for forming a film according to any one of claims 1 to 3, wherein the conductive film is a Cu film, a Co film, a Ru film, or a W film.

5. Processing container and The processing container includes a holding section for holding the substrate inside, A gas supply mechanism that supplies gas to the inside of the processing container, A gas discharge mechanism for discharging gas from inside the processing container, A transport mechanism for loading and unloading the substrate into and out of the processing container, A control unit that controls the gas supply mechanism, the gas discharge mechanism, and the transport mechanism, and carries out the film formation method according to any one of claims 1 to 4, A film deposition apparatus equipped with the following features.

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