JP2009120909A - Film deposition method, film deposition system, and storage medium - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a film deposition method which has a satisfactory step coverage, stably feeds raw materials, and can practically and inexpensively deposit a metal film of high quality without causing deterioration in the raw materials, and to provide a film deposition system. <P>SOLUTION: The film deposition method comprises: a stage where carbon monoxide, water and an oxygen-containing metal compound are reacted, so as to produce the formate gas of the same metal; a stage where the formate gas is fed to the surface of a substrate 1, so as to deposit a formate film 2; and a stage where energy is applied to the substrate 1 deposited with the formate film 2, and the formate film 2 is decomposed, so as to form a metal film 3. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a film forming method and a film forming apparatus for forming a metal film such as a copper film used as a semiconductor wiring, and a storage medium.

  Recently, in response to demands for higher speeds of semiconductor devices, finer wiring patterns, and higher integration, there has been a demand for lower capacitance between wirings, improved wiring conductivity, and improved electromigration resistance. As a corresponding technology, copper (Cu), which has higher conductivity than aluminum (Al) and tungsten (W) and has excellent electromigration resistance, is used as a wiring material, and a low dielectric constant film (Low-k) is used as an interlayer insulating film. Cu multilayer wiring technology using a film) has attracted attention.

  As a Cu film forming method for Cu multilayer wiring, a physical vapor deposition (PVD) method typified by sputtering, a plating method, and a chemical vapor deposition (MOCVD) method in which an organic metal material is vaporized and used are known. However, the PVD method has poor step coverage and is difficult to embed in a fine pattern. In the plating method, due to the additive contained in the plating solution, a large amount of impurities are contained in the Cu film. Although good step coverage can be easily obtained by the MOCVD method, impurities such as carbon (C), oxygen (O), fluorine (F), etc. from the side chain group coordinated to the Cu atom remain in the Cu film. It is difficult to improve the film quality. Furthermore, since the side chain group coordinated to Cu atom is complicated, the raw material is very expensive. Moreover, since it is thermally unstable and has a low vapor pressure, it is difficult to supply a stable raw material gas.

  On the other hand, in Patent Document 1, a CuCl plate is disposed in a chamber, Ar gas plasma is generated, and the CuCl plate is etched to generate a desorbed species of CuCl, and Ar gas plasma is generated from the desorbed species. A technique is disclosed in which a dissociated species of Cu and Cl is generated by the above, and the temperature of the substrate is made lower than the temperature of the CuCl plate to form a Cu film on the substrate by direct reduction. With this technique, it is said that an inexpensive raw material can be used with a high deposition rate, and a Cu film in which no impurities remain in the film can be produced.

  However, with the technique of Patent Document 1, it is difficult to completely remove Cl in the Cu film, and a trace amount of Cl may remain. Even if the residual amount of Cl is small, there are problems such as an increase in wiring resistance and a decrease in reliability due to corrosion of the Cu wiring. In addition, since the substrate surface is exposed to plasma at the initial stage of film formation, there is a concern that the substrate may be chemically or physically damaged. In particular, low-k films used for wiring tend to cause an increase in dielectric constant and destruction of fine structure due to these plasmas (plasma damage). Further, since the plasma also sputters members other than the CuCl plate inside the reactor, it causes damage to the members, impurities in the film due to the sputtered particles, and contamination contamination. Therefore, applying the technique of Patent Document 1 to a Cu multilayer wiring has the disadvantage that a costly mechanism or material must be required to overcome the above problems.

On the other hand, Patent Document 2 discloses a method of manufacturing Cu wiring by using a cheap raw material by a method other than the wet plating method other than the semiconductor manufacturing process. This is a copper thin film formed by applying copper diformate (Cu (OCHO) ₂ ), which is an inexpensive organic Cu compound, or a hydrate thereof to a substrate and applying heat in a non-oxidizing atmosphere. . Similarly, Non-Patent Document 1 reports that Cu wiring is formed by heating copper dihydrate diformate coated on a substrate with laser light with a narrowed optical diameter. All of these utilize the fact that cupric formate becomes Cu by a thermal decomposition reaction. Although these methods can form a metal Cu film at low cost, they are not suitable for embedding metal in a fine shape processed at the nanometer level, such as a wiring of a super integrated circuit (ULSI). Therefore, the electrical conductivity also becomes worse than the original value of Cu.

  An attempt to use inexpensive hydrated copper diformate as a raw material for MOCVD has been reported in Non-Patent Document 2. A powder of hydrated copper formate is placed in a raw material container, and a carrier gas is introduced into the heated container. The vaporized component generated by heating is transported through a pipe to the heated substrate surface in another reactor with a carrier gas. The transported vaporized component is thermally decomposed on the substrate surface, and a Cu film is formed.

According to Non-Patent Document 3, it is known that the vaporized component generated inside the raw material container is cuprous formate. Copper formate (Cu (OCHO)), which is easily vaporized, is generated as a gas from copper diformate which is difficult to be vaporized by the reaction formula shown in the following formula (1), and this is transported to the substrate.
2Cu (OCHO) ₂ → 2Cu (OCHO) + CO + CO ₂ + H ₂ O (1)
As reported in Non-Patent Document 3, copper primary formate is a substance that is very easily thermally decomposed. Therefore, Cu can be easily formed from copper formate by the reaction formula shown in the following formula (2) at low temperature. A thin film is formed.
_{2Cu (OCHO) → 2Cu + 2CO} 2 + H 2 ...... (2)
According to this method, the formate group (OCHO), which is a ligand, is easily taken out by being thermally decomposed into CO ₂ or H _2, and thus is hardly taken into the Cu film. Therefore, it is easy to produce a high-purity Cu film that does not contain impurities. However, in general, a method in which a gas vaporized from a solid raw material is carried by a carrier gas is greatly influenced by the heat conduction state inside the solid raw material container under reduced pressure, and stable supply is difficult. Further, the raw material cupric formate is thermally decomposed inside the solid material container, and Cu is formed there. That is, the raw material tends to deteriorate.

In Non-Patent Document 3, silver is cited as a metal species that exhibits the same reaction as an ant oxide, and silver can be formed as a wiring layer by a similar method. The same problem arises.
JP 2004-27352 A Patent No. 2745677 A. Gupta and R. Jagannathan, Applied Physics Letters, 51 (26), p2254, (1987). M.-J.Mouche et al, Thin SolidFilms 262, p1, (1995). A. Keller and F. Korosy, Nature, 162, p580, (1948).

The present invention has been made in view of such circumstances, has good step coverage, stably supplies raw materials, and forms a high-quality metal film practically and inexpensively without causing deterioration of the raw materials. An object of the present invention is to provide a film forming method and a film forming apparatus that can perform the above process.
Another object of the present invention is to provide a storage medium storing a program for executing such a method.

  In order to solve the above problems, in a first aspect of the present invention, a step of reacting carbon monoxide, water, and an oxygen-containing metal compound to generate a formate gas of the metal, and a formic acid of the metal on a substrate There is provided a film forming method comprising a step of supplying a salt gas, and a step of applying energy to the substrate to decompose the metal formate supplied on the substrate to form a metal film.

  In the first aspect, the oxygen-containing metal compound is in a powder form, and formate gas can be obtained by supplying gaseous carbon monoxide and gaseous water thereto.

  In a second aspect of the present invention, a step of placing a substrate in a processing container held in a vacuum, and a step of reacting carbon monoxide, water, and an oxygen-containing metal compound to generate a formate gas of the metal. And supplying the formate gas onto the substrate in the processing container; and applying energy to the substrate to decompose the formate supplied onto the substrate to form a metal film. A film forming method is provided.

  In the second aspect, the formate gas is formed by reacting gaseous carbon monoxide, gaseous water, and an oxygen-containing metal compound outside the processing container, and the inside of the processing container via a pipe. Can be introduced. In this case, it is possible to generate formate gas by supplying gaseous carbon monoxide and gaseous water to the oxygen-containing metal compound powder. In addition, for the pipe, an inner surface coated with an oxygen-containing metal compound is used, and formate gas is generated by passing gaseous carbon monoxide and gaseous water through the pipe. it can.

  In the second aspect, the formate gas can be generated by reacting carbon monoxide, water, and an oxygen-containing metal compound in the processing container. In this case, the processing container A formate gas can be generated by disposing a member made of copper oxide therein and supplying gaseous carbon monoxide and gaseous water to the member.

In the first and second aspects, formic acid is deposited on the substrate by supplying gaseous carbon monoxide and gaseous water onto the substrate, and energy is applied to the substrate on which the formate has been deposited. Thus, the formate on the substrate may be decomposed, or energy may be applied to the substrate while supplying the formate gas onto the substrate. Moreover, copper or silver can be suitably used as the metal. In this case, the oxygen-containing metal compound includes cuprous oxide (Cu ₂ O), cupric oxide (CuO), cupric hydroxide (Cu (OH) ₂ ), and cuprous oxide (Ag ₂ O). ) Or Ag ₂ O ₂ (secondary silver oxide).

  In the first and second aspects, thermal energy can be used as the energy given to the substrate. In this case, thermal energy may be given to the substrate by a resistance heating element provided on a substrate support member that supports the substrate, or thermal energy may be given to the substrate by a heating lamp provided at a position away from the substrate. Also good.

  In a third aspect of the present invention, a processing container that is held in a vacuum and in which a substrate is disposed, a substrate support member that supports the substrate in the processing container, carbon monoxide, water, and an oxygen-containing metal compound are reacted. Gas generating means for generating the metal formate gas, gas supply means for supplying the formate gas onto the substrate in the processing container, and energy applying means for supplying energy to the substrate on the substrate support member And exhaust means for exhausting the inside of the processing container, formate is supplied onto the substrate by the gas supply means, and the formate is decomposed by the energy from the energy application means to form a metal film on the substrate. A film forming apparatus is provided.

  In the third aspect, the gas generation means includes the carbon monoxide supply unit that supplies gaseous carbon monoxide, the water supply unit that supplies gaseous water, and the oxygen-containing metal compound. A gaseous carbon monoxide supplied from a carbon supply unit, and a reaction unit that generates a formate gas of the metal by a reaction between gaseous water supplied from the water supply unit and an oxygen-containing metal compound. The gas supply means for supplying the formate gas may have a formate introduction part that guides the generated formate gas to the processing container. In this case, the water supply unit may include a water vapor generator that generates water vapor with oxygen and hydrogen. Moreover, the said reaction part may have a reaction container which stores oxygen-containing metal compound powder, and may have a member consisting of an oxygen-containing metal compound. The carbon monoxide supply part has a carbon monoxide supply pipe, the water supply part has a water supply pipe, and the reaction part is a merged pipe in which the carbon monoxide supply pipe and the water supply pipe are merged. And the member made of an oxygen-containing metal compound in the reaction section may be an inner surface layer made of an oxygen-containing metal compound provided on the inner surface of the junction pipe. Furthermore, the formate introduction part may be configured to have a shower head that guides the formate gas into a shower.

  In a fourth aspect of the present invention, a processing container that is held in vacuum and in which a substrate is disposed, a substrate support member that supports the substrate in the processing container, and an oxygen-containing metal compound that is disposed in the processing container A member comprising: carbon monoxide supplying means for supplying gaseous carbon monoxide into the reaction vessel; water supply means for supplying gaseous water into the reaction vessel; and a substrate on the substrate support member An energy applying means for giving energy to the gas and an exhaust means for exhausting the inside of the processing vessel, and gaseous carbon monoxide supplied from the carbon monoxide supply means, and gas supplied from the water supply means The formate gas is generated by the reaction between the water-like water and the member made of the oxygen-containing metal compound, the formate gas is supplied onto the substrate, and the formate is decomposed by the energy applied by the energy applying means. To provide a film forming apparatus, wherein a metal film is formed on the plate.

  In the fourth aspect, the carbon monoxide supply means includes a carbon monoxide supply source, a carbon monoxide supply pipe for supplying gaseous carbon monoxide to the processing vessel, and gaseous carbon monoxide. A carbon monoxide introduction part to be introduced into the processing container, wherein the water supply means includes a water supply source, a water supply pipe for supplying gaseous water to the processing container, and the gaseous water for the treatment It may have a water introduction part led in to a container. In this case, the water supply source may include a water vapor generator that generates water vapor with oxygen and hydrogen. Further, the carbon monoxide introduction part and the water introduction part have a joining part, and a member made of an oxygen-containing metal compound may be provided in the joining part. The merging portion includes a shower head having a discharge member having a plurality of discharge holes, and the member made of the oxygen-containing metal compound constitutes part or all of the discharge member and is introduced into the shower head. It is preferable to discharge the formate gas by reacting with the oxygen-containing metal compound when the gaseous carbon monoxide and gaseous water pass through the discharge hole. In this case, the discharge member of the shower head has a base material and a coating layer made of an oxygen-containing metal compound formed on the surface of the base material, and the coating layer functions as a member made of the oxygen-containing metal compound. You may do it.

In the third and fourth aspects, the formate gas is supplied onto the substrate by the gas supply means to deposit formate, and the formate deposited on the substrate is decomposed by the energy from the energy application means. Alternatively, energy may be applied to the substrate by the energy applying means while formate gas is supplied onto the substrate by the gas supplying means. Moreover, copper or silver can be suitably used as the metal. In this case, the oxygen-containing metal compound used in the gas generating means is cuprous oxide (Cu ₂ O), cupric oxide (CuO), cupric hydroxide (Cu (OH) ₂ ), oxidized second Either single silver (Ag ₂ O) or dichroic oxide (Ag ₂ O ₂ ) can be used.

  In the third and fourth aspects, it is preferable that the energy applying unit is a unit that applies thermal energy to the substrate. In this case, the energy applying unit is a resistor provided on the substrate support member. Even if it has a heating element, it may have a heating lamp provided separately from the substrate support member.

  In a fifth aspect of the present invention, a formate formed by reacting carbon monoxide, water, and an oxygen-containing metal compound is supplied to the substrate that is held in a vacuum and disposed, and the substrate is disposed. A first processing container on which a formate film is deposited and a substrate on which a formate film is deposited are disposed in the first processing container, and energy is applied to the disposed substrate. A second processing container that decomposes formate on the substrate and forms a metal film on the substrate, and a substrate transport mechanism that transports the substrate from the first processing container to the second processing container without breaking the vacuum A film forming apparatus is provided.

  According to a sixth aspect of the present invention, there is provided a storage medium that stores a program that operates on a computer and controls a film forming apparatus, and the program is one of the first and second aspects when executed. There is provided a storage medium characterized by causing a computer to control a film forming apparatus so that the film forming method is performed.

  According to the present invention, carbon monoxide is reacted with water and an oxygen-containing metal compound, and a formate that is thermally decomposed with low energy to form a metal film is supplied onto the substrate, and energy is supplied to the formate. By providing, a metal film effective as a wiring layer such as a Cu film can be obtained with high step coverage. In particular, copper formate, preferably copper formate, is supplied onto the substrate, and energy is applied to the copper formate to obtain a copper film, whereby a Cu film can be formed with very low energy and good step coverage. . At this time, step coverage is further improved by using a technique in which a formate, for example, copper formate, is supplied and deposited on the substrate, and then a formate is formed on the substrate by applying energy to the formate. be able to. Organic ligands to metal atoms in formate as raw materials, specifically copper formate, especially organic ligands to Cu atoms in cuprous formate, are thermally decomposed into metal films (typically Is exhausted as a gas that does not affect the Cu film), so that an extremely high quality film can be obtained with very few impurities in the film. When cuprous oxide or the like is used as a raw material, it is extremely cheaper than the case of using an existing Cu-CVD raw material organic compound, and there is an advantage that the raw material cost can be reduced.

  Furthermore, carbon monoxide, water, and an oxygen-containing metal compound are reacted to produce formate gas, preferably copper formate gas. Formic acid produced by adjusting the amount of carbon monoxide and water to be supplied The amount of salt can be adjusted. For this reason, the raw material can be supplied in a stable and adjustable manner, and the deterioration of the raw material is less than the conventional method of heating the powdery cupric formate to obtain the cuprous formate gas. . In this case, the oxygen-containing metal compound used as a raw material, particularly cuprous oxide, can be formed as a dense film, unlike copper formate, which must be used as a powder. There is a high degree of freedom in the installation location, such as installation and coating on the piping, and it is possible to devise on the equipment such as shortening the transport length from the substrate to the film to the raw material, and during transportation to the substrate It is possible to effectively prevent copper from being formed by pyrolysis or solidification due to cooling of the decomposition products.

Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings.
First, the concept of the film forming method according to the present invention will be described. FIG. 1 is a schematic diagram for explaining the concept of a film forming method according to the present invention.

  First, as shown in FIG. 1 (a), an oxygen-containing metal compound containing a metal of the metal film to be obtained, carbon monoxide, and water are reacted to form a formate gas, for example, cuprous formate. Generate gas. By doing in this way, the amount of formate produced | generated can be adjusted by adjusting the quantity of the carbon monoxide and water to supply, and a raw material can be supplied stably with sufficient controllability.

  As described above, a metal film can be formed by reacting carbon monoxide, water, and an oxygen-containing metal compound. As carbon monoxide, gaseous (typically carbon monoxide gas) water is used. Water vapor is preferably used, and typical examples of the oxygen-containing metal compound include metal oxides. Metal hydroxides can also be used. Since the metal hydroxide is more thermally unstable than the metal oxide, it may have an advantage that the reaction temperature can be further lowered.

As such a metal, copper (Cu) and silver (Ag) are preferable. By reacting these oxygen-containing compounds, carbon monoxide, and water, a formate salt that is easily thermally decomposed can be formed, the resistance is very low, and it is suitable as a wiring material. When Cu or Ag is used as the metal, examples of the oxygen-containing metal compound include cuprous oxide (Cu ₂ O), cupric oxide (CuO), cupric hydroxide (Cu (OH) ₂ ), and oxidation. Examples include primary silver (Ag ₂ O) and secondary silver oxide (Ag ₂ O ₂ ). From the viewpoint of reactivity, divalent oxides in a cupric oxide (CuO) and than (II) oxide and silver (Ag 2 _{O 2),} cuprous oxide is an oxide of a monovalent (Cu ₂ O ) And primary silver oxide (Ag ₂ O) are preferred. Since cupric hydroxide (Cu (OH) ₂ ) is thermally more unstable, the temperature for forming the carboxylate can be lowered, but the storage stability and the like may be low. In the case of silver, Ag (OH) is present but it is too thermally unstable and decomposes at room temperature, making it difficult to apply.

The formate formation reaction when Cu ₂ O is used as the oxygen-containing metal compound is as shown in the following formula (3), and first copper formate is generated.
Cu ₂ O + 2CO + H ₂ O → 2Cu (HCOO) (3)

  Next, as shown in FIG. 1B, the formate gas generated as described above is supplied onto the substrate 1. Since formate has a high vapor pressure and is easily thermally decomposed, it can be easily decomposed into metal by applying energy, and a metal film can be easily formed. In order to suppress the oxidation of formate as much as possible and maintain a desired component, it is preferable to supply the formate in a vacuum. Copper formate, which is the preferred formate described above, is an unstable substance and is known to be easily decomposed into copper, and a copper film can be formed relatively easily by utilizing its properties. . In addition, although cuprous formate exists as a gas in a vacuum, it is easily oxidized in the atmosphere to become cuprous oxide. Therefore, the cuprous formate is supplied in a vacuum. At this time, the cuprous formate is brought to a temperature of about 50 to 150 ° C. so as to be kept in a gaseous state. The cuprous formate of the present invention includes not only monomers but also multimers. In addition, in order to produce | generate a large amount of cuprous formate gas and to suppress decomposition | disassembly in the gaseous phase of the produced cuprous formate, it is necessary to raise the partial pressure conditions of carbon monoxide gas and water vapor to some extent. However, if the pressure is too high, it is disadvantageous for the vaporized supply of water vapor. Therefore, the partial pressure of water vapor during the reaction for producing cuprous formate is preferably about 133 to 6650 Pa (1 to 50 Torr). The partial pressure of carbon monoxide gas is preferably about twice the partial pressure of water vapor.

  Next, as shown in FIG. 1C, formate is adsorbed on the substrate 1 and deposited in a predetermined amount to form a formate film 2 as a precursor of the metal film. At this time, the temperature of the substrate 1 is preferably about −30 to 50 ° C.

Next, as shown in FIG. 1D, energy is applied to the substrate on which the formate film 2 is formed, the reaction proceeds, the formate is decomposed, and the metal film 3 is formed.
At this time, heat energy is typically used as the energy. Since the heat energy can be applied by a resistance heating element, a heating lamp, or the like used in a normal film forming apparatus, the application is easy.

  According to such a method, formate formed by reacting carbon monoxide, water, and an oxygen-containing metal compound without causing thermal decomposition in the gas phase is adsorbed on the substrate surface in a gas state, Since energy is applied to form a metal film, step coverage can be improved as in the case of normal CVD. Therefore, it can be applied to a fine pattern in the ULSI wiring process. In addition, since a raw material cheaper than MOCVD can be used, film formation for metal wiring can be performed at low cost.

  Considering step coverage, as shown in FIG. 1, it is preferable that formate is adsorbed on the substrate surface, and then energy is applied to form a metal film, but it can also be as shown in FIG. 2. In FIG. 2 (a), as in FIG. 1 (a), formate is generated, and then, as shown in FIG. 2 (b), the substrate 1 is generated in a state where energy such as thermal energy is applied. The first copper formate gas may be supplied onto the substrate 1. In this case, as shown in FIG. 2 (c), when the formate gas reaches the substrate 1, it is immediately decomposed and the metal film 3 is formed. In such a method, the step coverage tends to be slightly inferior to the method of FIG. 1, but when a metal film is formed by applying energy after adsorbing the carboxylate as shown in FIG. 1 to the substrate surface. There is an advantage that the metal film can be formed in a shorter time.

Further, since only C, O and H are used as raw materials other than the metal, a high quality film with few impurities can be obtained, and Cu wiring by chlorine as in the technique disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 2004-27352. There is no problem of corrosion. Furthermore, since no plasma is used, plasma damage to the substrate substrate does not occur. Furthermore, when a cuprous formate film is used as the formate film, it is easily decomposed at a low temperature of about 100 ° C., so that it is possible to form a film at a lower temperature than in conventional MOCVD. When the process is applied to a semiconductor device, there is almost no risk of thermal degradation of the underlying film. In particular, since the low-k film used as an interlayer insulating film is vulnerable to heat, it is extremely advantageous that it can be formed at such a low temperature. Furthermore, when carbon monoxide, water, and cuprous oxide are reacted, the reactivity is high, and the flow rate of the generated cuprous formate gas is much higher than that using the existing organic copper compound. be able to. Therefore, a large amount of cuprous formate can be deposited on the substrate in a short time, and the film formation rate can be increased. As described above, when forming a Cu film as a typical example, cuprous oxide is suitable as copper oxide which is an oxygen-containing copper compound, but cupric oxide (CuO) can also be used. . Although cupric oxide is inferior to cuprous oxide in reactivity, cupric oxide is more stable, so the processing form of the raw material includes many forms such as pellets and polycrystalline plates in addition to powder. It is commercially available and has the advantage of low cost. In addition to copper oxide, cupric hydroxide (Cu (OH) ₂ ) can also be used as the oxygen-containing copper compound in forming the Cu film. Copper hydroxide is thermally unstable than copper oxide. Therefore, there is a possibility that the temperature of the production reaction of cuprous formate can be lowered.

  Next, specific embodiments of the present invention will be described. In the following embodiments, as a typical example of forming formate from carbon monoxide, water, and an oxygen-containing metal compound, an example of forming cuprous formate using cuprous oxide in an oxygen-containing metal compound is given. A case where a copper film is formed as a metal film by supplying energy to a semiconductor wafer as a substrate and applying energy will be described.

[First Embodiment]
FIG. 3 is a cross-sectional view illustrating a schematic configuration of the film forming apparatus according to the first embodiment.
The film forming apparatus shown in FIG. 3 has a chamber 11 formed into a cylindrical shape or a box shape using aluminum or the like, for example, and inside the chamber 11 is a semiconductor wafer (hereinafter simply referred to as a wafer) to be processed. A susceptor 12 for horizontally supporting W is arranged in a state where it is supported by a cylindrical support member 13 provided at the lower center of the susceptor 12. A heater 14 is embedded in the susceptor 12, and the heater 14 is heated by a heater power supply 15 to heat the wafer W as a substrate to be processed to a predetermined temperature. The susceptor 12 can be made of ceramics such as AlN.

  A shower head 20 is formed on the top wall 11 a of the chamber 11. The shower head 20 includes a flat gas diffusion space 21 formed in the top wall 11a of the chamber 11 and extending horizontally, and a shower plate 22 having a large number of gas discharge holes 23 provided below the gas diffusion space 21. is doing. A heater 20 a is provided on the inner surface of the shower head 20.

  An exhaust port 24 is formed in the lower portion of the side wall of the chamber 11, and an exhaust pipe 25 is connected to the exhaust port 24. An exhaust device 26 having a vacuum pump is connected to the exhaust pipe 25. By operating the exhaust device 26, the inside of the chamber 11 is depressurized to a predetermined degree of vacuum via the exhaust pipe 25. On the side wall of the chamber 11, a loading / unloading port 27 for loading / unloading the wafer W and a gate valve 28 for opening / closing the loading / unloading port 27 are provided.

On the other hand, a carbon monoxide supply source 31 a that supplies carbon monoxide (CO) and a water storage container 31 b that stores water (H ₂ O) are disposed outside the chamber 11. A pipe 32a extends from 31a, and a pipe 32b extends from the water storage container 31b. The pipe 32a is provided with a valve 33a and a mass flow controller (MFC) 34a for flow control, and the pipe 32b is provided with a valve 33b and a mass flow controller (MFC) 34b for flow control.
The pipe 32 a and the pipe 32 b merge to form a pipe 32. A reaction vessel 35 that stores cuprous oxide powder 36 is disposed in the vicinity of the chamber 11, and the pipe 32 is inserted into the reaction vessel 35. A heater 35 a is provided around the reaction vessel 35. A pipe 37 is connected to the upper part of the reaction vessel 35, and this pipe 37 extends from above the chamber 11 to a position facing the gas diffusion space 21 inside the shower head 20. A heater 37 a is provided around the pipe 37.

  The water in the water storage container 31b is vaporized (gaseous) by appropriate means such as heating or bubbling, and is introduced into the reaction container 35 through the pipe 32b. In addition, gaseous carbon monoxide (hereinafter referred to as carbon monoxide gas) is introduced into the reaction vessel 35 from a carbon monoxide gas supply source 31 a such as a gas cylinder. In the reaction vessel 35, the cuprous oxide powder 36, carbon monoxide gas, and water vapor (gaseous water) react with each other while being held at 50 to 150 ° C. by the heater 35 a, and the above-described formula (1) In accordance with the reaction formula shown below, cuprous formate gas is produced.

  In addition, as shown in FIG. 4, instead of using the water storage container 31b, a steam generator 151 can be used. A hydrogen gas pipe 152 and an oxygen gas pipe 153 are connected to the steam generator 151, and a hydrogen gas supply source 154 and an oxygen gas supply source 155 are connected to the pipes 152 and 153, respectively. The pipes 152 and 153 are provided with mass flow controllers 156 and 157, respectively, and valves 158 and 159 are provided upstream thereof. Water vapor can be generated by introducing hydrogen gas and oxygen gas from the hydrogen gas supply source 154 and the oxygen gas supply source 155 to the water vapor generator 151 via the pipes 152 and 153.

  A gas line 16 a for purging the pipe 32 with an inert gas is connected to the pipe 32. The gas line 16a is provided with a valve 17a and a mass flow controller (MFC) 18a from the upstream side. Further, a gas line 16 b for supplying by-product purge and dilution gas is connected in the gas diffusion space 21 of the shower head 20. The gas line 16b is provided with a valve 17b and a mass flow controller (MFC) 18b from the upstream side.

  Each component constituting the film forming apparatus is connected to and controlled by a process controller 80 having a microprocessor (computer). Also connected to the process controller 80 is a user interface 81 including a keyboard for an operator to input commands for managing the film forming apparatus, a display for visualizing and displaying the operating status of the film forming apparatus, and the like. ing. Further, the process controller 80 causes each component of the film forming apparatus to execute processing according to a control program for realizing various processes executed by the film forming apparatus under the control of the process controller 80 and processing conditions. A storage unit 82 that stores a program for storing the recipe is connected. The recipe is stored in the storage medium in the storage unit 82. The storage medium may be a fixed one such as a hard disk or a portable one such as a CDROM or DVD. Furthermore, you may make it transmit a recipe suitably from another apparatus via a dedicated line, for example. Then, if necessary, an arbitrary recipe is called from the storage unit 82 by an instruction from the user interface 81 and is executed by the process controller 80, so that a desired value in the film forming apparatus is controlled under the control of the process controller 80. Processing is performed.

Next, a film forming process performed using the film forming apparatus configured as described above will be described.
First, the gate valve 28 is opened, and the wafer W is loaded into the chamber 11 from the loading / unloading port 27 and placed on the susceptor 12. By exhausting the chamber 11 through the exhaust port 24 and the exhaust pipe 25 by the exhaust device 26, the inside of the chamber 11 is brought to a predetermined pressure.

  In this state, the valves 33a and 33b are opened, and the carbon monoxide gas and water vapor adjusted to a predetermined flow rate by the mass flow controllers (MFC) 34a and 34b are guided to the reaction vessel 35 through the pipes 32a and 32b and the pipe 32. The reaction vessel 35 is heated to about 50 to 150 ° C. by the heater 35a, whereby the cuprous oxide powder 36, carbon monoxide and water vapor in the reaction vessel 35 are in accordance with the reaction equation shown in the above-described equation (3). Reacts to produce copper formate gas. The first copper formate gas reaches the gas diffusion space 21 of the shower head 20 through the pipe 37 and is discharged toward the wafer W from a number of gas discharge holes 23 formed in the shower plate 22. At this time, the copper formate gas is held at 50 to 150 ° C. by the heater 37 a provided on the outer periphery of the pipe 37 and the heater 20 a provided on the inner surface of the shower head 20. Supplied.

  The first copper formate gas is adsorbed on the wafer W held at a temperature of about room temperature to about 50 ° C. to form a first copper formate film as a precursor. The film thickness of the first copper formate film at this time can be controlled by the supply time of the first copper formate gas and the wafer temperature.

  In this way, the film formation of the first copper formate as the precursor is performed for a predetermined time, and when the predetermined thickness is reached, the supply of the first copper formate gas is stopped, and then the wafer W is moved to 100 by the heater 14. By heating and raising the temperature to ˜250 ° C., the copper formate is decomposed according to the reaction formula shown in the above formula (2) by the thermal energy at that time, and a copper film having a predetermined thickness is formed.

Thereafter, the output of the heater 14 is stopped, the gas lines are switched to the purge gas lines 16a and 16b, and the by-product gas and excess formic acid gas are purged with an inert gas such as N ₂ or Ar. Next, after adjusting the pressure in the chamber 11 to the external pressure, the gate valve 28 is opened and the wafer W is unloaded.

  According to the apparatus having the above configuration, a good quality Cu film with good step coverage can be formed at low cost. In addition, formic acid gas is introduced into the reaction vessel 35 to generate a first copper formate gas, and the first copper formate gas thus generated is guided into the chamber to adsorb the first copper formate to the wafer W; Thereafter, a copper film can be formed by an extremely simple method such as heating.

  In the apparatus having the above-described configuration, the wafer W is placed on the susceptor 12 and the inside of the chamber 11 is adjusted to a predetermined pressure, and then the wafer W is heated to 100 to 250 ° C. by the heater 14 in the reaction vessel 35. The generated copper formate gas may be discharged toward the wafer W by the shower head 20. Thereby, before depositing the first copper formate on the wafer W, the copper formate can be decomposed according to the reaction formula (2) described above to form a copper film having a predetermined thickness on the wafer W. For this reason, according to the apparatus of the said structure, it becomes possible to shorten the film-forming time of a copper film.

[Second Embodiment]
Next, a second embodiment will be described.
FIG. 5 is a cross-sectional view illustrating a schematic configuration of a film forming apparatus according to the second embodiment.
In this film forming apparatus, the mechanism for supplying the first copper formate is different from that of FIG. 3 according to the first embodiment, and other configurations are basically the same as those of the apparatus of FIG. The same reference numerals are given and description thereof is omitted.

  In the present embodiment, a pipe 41 having cuprous oxide on its inner surface is provided up to a portion facing the gas diffusion space 21 of the shower head 20 so as to be continuous with the pipe 32 for supplying carbon monoxide and water. A copper formate gas is formed inside. Specifically, the pipe 41 includes a main body 42 made of, for example, stainless steel, and a cuprous oxide film 43 coated on the inner side of the main body 42. The cuprous oxide film 43 can be easily formed as a dense film by performing reactive sputtering under conditions that reduce cupric oxide as much as possible, for example, as disclosed in Japanese Patent Application Laid-Open No. 2003-282897. it can. Instead of providing the cuprous oxide film 43, a pipe material made of cuprous oxide may be provided. A heater 41 a is provided outside the pipe 41. Therefore, while carbon monoxide gas and water vapor are flowing through the pipe 41, the carbon monoxide, water, and the cuprous oxide film 43 are maintained in the pipe 41 at 50 to 150 ° C. by the heater 41a. By reacting, a copper formate gas is generated according to the reaction formula shown in the above-described formula (3).

  In the film forming apparatus of the second embodiment configured as described above, the wafer W is loaded into the chamber 11 and placed on the susceptor 12 basically in the same manner as in the first embodiment. Is maintained at a predetermined pressure, the valves 33a and 33b are opened, and the carbon monoxide gas and water vapor adjusted to a predetermined flow rate by the mass flow controllers (MFC) 34a and 34b are supplied to the pipe 41 through the pipes 32a and 32b and the pipe 32. Lead. The pipe 41 is heated to about 50 to 150 ° C. by the heater 41a. For this reason, the pipe 41 and the cuprous oxide film 43 coated on the inner side of the pipe 41 in the process of passing the carbon monoxide gas and water vapor through the pipe 41 are combined. Carbon oxide and water vapor react with each other according to the reaction formula shown in the above-described formula (3) to generate copper formate gas. The first copper formate gas reaches the gas diffusion space 21 of the shower head 20 through the pipe 41 and is discharged toward the wafer W from a number of gas discharge holes 23 formed in the shower plate 22. Also at this time, as in the first embodiment, the first copper formate gas is held at 50 to 150 ° C. by the heater 20a and is supplied to the wafer W in a gas state. And, just like the first embodiment, this first copper formate gas is adsorbed to the wafer W held at a temperature of room temperature to about 50 ° C., and the solid first copper formate film as the precursor is removed. Form. Further, in exactly the same manner as in the first embodiment, the wafer W is heated to 100 to 250 ° C. and heated by the heater 14, and the copper formate is added according to the reaction formula shown in the above formula (2) by the thermal energy at that time. Decomposing to form a copper film having a predetermined thickness.

  According to the apparatus of the present embodiment, the cuprous oxide film 43 reacts with the carbon monoxide gas and the water vapor while the carbon monoxide gas and the water vapor pass through the pipe 41 to produce the cuprous formate gas. The copper formate gas generated in this way can be introduced into the chamber to adsorb the copper formate to the wafer W, and then heated to form a copper film by a very simple method, And the above effects can be produced.

  In the apparatus of the present embodiment, the wafer W is placed on the susceptor 12 and the inside of the chamber 11 is adjusted to a predetermined pressure, and then the wafer W is heated to 100 to 250 ° C. by the heater 14 while inside the pipe 41. The generated copper formate gas may be discharged toward the wafer W by the shower head 20. Thereby, before depositing the first copper formate on the wafer W, the copper formate can be decomposed according to the reaction formula (2) described above to form a copper film having a predetermined thickness on the wafer W. For this reason, it is possible to shorten the film formation time of the copper film also by the apparatus of this embodiment. In this embodiment also, the steam generator 151 may be used to supply the steam.

[Third Embodiment]
Next, a third embodiment will be described.
FIG. 6 is a cross-sectional view illustrating a schematic configuration of a film forming apparatus according to the third embodiment.
This film forming apparatus is different from FIG. 3 according to the first embodiment in the mechanism for heating the wafer on the susceptor and the exhaust path, and the other configuration is basically the same as the apparatus in FIG. The members are denoted by the same reference numerals and the description thereof is omitted.

  In the present embodiment, a susceptor 12 'having no heater is provided instead of the susceptor 12, and a lamp heating unit 50 is provided below the susceptor 12'. The lamp heating unit 50 is configured by arranging a plurality of lamp heaters 51 made of ultraviolet lamps and providing a transmission window 52 made of a heat ray transmitting material such as quartz on the lamp heater 51. The susceptor 12 'is placed thereon.

  Further, an exhaust port 53 is opened at a height position corresponding to the susceptor 12 ′ on the side wall of the chamber 11. The side wall of the chamber 11 extends horizontally from the exhaust port 53 and extends downward in the middle to reach the bottom surface of the chamber 11. An open exhaust passage 54 is formed, and an exhaust pipe 55 is connected to the exhaust passage 54. An exhaust device 56 having a vacuum pump is connected to the exhaust pipe 55. Then, by operating the exhaust device 56, the inside of the chamber 11 is depressurized to a predetermined degree of vacuum via the exhaust path 54 and the exhaust pipe 55.

  In the third embodiment as well, basically the wafer W is loaded and placed on the susceptor 12 ', the chamber 11 is kept at a predetermined pressure, and the valves 33a and 33b are opened, as in the first embodiment. The carbon monoxide gas and water vapor adjusted to a predetermined flow rate by the mass flow controllers (MFC) 34a and 34b are led to the reaction vessel 35 through the pipes 32a and 32b and the pipe 32, and the inside of the reaction vessel 35 is heated by a heater 35a. In the state maintained at 150 ° C., the cuprous oxide powder 36 therein, the carbon monoxide gas gas and the water vapor are reacted to generate a cuprous formate gas. As in the first embodiment, the first copper formate gas reaches the shower head 20 through the pipe 37 and is discharged toward the wafer W from the discharge hole 23. The first copper formate gas is maintained at 50 to 150 ° C. and supplied to the wafer W in a gas state by the heater 37 a provided on the outer periphery of the pipe 37 and the heater 20 a provided on the inner surface of the shower head 20. Here, the first copper formate gas discharged from the shower head 20 is adsorbed to the wafer W, and a solid first copper formate film as a precursor is formed on the wafer W. And the wafer in which the 1st copper formate film | membrane of desired thickness was formed is heated and heated to 100-250 degreeC like 1st Embodiment, and it is in Formula (2) mentioned above with the thermal energy in that case According to the reaction formula shown, the copper formate is decomposed to form a copper film having a predetermined thickness.

  In this embodiment, since the wafer W is heated by the lamp heating unit 50, the temperature increase rate after forming the first copper formate film is fast. Therefore, the reaction formula shown in the above formula (2) can be rapidly advanced, and in addition to the extremely simple technique, a copper film can be formed with high throughput.

  In the apparatus of the present embodiment, the wafer W is placed on the susceptor 12 and the inside of the chamber 11 is adjusted to a predetermined pressure, and then the wafer W is heated to 100 to 250 ° C. by the lamp heating unit 50, The copper formate gas generated in 35 may be discharged toward the wafer W by the shower head 20. Thereby, before depositing the first copper formate on the wafer W, the copper formate can be decomposed according to the reaction formula (2) described above to form a copper film having a predetermined thickness on the wafer W. For this reason, it is possible to shorten the film formation time of the copper film also by the apparatus of this embodiment.

  In the third embodiment, the first copper formate manufacturing method may be the same as that of the second embodiment shown in FIG. Also in this embodiment, the steam generator 151 may be used to supply steam.

[Fourth Embodiment]
Next, a fourth embodiment will be described.
FIG. 7 is a cross-sectional view showing a schematic configuration of a film forming apparatus according to the fourth embodiment.
This film forming apparatus is different from FIG. 3 according to the first embodiment in the method and mechanism for reacting formic acid and cuprous oxide, and the other configuration is basically the same as the apparatus in FIG. Therefore, the same members are denoted by the same reference numerals and description thereof is omitted.

  In the present embodiment, a shower head 20 ′ is provided instead of the shower head 20 in the first embodiment. The shower head 20 ′ includes a gas diffusion space 21 ′ and a shower plate 22 ′ provided below the gas diffusion space 21 ′ and having a structure in which a detachable cuprous oxide-containing plate 22 b is attached to a base plate 22 a integral with the chamber 11. have. Part or all of the cuprous oxide-containing plate 22b is made of cuprous oxide. Specifically, the cuprous oxide-containing plate 22b may be one in which the surface of the base of another material such as stainless steel is coated with cuprous oxide, or a copper plate is thermally oxidized. Part or all of them may be cuprous oxide. As described above, the cuprous oxide coating film can be easily formed as a dense film by performing reactive sputtering under conditions that reduce cupric oxide as much as possible. A large number of gas discharge holes 23 'are formed in the shower plate 22', and a plate heater 57 is embedded in the base plate 22a.

  In addition, as shown in FIG. 8, you may make it provide the cuprous oxide containing plate 22b inside the base plate 22a.

  In addition, a carbon monoxide supply source 31a and a water storage container 31b are arranged outside the chamber 11, the pipes 32a and 32b extend from these, and the pipe 32 where the pipes 32a and 32b merge is arranged. 3 except that the pipe 32 is directly inserted into the showerhead 20 '. That is, carbon monoxide gas and water vapor are directly introduced into the gas diffusion space 21 'of the shower head 20' without reacting. Then, the carbon monoxide gas and water vapor introduced into the gas diffusion space 21 ′ with the shower plate 22 ′ held at 50 to 150 ° C. by the plate heater 57 are oxidized when passing through the gas discharge holes 23 ′. The carbon and water vapor react with the cuprous oxide of the cuprous oxide-containing plate 22b, and become cuprous formate gas and discharged toward the wafer W according to the reaction formula shown in the above-described formula (3).

  In the film forming apparatus of the fourth embodiment configured as described above, the wafer W is loaded into the chamber 11 and placed on the susceptor 12 basically as in the first embodiment. Is maintained at a predetermined pressure, the valves 33a and 33b are opened, and the carbon monoxide gas and water vapor adjusted to a predetermined flow rate by the mass flow controllers (MFC) 34a and 34b are supplied to the shower head 20 via the pipes 32a, 32b and the pipe 32. It is directly introduced into the gas diffusion space 21 '. At this time, the shower plate 22 ′ is set to a temperature suitable for the production of cuprous formate by 50 to 150 ° C. by the plate heater 57, and the carbon monoxide and water vapor introduced into the gas diffusion space 21 ′ are gas discharge holes 23 ′. The carbon monoxide and water vapor react with the cuprous oxide of the cuprous oxide-containing plate 22b when passing through the above, and become a cuprous formate gas according to the above-described reaction formula (3). It is discharged toward. Then, just as in the first embodiment, this first copper formate gas is adsorbed to the wafer W held at a temperature of room temperature to about 50 ° C. to form a solid first copper formate film as a precursor. To do. Further, in exactly the same manner as in the first embodiment, the wafer W is heated and heated to 100 to 250 ° C. by the heater 14, and the copper formate is added according to the reaction formula shown in the above formula (2) by the thermal energy at that time. Decomposing to form a copper film having a predetermined thickness.

  According to the apparatus of this embodiment, in addition to the basic effect that the step coverage is good and a good-quality Cu film can be formed at low cost, carbon monoxide gas and water vapor are directly introduced into the shower head 20 '. When the gas is discharged from the gas discharge hole 23 ', carbon monoxide and water vapor react with the cuprous oxide of the cuprous oxide-containing plate 22b to generate a cuprous formate gas. A copper film can be formed by an extremely simple method of adsorbing copper formate and then heating, and the path length transported to the surface of wafer W after the formation of copper formate gas is very long Therefore, the thermally unstable cuprous formate gas can be uniformly supplied to the surface of the wafer W without being decomposed.

  In the apparatus of this embodiment, after the wafer W is placed on the susceptor 12 and the inside of the chamber 11 is adjusted to a predetermined pressure, the formic acid gas and oxidation are performed while the wafer W is heated to 100 to 250 ° C. by the heater 14. The cuprous formate gas generated by reacting with the cuprous oxide of the cuprous-containing plate 22b may be discharged toward the wafer W. Thereby, before depositing the first copper formate on the wafer W, the copper formate can be decomposed according to the reaction formula (2) described above to form a copper film having a predetermined thickness on the wafer W. For this reason, it is possible to shorten the film formation time of the copper film also by the apparatus of this embodiment.

  Instead of providing the heater 14 as the susceptor heating means, a heating lamp unit 50 may be provided as shown in FIG. 6 according to the third embodiment. Also in this embodiment, the steam generator 151 may be used to supply steam.

[Fifth Embodiment]
Next, a fifth embodiment will be described.
FIG. 9 is a cross-sectional view showing a schematic configuration of a film forming apparatus according to the fifth embodiment.
The film forming apparatus shown in FIG. 9 has a flat chamber 61 made of the same material as the chamber 11 shown in FIG. A susceptor 62 on which the wafer W is placed is disposed at the bottom of the chamber 61. The susceptor 62 is made of the same material as that of the susceptor 12, and is provided with a refrigerant flow path 19 for temperature control.

  Similar to the third embodiment shown in FIG. 6, the top wall portion of the chamber 61 has a lamp heating unit 50 including a plurality of lamp heaters 51 and transmission windows 52, with the transmission windows 52 facing downward. It arrange | positions so that a heat ray may be irradiated below.

  A gas inlet 66 is provided on the side wall of the chamber 61, and a cuprous formate gas is introduced from the gas inlet 66. Similarly to the second embodiment, the carbon monoxide supply source 31a and the water storage container 31b are arranged outside the chamber 11, and the pipes 32a and 32b extend from these, and the pipe 32 into which the pipes 32a and 32b merge. A pipe 41 having a main body 42 and a cuprous oxide film 43 coated on the inner side of the main body 42 is provided from the end of the pipe 32 to the gas inlet 66. Further, the inside of the pipe 41 is heated to 50 to 150 ° C. suitable for the production of the first copper formate gas by the heater 41 a provided outside the pipe 41. Accordingly, the carbon monoxide gas, water, and the cuprous oxide film 43 react with each other while being maintained at 50 to 150 ° C. in the pipe 41, and cuprous formate according to the reaction formula shown in the above-described formula (3). A gas is generated and introduced into the chamber 61 from the gas inlet 66.

  An exhaust port 63 is formed on the side wall of the chamber 61 opposite to the gas introduction port 66, and an exhaust pipe 64 is connected to the exhaust port 63. An exhaust device 65 having a vacuum pump is connected to the exhaust pipe 64. By operating the exhaust device 65, the inside of the chamber 61 is decompressed to a predetermined degree of vacuum via the exhaust pipe 64.

  In the film forming apparatus configured as described above, first, a gate valve (not shown) is opened, and the wafer W is loaded into the chamber 61 and placed on the susceptor 62. The susceptor 62 is previously held at a temperature of about −30 to 50 ° C. by the refrigerant flowing through the refrigerant flow path 19. Then, the inside of the chamber 61 is evacuated through the exhaust port 63 and the exhaust pipe 64 by the exhaust device 65 to bring the inside of the chamber 61 to a predetermined pressure. Next, the valves 33 a and 33 b are opened, and the carbon monoxide gas and water vapor adjusted to a predetermined flow rate by the mass flow controllers (MFC) 34 a and 34 b are passed through the pipe 32 through the pipes 32 a and 32 b and the pipe 32. In the present embodiment, carbon monoxide gas and water vapor are guided from the pipe 32 to the pipe 41. The pipe 41 is heated to about 50 to 150 ° C. by the heater 41a. Therefore, the pipe 41 and the cuprous oxide film 43 coated on the inner side of the pipe 41 in the process of passing the carbon monoxide gas and the water vapor through the pipe 41 are combined. Carbon oxide gas and water vapor react with each other according to the reaction formula shown in the above formula (3) to produce copper formate gas. The first copper formate gas is introduced into the chamber 61 from the pipe 41 through the gas inlet 66, flows along the surface of the wafer W, and reaches the exhaust outlet 63. In this process, the copper formate is adsorbed on the wafer W held at −30 to 50 ° C. to form a solid first copper formate film as a precursor. Thereafter, the wafer W is heated and heated to 100 to 250 ° C. by irradiating the lamp heater 51 of the lamp heating unit 50, and the cuprous formate according to the reaction formula shown in the above formula (2) by the thermal energy at that time. And a copper film having a predetermined thickness is formed.

  According to the apparatus of this embodiment, since gas is introduced from the side wall and exhausted from the opposite side wall, the apparatus can be made compact, and the lamp light is directly applied to the cuprous formate to supply energy. Compared with the method of heating from the back surface of the susceptor and indirectly supplying energy by heat transfer, the reaction can be made extremely fast. Further, in the method in which energy is directly applied from above, it is not necessary to provide a heating mechanism behind the wafer W, so that a cooling mechanism like the susceptor 62 can be provided. Since the amount of adsorption of the first copper formate gas on the surface of the wafer W is larger as the temperature is lower, this method is more advantageous than the first to fourth embodiments described above.

  In the apparatus of this embodiment, the wafer W is placed on the susceptor 62 and the inside of the chamber 61 is adjusted to a predetermined pressure, and then the lamp W is heated to 100 to 250 ° C. by the lamp heating unit 50 while the pipe 41 The copper formate gas generated in the inside may be introduced from the gas inlet 66 onto the wafer W in the chamber 61. Thereby, before depositing the first copper formate on the wafer W, the copper formate can be decomposed according to the reaction formula (2) described above to form a copper film having a predetermined thickness on the wafer W. For this reason, it is possible to shorten the film formation time of the copper film also by the apparatus of this embodiment.

  In addition, the formation method of cuprous formate may use the reaction container which stored the powdered cuprous oxide similarly to 1st Embodiment. Also in this embodiment, the steam generator 151 may be used to supply steam.

[Sixth Embodiment]
Next, a sixth embodiment will be described.
FIG. 10 is a cross-sectional view showing a schematic configuration of a film forming apparatus according to the sixth embodiment.
This film forming apparatus supplies carbon monoxide gas and water vapor directly from the carbon monoxide supply source 31 a and the water storage container 31 b to the chamber 61 through the pipes 32 a and 32 b and the pipe 32, and contains the cuprous formate in the chamber 61. Other than the generation, the apparatus is basically the same as the apparatus of the fifth embodiment shown in FIG. That is, the pipe 32 extends to the gas inlet 66 of the chamber, and the cuprous oxide-containing member 67 is disposed near the gas inlet 66 in the chamber 61. At least the surface of the cuprous oxide-containing member 67 is made of cuprous oxide. Specifically, the cuprous oxide-containing member 67 may be one in which the surface of the base of another material such as stainless steel is coated with cuprous oxide, or at least the surface portion of the copper plate is formed. It may be one obtained by thermal oxidation to form cuprous oxide. A heater 68 is embedded in the cuprous oxide-containing member 67, whereby the cuprous oxide-containing member 67 can be maintained at 50 to 150 ° C. suitable for producing cuprous formate.

  In the film forming apparatus configured as described above, the wafer W is loaded into the chamber 61 and placed on the susceptor 62 as in the fifth embodiment, and is kept at a predetermined temperature. Of pressure. Next, the valves 33 a and 33 b are opened, and carbon monoxide gas and water vapor adjusted to a predetermined flow rate by the mass flow controllers (MFC) 34 a and 34 b are introduced into the chamber 61 through the pipes 32 a and 32 b and the pipe 32. The carbon monoxide gas and the water vapor introduced into the chamber 61 flow along the cuprous oxide-containing member 67 provided in the vicinity of the gas inlet 66. It is heated to about ~ 150 ° C. Therefore, carbon monoxide gas and water vapor produce cuprous formate gas in accordance with the reaction formula shown in the above formula (3) with cuprous oxide of cuprous oxide-containing member 67. To do. The first copper formate gas flows along the surface of the wafer W, and is adsorbed to the wafer W held at -30 to 50 ° C. in the process to form a solid first copper formate film as a precursor. To do. Thereafter, by irradiating the lamp heater 51 of the lamp heating unit 50, the wafer W is heated to 100 to 250 ° C. and heated in the same manner as in the fifth embodiment. According to the reaction formula shown, the copper formate is decomposed to form a copper film having a predetermined thickness.

  According to the apparatus of this embodiment, in addition to the same effects as those of the fifth embodiment, since cuprous formate gas is generated immediately before the wafer W, deterioration of chemically unstable cuprous formate gas is prevented. Can be reduced.

  In the apparatus of the present embodiment, after the wafer W is placed on the susceptor 62 and the inside of the chamber 61 is adjusted to a predetermined pressure, the cuprous oxide-containing member 67 is heated to about 50 to 150 ° C. by the heater 68. In addition, carbon monoxide and water vapor may be introduced into the chamber 61 from the gas inlet 66 while the wafer W is heated to 100 to 250 ° C. by the lamp heating unit 50. As a result, the cuprous formate produced by the reaction of carbon monoxide and water vapor with the cuprous oxide of the cuprous oxide-containing member 67 according to the above-described reaction formula (3) is formed on the wafer W. Prior to deposition, a copper film having a predetermined thickness can be formed on the wafer W by being decomposed in accordance with the reaction formula shown in the above formula (2). For this reason, it is possible to shorten the film formation time of the copper film also by the apparatus of this embodiment. In this embodiment also, the steam generator 151 may be used to supply the steam.

[Seventh Embodiment]
Next, a seventh embodiment will be described.
FIG. 11 is a cross-sectional view illustrating a schematic configuration of a film forming apparatus according to a seventh embodiment.
The film forming apparatus shown in FIG. 11 is the same as the film forming apparatus shown in FIG. 3 according to the first embodiment, but instead of providing the susceptor 12 with a heater, a lamp heating unit 50 is provided above the chamber 11 and a shower head is provided. A gas inlet 71 is provided on the top wall of 11 and a heater 71a is provided on the inner surface thereof. The other configurations are basically the same as those in FIG. 3, and the same components as those in FIG.

  In the film forming apparatus of the seventh embodiment configured as described above, the wafer W is loaded into the chamber 11 and placed on the susceptor 12 basically as in the first embodiment. Is maintained at a predetermined pressure, the valves 33a and 33b are opened, and the carbon monoxide gas and water vapor adjusted to a predetermined flow rate by the mass flow controllers (MFC) 34a and 34b are supplied to the reaction vessel 35 through the pipes 32a, 32b and the pipe 32. Lead to. The reaction vessel 35 is heated to about 50 to 150 ° C. by the heater 35a, whereby the cuprous oxide powder 36, carbon monoxide and water vapor in the reaction vessel 35 are in accordance with the reaction equation shown in the above-described equation (3). Reacts to produce copper formate gas. The first copper formate gas is introduced into the chamber 11 through the pipe 37 and the gas inlet 71. At this time, the copper formate gas is maintained at 50 to 150 ° C. by the heater 37 a of the pipe 37 and the heater 71 a of the gas inlet 71 and is supplied to the wafer W in a gas state. The wafer W held at a temperature of about 0 ° C. is contacted and adsorbed. Therefore, a solid copper formate film having a predetermined thickness is formed by supplying the cuprous formate gas for a predetermined time.

  Thereafter, the wafer W is heated by the lamp heating unit 50, and the copper formate is decomposed according to the reaction represented by the equation (2) by the thermal energy at that time, thereby forming a copper film having a predetermined thickness.

  According to such a configuration, although there is a concern that the uniformity of the gas supply is slightly reduced by the absence of the shower head, the cuprous formate is decomposed by the lamp heating from above, so that the lamp heating unit is connected to the susceptor. The wafer W can be heated more quickly than the apparatus of FIG. 6 provided below 12, and the throughput can be further improved. As in the fifth embodiment, since no heating mechanism is provided in the susceptor 12, a cooling mechanism can be provided. Since the amount of adsorption of the first copper formate gas on the surface of the wafer W is larger as the temperature is lower, this method is more advantageous than the first to fourth embodiments described above.

  In the apparatus of the present embodiment, the wafer W is placed on the susceptor 12 and the inside of the chamber 11 is adjusted to a predetermined pressure, and then the wafer W is heated to 100 to 250 ° C. by the lamp heating unit 50, The copper formate gas generated in 35 may be supplied toward the wafer W from the gas inlet 71. Thereby, before depositing the first copper formate on the wafer W, the copper formate can be decomposed according to the reaction formula (2) described above to form a copper film having a predetermined thickness on the wafer W. For this reason, it is possible to shorten the film formation time of the copper film also by the apparatus of this embodiment.

  In this embodiment, the form of cuprous formate may be formed by reacting with formic acid by forming a cuprous oxide film inside the pipe as in the apparatus of FIG. A cuprous oxide-containing member may be disposed therein and reacted with carbon monoxide and water vapor introduced into the chamber 11. In this embodiment also, the steam generator 151 may be used to supply the steam.

[Eighth Embodiment]
In the first to seventh embodiments, an example in which both the cuprous oxide adsorption process and the copper film formation process by heating are performed in one chamber is shown. In this embodiment, throughput and processing freedom are shown. From the viewpoint of the degree, etc., an example will be shown in which these steps are performed in different chambers and the devices are clustered.

  FIG. 12 is a plan view showing a schematic structure of such a clustered system. In this system, an adsorption processing unit 101 that adsorbs copper first formate on the wafer W and a thermal energy is applied to the first copper formate adsorbed on the wafer W by annealing the wafer W to form a copper film. An annealing unit 102 and a cooling unit 103 for cooling the annealed wafer W are provided, and these are provided corresponding to the three sides of the heptagonal wafer transfer chamber 104. Load lock chambers 105 and 106 are provided on the other two sides of the wafer transfer chamber 104, respectively. A wafer loading / unloading chamber 108 is provided on the opposite side of the load lock chambers 105 and 106 from the wafer transfer chamber 104, and a wafer W can be accommodated on the opposite side of the wafer loading / unloading chamber 108 to the load lock chambers 105 and 106. Ports 109, 110, and 111 for attaching three carriers C are provided.

  The adsorption processing unit 101, the annealing unit 102, the cooling unit 103, and the load lock chambers 105 and 106 are connected to each side of the wafer transfer chamber 104 via a gate valve G as shown in FIG. Opening the gate valve G communicates with the wafer transfer chamber 104, and closing the corresponding gate valve G blocks the wafer transfer chamber 104. A gate valve G is also provided at a portion of the load lock chambers 105 and 106 connected to the wafer loading / unloading chamber 108, and the load lock chambers 105 and 106 open the corresponding gate valves G by opening the corresponding gate valves G. When the corresponding gate valve G is closed, the wafer loading / unloading chamber 108 is shut off.

  In the wafer transfer chamber 104, a wafer transfer device 112 that loads and unloads the wafer W with respect to the adsorption processing unit 101, the annealing unit 102, the cooling unit 103, and the load lock chambers 105 and 106 is provided. The wafer transfer device 112 is disposed substantially at the center of the wafer transfer chamber 104, and has two blades 114a and 114b that hold the wafer W at the tip of a rotatable / extensible / retractable portion 113 that can rotate and expand / contract. These two blades 114a and 114b are attached to the rotating / extending / contracting portion 113 so as to face opposite directions. The inside of the wafer transfer chamber 104 is maintained at a predetermined degree of vacuum.

  The three ports 109, 110, and 111 for attaching the carrier C in the wafer loading / unloading chamber 108 are provided with shutters (not shown), respectively, so that the wafer C containing the wafer W or an empty carrier C can be directly attached to these ports. It has become. An alignment chamber 115 is provided on the side surface of the wafer loading / unloading chamber 108, where the wafer W is aligned.

  In the wafer loading / unloading chamber 108, a wafer transfer device 116 for loading / unloading the wafer W into / from the carrier C and loading / unloading the wafer W into / from the load lock chambers 105 and 106 is provided. The wafer transfer device 116 has an articulated arm structure and can run on the rail 118 along the arrangement direction of the carrier C. The wafer W is placed on the hand 117 at the tip thereof and transferred. I do. Control of the entire system, such as operations of the wafer transfer apparatuses 112 and 116, is performed by the control unit 119. The control unit 119 has the functions of the process controller 80, the user interface 81, and the storage unit 82.

  As the adsorption processing unit 101, a unit basically having a configuration in which the heating unit is removed from the apparatuses of the first to seventh embodiments can be used.

  The annealing unit 102 may be any unit that can heat the wafer W, but the unit shown in FIG. 13 can be preferably used. The annealing unit 102 has a flat chamber 121 similar to the chamber 61 of the apparatus shown in FIG. 9, and a susceptor on which the wafer W on which the first copper formate film 200 is formed is placed on the bottom of the chamber 121. 122 is arranged.

  The top wall portion of the chamber 121 has a lamp heating unit 130 composed of a lamp heater 131 composed of a plurality of ultraviolet lamps and a transmission window 132 so that heat rays are irradiated downward with the transmission window 132 facing down. Is arranged.

A gas inlet 141 is provided on the side wall of the chamber 121, and a gas inlet pipe 142 is connected to the gas inlet 141. A gas supply mechanism 143 that supplies an inert gas such as N ₂ gas, Ar gas, or He gas is connected to the gas introduction pipe 142.

  An exhaust port 144 is formed on the side wall of the chamber 121 opposite to the gas inlet 141, and an exhaust pipe 145 is connected to the exhaust port 144. An exhaust device 146 having a vacuum pump is connected to the exhaust pipe 145. By operating the exhaust device 146, the inside of the chamber 121 is depressurized to a predetermined degree of vacuum via the exhaust pipe 145.

  In such an apparatus, rapid heating by lamp heating and rapid cooling by an inert gas are possible, an extremely rapid annealing process can be performed, and throughput can be increased. In addition, since this unit is a module dedicated to annealing, the degree of freedom of processing is high, and for example, it is easy to reduce the carbon and oxygen in the film by annealing at a temperature higher than the Cu film forming wafer temperature.

  Although not shown, the cooling unit 103 has a simple configuration in which a cooling stage having a refrigerant flow path is arranged in the chamber, and is for cooling the wafer W that has been heated to a high temperature due to the annealing process.

  In the system configured as described above, the wafer W is taken out from one of the carriers C by the wafer transfer device 116 and loaded into the load lock chamber 105, and transferred from the load lock chamber 105 to the transfer chamber 104 by the wafer transfer device 112. . First, the wafer W is transported to the adsorption processing unit 101 and the first copper formate adsorption process is performed. The wafer W on which the first copper formate film having a predetermined thickness is formed in the adsorption processing unit 101 is taken out from the adsorption processing unit 101 by the wafer transfer device 112 and subsequently carried into the annealing unit 102. In the annealing unit 102, the cuprous oxide film is decomposed by lamp heating to form a copper film. Thereafter, the wafer W on which the copper film is formed is taken out from the annealing unit 102 by the wafer transfer device 112 and subsequently carried into the cooling unit 103. The cooling unit 103 cools the wafer W to a predetermined temperature on the wafer stage. The wafer W cooled by the cooling unit 103 is transferred to the load lock chamber 106 by the wafer transfer device 112, and is carried into the predetermined carrier C from the load lock chamber 106 by the wafer transfer device 116. Such a series of processing is continuously performed on the number of wafers W accommodated in the carrier C.

  In this way, each process is performed by different devices, and by clustering them, the processing can be dedicated to each device (unit), and throughput can be increased compared to performing all the steps with one device. Can be improved.

  In addition, you may cluster the unit which performs the film-forming process of the copper film based on this invention, and the other unit which performs sputtering etc. similarly to FIG.

  The present invention is not limited to the above-described embodiment, and various modifications can be made. For example, the means for producing copper formate and the means for heating the first copper formate film are merely examples, and any other means may be used. Moreover, in the said embodiment, the case where the copper formate is produced | generated using carbon monoxide, water, copper oxide, etc., this is supplied to a board | substrate, energy is given, and it decomposes | disassembles and forms Cu film | membrane is an example. Although explained, it is possible to produce a formate using another oxygen-containing metal compound instead of cuprous formate and decompose it to produce a metal film, and the metal film is not limited to a Cu film, The above Ag film can also be formed. Further, a Ni film or a Co film can be formed using cobalt oxide or nickel oxide instead of copper oxide or silver oxide. In the case of different metals, the formation temperature, pressure and decomposition temperature of the carboxylate may be different from those of Cu. Furthermore, although the case where the semiconductor wafer was used as a board | substrate was shown in the said embodiment, it is applicable also to other board | substrates, such as a glass substrate for flat panel displays (FPD). Furthermore, unless the scope of the present invention is deviated, it is within the scope of the present invention to appropriately combine the constituent elements of the above-described embodiment or to partially remove the constituent elements of the above-described embodiment.

  The method for forming a copper film according to the present invention is suitable as a Cu wiring of a semiconductor device because a good film can be obtained at a low cost with good step coverage.

The schematic diagram for demonstrating the film-forming method which concerns on this invention. The schematic diagram for demonstrating the other example of the film-forming method which concerns on this invention. 1 is a cross-sectional view showing a schematic configuration of a film forming apparatus according to a first embodiment of the present invention. The figure which shows the case where a water vapor generator is used as a water supply part. Sectional drawing which shows schematic structure of the film-forming apparatus which concerns on the 2nd Embodiment of this invention. Sectional drawing which shows schematic structure of the film-forming apparatus which concerns on the 3rd Embodiment of this invention. Sectional drawing which shows schematic structure of the film-forming apparatus which concerns on the 4th Embodiment of this invention. Sectional drawing which shows the modification of the film-forming apparatus of FIG. Sectional drawing which shows schematic structure of the film-forming apparatus which concerns on the 5th Embodiment of this invention. Sectional drawing which shows schematic structure of the film-forming apparatus which concerns on the 6th Embodiment of this invention. Sectional drawing which shows schematic structure of the film-forming apparatus which concerns on the 7th Embodiment of this invention. The top view which shows schematic structure of the system which concerns on the 8th Embodiment of this invention. Sectional drawing which shows the annealing unit used for the system of FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1; Board | substrate 2; Carboxylate film | membrane 3; Metal film 4; First copper formate film | membrane 5; Copper film | membrane 11,61; Chamber 12,62; Susceptor 14; Heater 19; Refrigerant flow path 20; Shower head 20a, 35a, 37a, 71a; heater 22, 22 '; shower plate 22b; cuprous oxide-containing plate 31a; carbon monoxide source 31b; water storage vessel 32, 37, 41; pipe 35; reaction vessel 36; 43; Cuprous oxide film 50; Lamp heating unit 57, 68; Plate heater 80; Process controller 81; User interface 82; Storage unit 101; Adsorption processing unit 102; Annealing unit 103; Cooling unit 119; Generator 152, 153; Pipe 154; Hydrogen gas supply source 155; Oxygen gas supply Supply W: Semiconductor wafer (substrate)

Claims (37)

Reacting carbon monoxide, water, and an oxygen-containing metal compound to produce a formate gas of the metal;
Supplying the metal formate gas onto the substrate;
Forming a metal film by applying energy to the substrate and decomposing the metal formate supplied on the substrate to form a metal film.   The film forming method according to claim 1, wherein the oxygen-containing metal compound is in a powder form, and formate gas is obtained by supplying gaseous carbon monoxide and gaseous water thereto. Placing the substrate in a processing vessel held in vacuum;
Reacting carbon monoxide, water, and an oxygen-containing metal compound to produce a formate gas of the metal;
Supplying the formate gas onto a substrate in the processing vessel;
Forming a metal film by applying energy to the substrate and decomposing the formate supplied on the substrate to form a metal film.   The formate gas is formed by reacting gaseous carbon monoxide, gaseous water, and an oxygen-containing metal compound outside the processing vessel, and is introduced into the processing vessel through a pipe. The film forming method according to claim 3.   5. The film forming method according to claim 4, wherein formate gas is generated by supplying gaseous carbon monoxide and gaseous water to the oxygen-containing metal compound powder.   The formate gas is generated by using a gas pipe coated with an oxygen-containing metal compound on the inner surface as the pipe, and passing gaseous carbon monoxide and gaseous water through the pipe. 5. The film forming method according to 4.   The film forming method according to claim 3, wherein the formate gas is generated by reacting carbon monoxide, water, and an oxygen-containing metal compound in the processing container.   The member made of copper oxide is disposed in the processing vessel, and formate gas is generated by supplying gaseous carbon monoxide and gaseous water to the member. The film forming method. Formate is deposited on the substrate by supplying gaseous carbon monoxide and gaseous water on the substrate,
9. The film forming method according to claim 1, wherein the formate on the substrate is decomposed by applying energy to the substrate on which the formate is deposited.   The film forming method according to claim 1, wherein energy is applied to the substrate while supplying a formate gas onto the substrate.   The film formation method according to any one of claims 1 to 10, wherein the metal is copper or silver. The oxygen-containing metal compound includes cuprous oxide (Cu ₂ O), cupric oxide (CuO), cupric hydroxide (Cu (OH) ₂ ), cuprous silver (Ag ₂ O), oxidized first The film forming method according to claim 11, wherein the film forming method is any one of two silver (Ag ₂ O ₂ ).   13. The film forming method according to claim 1, wherein the energy given to the substrate is thermal energy.   14. The film forming method according to claim 13, wherein thermal energy is applied to the substrate by a resistance heating element provided on a substrate support member that supports the substrate.   14. The film forming method according to claim 13, wherein thermal energy is applied to the substrate by a heating lamp provided at a position distant from the substrate. A processing vessel held in a vacuum and in which a substrate is placed;
A substrate support member for supporting the substrate in the processing container;
A gas generating means for reacting carbon monoxide, water, and an oxygen-containing metal compound to generate a formate gas of the metal;
Gas supply means for supplying the formate gas onto the substrate in the processing vessel;
Energy applying means for applying energy to the substrate on the substrate support member;
An exhaust means for exhausting the inside of the processing container,
A film forming apparatus, wherein formate is supplied onto a substrate by the gas supply means, and the formate is decomposed by energy from the energy applying means to form a metal film on the substrate.   The gas generation means is supplied from the carbon monoxide supply unit including a carbon monoxide supply unit that supplies gaseous carbon monoxide, a water supply unit that supplies gaseous water, and an oxygen-containing metal compound. A gaseous carbon monoxide and a reaction unit that generates a formate gas of the metal by a reaction between gaseous water supplied from the water supply unit and an oxygen-containing metal compound, and supplies the formate gas The film forming apparatus according to claim 16, wherein the gas supply unit includes a formate introduction unit that guides the generated formate gas to the processing container.   The film forming apparatus according to claim 17, wherein the water supply unit includes a water vapor generator that generates water vapor using oxygen and hydrogen.   The film forming apparatus according to claim 17, wherein the reaction unit includes a reaction container that stores oxygen-containing metal compound powder.   The film forming apparatus according to claim 17, wherein the reaction unit includes a member made of an oxygen-containing metal compound.   The carbon monoxide supply section has a carbon monoxide supply pipe, the water supply section has a water supply pipe, and the reaction section has a junction pipe where the carbon monoxide supply pipe and the water supply pipe merge. 21. The film forming apparatus according to claim 20, wherein the member made of an oxygen-containing metal compound in the reaction part is an inner surface layer made of an oxygen-containing metal compound provided on an inner surface of the junction pipe.   The film forming apparatus according to any one of claims 17 to 21, wherein the formate introduction unit includes a shower head that guides the formate gas into a shower shape. A processing vessel held in a vacuum and in which a substrate is placed;
A substrate support member for supporting the substrate in the processing container;
A member made of an oxygen-containing metal compound disposed in the processing vessel;
Carbon monoxide supply means for supplying gaseous carbon monoxide into the reaction vessel;
Water supply means for supplying gaseous water into the reaction vessel;
Energy applying means for applying energy to the substrate on the substrate support member;
An exhaust means for exhausting the inside of the processing container,
The gaseous carbon monoxide supplied from the carbon monoxide supply means, the gaseous water supplied from the water supply means, and the member made of the oxygen-containing metal compound react to generate formate gas. Then, the formate gas is supplied onto the substrate, and the formate is decomposed by the energy applied by the energy applying means to form a metal film on the substrate.   The carbon monoxide supply means includes a carbon monoxide supply source, a carbon monoxide supply pipe for supplying gaseous carbon monoxide to the processing vessel, and a gaseous carbon monoxide for introducing the gaseous carbon monoxide into the processing vessel. The water supply means includes a water supply source, a water supply pipe for supplying gaseous water to the processing vessel, and water introduction for introducing gaseous water into the processing vessel. The film forming apparatus according to claim 23, further comprising:   25. The film forming apparatus according to claim 24, wherein the water supply source includes a water vapor generator that generates water vapor using oxygen and hydrogen.   The said carbon monoxide introducing | transducing part and the said water introducing | transducing part have a confluence | merging part, and the member consisting of an oxygen containing metal compound is provided in the said confluence | merging part. Deposition device.   The merging portion includes a shower head having a discharge member having a plurality of discharge holes, and the member made of the oxygen-containing metal compound constitutes part or all of the discharge member, and gas introduced into the shower head 27. The film forming apparatus according to claim 26, wherein when the carbon monoxide and the gaseous water pass through the discharge hole, the formate gas reacts with the oxygen-containing metal compound and is discharged.   The discharge member of the shower head has a base material and a coating layer made of an oxygen-containing metal compound formed on the surface of the base material, and the coating layer functions as a member made of the oxygen-containing metal compound. The film forming apparatus according to claim 27.   29. The formate gas is supplied onto the substrate by the gas supply means to deposit formate, and the formate deposited on the substrate is decomposed by the energy from the energy applying means. The film forming apparatus according to any one of the above.   30. The film formation according to claim 16, wherein energy is applied to the substrate by the energy applying unit while formate gas is supplied onto the substrate by the gas supplying unit. apparatus.   The film forming apparatus according to any one of claims 16 to 30, wherein the metal is copper or silver. The oxygen-containing metal compound used in the gas generating means is cuprous oxide (Cu ₂ O), cupric oxide (CuO), cupric hydroxide (Cu (OH) ₂ ), cuprous oxide (Ag). The film forming apparatus according to claim 31, wherein the film forming apparatus is any one of ₂ O) and silver oxide (Ag ₂ O ₂ ).   The film deposition apparatus according to any one of claims 16 to 32, wherein the energy applying unit applies thermal energy to the substrate.   34. The film forming apparatus according to claim 33, wherein the energy applying unit includes a resistance heating element provided on the substrate support member.   34. The film forming apparatus according to claim 33, wherein the energy applying unit includes a heating lamp provided apart from the substrate support member. The substrate is placed in a vacuum, the substrate is placed, and the formate formed by reacting carbon monoxide, water, and an oxygen-containing metal compound is supplied to the placed substrate to deposit a formate film on the substrate. 1 processing container;
A substrate on which a formate film is deposited is disposed in the first processing vessel while being held in a vacuum, energy is applied to the disposed substrate to decompose the formate on the substrate, and a metal film is formed on the substrate. A second processing vessel to be formed;
A film forming apparatus comprising: a substrate transfer mechanism that transfers a substrate from the first processing container to the second processing container without breaking a vacuum.   A storage medium that operates on a computer and stores a program for controlling a film forming apparatus, wherein the program executes the film forming method according to any one of claims 1 to 15 at the time of execution. A storage medium which causes a computer to control a film forming apparatus.

Images