TWI552225B - Sicn film formation method and apparatus - Google Patents

Description

Method and device for forming SiCN film

The present invention relates to a film forming method and apparatus for forming a SiCN film on a target substrate such as a semiconductor wafer. The term "semiconductor processing" as used herein includes various types of processing that are performed on a target substrate such as a semiconductor wafer or a glass substrate for an FPD (flat panel display) such as an LCD (Liquid Crystal Display). A semiconductor layer, an insulating layer, and a conductive layer are formed on a target substrate in a predetermined pattern to fabricate a semiconductor device or a structure having a wiring layer, an electrode, and the like connected to the semiconductor device.

In manufacturing a semiconductor device for constituting a semiconductor integrated circuit, a target substrate such as a semiconductor wafer is subjected to various processes such as film formation, etching, oxidation, diffusion, recombination, annealing, and natural oxide film removal. US 2006/0286817 A1 discloses a semiconductor processing method of this kind performed in a vertical heat treatment apparatus (so-called batch type). According to this method, the semiconductor wafer is first transferred from the wafer cassette to the vertical boat and supported thereon at a distance in the vertical direction. The wafer cassette can store, for example, 25 wafers, while the wafer boat can support 30 to 150 wafers. Next, the boat is loaded into the process vessel from below and the process vessel is hermetically sealed. Next, predetermined thermal processing is performed while controlling processing conditions such as process gas flow rate, processing pressure, and processing temperature.

In order to improve the performance of the semiconductor integrated circuit, it is important to improve the properties of the insulating film used in the semiconductor device. The semiconductor device includes, for example, SiO ₂ , PSG (phosphorus phosphide), P-SiO (formed by plasma CVD), P-SiN (formed by plasma CVD), and SOG (spin on glass), Si ₃ N ₄ ( An insulating film made of a material of tantalum nitride. In particular, since the tantalum nitride film has better insulating properties than the tantalum oxide film, and it can sufficiently function as an etching stopper film or an interlayer insulating film, it is widely used.

Several methods for forming a tantalum nitride film by thermal CVD (Chemical Vapor Deposition) on the surface of a semiconductor wafer are known. In the thermal CVD, such as monodecane (SiH ₄ ), dichlorodecane (DCS: SiH ₂ Cl ₂ ), hexachlorodioxane (HCD: Si ₂ Cl ₆ ) or bis-tert-butylamino decane (BTBAS: A decane gas of SiH ₂ (NH(C ₄ H ₉ )) ₂ ) is used as a helium source gas. For example, a tantalum nitride film is formed by thermal CVD using a gas combination of SiH ₂ Cl ₂ +NH ₃ (see US 5,874,368 A) or Si ₂ Cl ₆ +NH ₃ .

In recent years, due to the demand for increasing the miniaturization and integration of semiconductor integrated circuits, it is necessary to reduce the thermal history of semiconductor devices in the manufacturing steps, thereby improving the characteristics of the devices. For vertical processing devices, it is also desirable to modify the semiconductor processing method in accordance with the needs described above. For example, as a film formation process derived from CVD (Chemical Vapor Deposition), there is a case where a source gas or the like is intermittently supplied so as to repeatedly form a plurality of layers one at a time or several times each time (each having A method of performing film formation at the time of atomic or molecular-level thickness (for example, Japanese Patent Application KOKAI Publication No. 2-93071 and No. 6-45256 and US Pat. No. 6,165,916 A). Generally, this film formation method is called ALD (Atomic Layer Deposition) or MLD (Molecular Layer Deposition), which allows predetermined processing to be performed without exposing the wafer to extremely high temperatures.

For example, when dichlorosilane (DCS) and NH ₃ which are respectively a decane gas and a nitriding gas are supplied to form a tantalum nitride film (SiN), the following processing is performed. Specifically, DCS and NH ₃ gases are alternately and intermittently supplied into the process vessel with a purge period interposed therebetween. When NH ₃ gas is supplied, RF (Radio Frequency) is applied to generate a plasma in the process vessel to promote the nitridation reaction. More specifically, when the DCS is supplied to the process vessel, a layer having the thickness of one or more DCS molecules is adsorbed onto the surface of the wafer. Excess DCS is removed during the purge period. Next, NH _{3 is} supplied and a plasma is generated, thereby performing low temperature nitridation to form a tantalum nitride film. These successive steps are repeated to complete a film having a predetermined thickness.

When an insulating film such as one of those described above is formed and then another film is formed thereon, contaminants such as organic substances and particles may have adhered to the surface of the insulating film. Therefore, cleaning processing is performed to remove contaminants as needed. In this cleaning process, the semiconductor wafer is immersed in a cleaning solution such as dilute hydrofluoric acid to perform etching on the surface of the insulating film. Therefore, the surface of the insulating film is etched to a very small amount to remove contaminants.

When the insulating film is formed by CVD at a high processing temperature of, for example, about 760 ° C, the etching rate of the insulating film during the cleaning process is extremely low. Accordingly, the insulating film is not excessively etched by cleaning, and thus the cleaning process is performed with a high degree of control of the film thickness. However, when a film having low heat resistance exists as a lower layer, thermal CVD processing at a high temperature is not suitable.

On the other hand, when the insulating film is formed of an ALD film at a lower processing temperature of, for example, about 400 ° C, the etching rate of the insulating film during the cleaning process is relatively high. Accordingly, the insulating film can be excessively etched by cleaning, and thus the cleaning process requires lower controllability of the film thickness.

In addition, the tantalum nitride film can be used as an etching stopper film or an interlayer insulating film. In this case, the etching rate of the tantalum nitride film must be extremely low. However, the conventional film formation method cannot satisfy this requirement.

It is an object of the present invention to provide a method and apparatus for forming a SiC film that can use relatively low processing temperatures in film formation and that etches the film a small amount during the cleaning process so that the film thickness can be highly controlled The cleaning process is performed while allowing the film to sufficiently function as an etch stop film or an interlayer insulating film. It should be noted that the present invention is an improvement of the invention disclosed in US 2005/095770 A1 and US 2007/167028 A1.

According to a first aspect of the present invention, there is provided a method for forming a SiCN film on a target substrate in a process field, the process field being configured to selectively supply a first process gas containing a decane gas, containing nitrogen a second process gas of the gas and a third process gas containing a hydrocarbon gas, the method being arranged to perform a plurality of cycles to laminate the films respectively formed by the cycles, thereby forming a SiCN film having a predetermined thickness, Each of the equal periods includes: performing a first step of supplying the first process gas to the process field; performing a second step of supplying the second process gas to the process field; and performing a third step of supplying the third process gas to the process field And a fourth step of discontinuing the supply of the first process gas to the process plant, wherein each of the cycles is arranged such that none of the first, second and third process gases are during their supply The outside of the process field is converted into a plasma, but the process field is heated to a first temperature during the first, second, third, and fourth steps, and the decane gas, the nitriding gas, and the hydrocarbon gas are The reaction with each other at a first temperature.

In accordance with a second aspect of the present invention, an apparatus for forming a SiCN film on a target substrate is provided, the apparatus comprising: a process vessel having a process field configured to receive a target substrate; configured to support a process in the process a support member of the target substrate; a heater configured to heat the target substrate in the process field; an exhaust system configured to vent gas in the process field; configured to supply a first process gas containing a decane gas a first process gas supply line to the process plant; configured to supply a second process gas containing a nitriding gas to a second process gas supply line of the process plant; configured to contain a hydrocarbon gas a third process gas is supplied to the third process gas supply line of the process plant; and a control portion configured to control operation of the device, wherein the control portion is preset for forming SiCN on the target substrate in the process field A method of forming a SiCN film having a predetermined thickness by performing a plurality of cycles to laminate a film formed by the cycles, each of the cycles comprising: a first step of supplying the first process gas to the process field; performing a second step of supplying the second process gas to the process field; performing a third step of supplying the third process gas to the process field; and stopping supplying the first process gas to Fourth of the process a step wherein each of the cycles is arranged such that not any of the first, second and third process gases are converted to plasma outside of the process plant during their supply, but at first The process field is heated to a first temperature during the second, third, and fourth steps, and the decane gas, the nitriding gas, and the hydrocarbon gas are reacted with each other at the first temperature.

According to a third aspect of the present invention, there is provided a computer readable medium containing program instructions for execution on a processor for having a first process gas configured to selectively supply a decane-containing gas, a film forming apparatus comprising a process gas of a second process gas of a nitriding gas and a third process gas containing a hydrocarbon gas, wherein the program command causes the film forming apparatus to perform a target for use in the process field when executed by the processor A method of forming a SiCN film on a substrate by laminating a plurality of cycles to form a film respectively formed by the cycles, thereby forming a SiCN film having a predetermined thickness, each of the cycles comprising: performing a supply a first step of processing a process gas to the process field; performing a second step of supplying the second process gas to the process field; performing a third step of supplying the third process gas to the process field; and stopping supplying the first process gas to the process site a fourth step, wherein each of the cycles is arranged such that none of the first, second, and third process gases are outside the process site during their supply Turning into a plasma, the process field is heated to a first temperature during the first, second, third and fourth steps, and the decane gas, the nitriding gas and the hydrocarbon gas react with each other at the first temperature .

The additional objects and advantages of the invention will be set forth in the description of the appended claims. The objects and advantages of the invention may be realized and obtained by means of the <RTIgt;

2‧‧‧film forming device

4‧‧‧Process Container

5‧‧‧Processing field

6‧‧‧Quartz top plate

8‧‧‧Management

10‧‧‧ Sealing members

12‧‧‧ Boat

12A‧‧‧ poles

14‧‧‧Insulation cylinder

16‧‧‧

18‧‧‧ Cover

20‧‧‧Rotary axis

22‧‧‧Seal

24‧‧‧ Sealing members

25‧‧‧ Lifting mechanism

26‧‧‧ Arm

28‧‧‧ Third process gas supply line

28S‧‧‧ gas source

30‧‧‧First process gas supply line

30S‧‧‧ gas source

32‧‧‧Second process gas supply line

32S‧‧‧ gas source

36‧‧‧Clean gas supply pipeline

36S‧‧‧ gas source

38‧‧‧Gas distribution nozzle

38A‧‧‧ gas injection hole

40‧‧‧ gas distribution nozzle

40A‧‧‧ gas injection hole

42‧‧‧ gas distribution nozzle

42A‧‧‧ gas injection hole

46‧‧‧Short gas nozzle

48‧‧‧ gas supply pipeline

48A‧‧‧ switch valve

48B‧‧‧Flow rate controller

48C‧‧‧ storage tank

48D‧‧‧Second on-off valve

50‧‧‧ gas supply pipeline

50A‧‧‧ switch valve

50B‧‧‧ flow rate controller

50C‧‧‧ storage tank

50D‧‧‧Second on-off valve

52‧‧‧ gas supply pipeline

52A‧‧‧ switch valve

52B‧‧‧Flow rate controller

56‧‧‧ gas supply pipeline

56A‧‧‧ switch valve

56B‧‧‧Flow rate controller

60‧‧‧Nozzle receiving groove

62‧‧‧Drainage

64‧‧‧ openings

66‧‧‧Quartz covering

68‧‧‧Drainage cover member

70‧‧‧ gas export

71‧‧‧Shell

72‧‧‧heater

73‧‧‧Vacuum Emission System

74‧‧‧Control Department

76‧‧‧ storage area

77‧‧‧Drainage channel

78‧‧‧Valve unit

79‧‧‧Vacuum pump

80‧‧‧Steps for supplying the first process gas

82‧‧‧Steps to stop supplying the first process gas

84‧‧‧Steps for supplying the second process gas

86‧‧‧Steps to stop supplying the second process gas

88‧‧‧Steps for supplying a third process gas

90‧‧‧Steps to stop supplying third process gas

94‧‧‧First Process Gas Storage Procedure

96‧‧‧ Third Process Gas Storage Procedure

P1‧‧‧ purification steps

P2‧‧‧ purification steps

P3‧‧‧ purification steps

First time of T1‧‧

T2‧‧‧ second period

T3‧‧‧ third period

T4‧‧‧ fourth period

T5‧‧‧ fifth period

T6‧‧‧ sixth period

W‧‧‧ wafer

1 is a cross-sectional view showing a vertical film forming apparatus according to an embodiment of the present invention; FIG. 2 is a cross-sectional plan view showing a part of the apparatus shown in FIG. 1; and FIGS. 3A, 3B, and 3C are views showing a first aspect of the present invention. Film forming method of one embodiment Timing chart of gas supply and its modification; FIG. 4 is a graph showing the relationship between the carbon content of the SiCN film obtained by experiment and the etching rate; FIGS. 5A, 5B and 5C are films showing the second embodiment according to the present invention. Timing chart of gas supply forming method and modification thereof; FIGS. 6A, 6B, 6C and 6D are timing charts showing a gas supply method according to a third embodiment of the present invention and modifications thereof; FIGS. 7A, 7B, and 7C And 7D are timing charts showing the gas supply of the film formation method according to the fourth embodiment of the present invention and modifications thereof; and FIGS. 8A, 8B, 8C and 8D are gases showing the film formation method according to the fifth embodiment of the present invention. Timing diagram of supply and modification thereof; FIGS. 9A, 9B, 9C and 9D are timing charts showing a gas supply method according to a sixth embodiment of the present invention and modifications thereof; FIGS. 10A, 10B and 10C are diagrams showing The timing chart of the gas supply of the film formation method of the seventh embodiment of the invention and its modification; FIGS. 11A, 11B and 11C are timing charts showing the gas supply of the film formation method according to the eighth embodiment of the present invention and modifications thereof; Figures 12A, 12B and 12C show A timing chart showing a gas supply according to a film formation method of a ninth embodiment of the present invention and a modification thereof; and FIGS. 13A, 13B and 13C are timing charts showing a gas supply of a film formation method according to a tenth embodiment of the present invention; FIG. 14 is a structural view showing a portion of a gas supply line for use in a film forming apparatus according to a modification; FIGS. 15A, 15B, and 15C are diagrams showing a film forming method according to an eleventh embodiment of the present invention. Timing chart of gas supply and modification thereof; FIGS. 16A, 16B and 16C are diagrams showing film formation according to the twelfth embodiment of the present invention. FIG. 17A, 17B, 17C, and 17D are timing charts showing a gas supply method according to a thirteenth embodiment of the present invention, and modifications thereof; FIGS. 18A, 18B, and 18C; And 18D are timing charts showing the gas supply of the film forming method according to the fourteenth embodiment of the present invention and modifications thereof; and FIGS. 19A, 19B, 19C and 19D are film forming methods according to the fifteenth embodiment of the present invention. FIG. 20A, 20B, 20C, and 20D are timing charts and modifications of the gas supply of the film formation method according to the sixteenth embodiment of the present invention; FIGS. 21A, 21B, and 21C are A timing chart and a modification of the gas supply of the film formation method according to the seventeenth embodiment of the present invention; and FIGS. 22A, 22B and 22C are timings showing the gas supply of the film formation method according to the eighteenth embodiment of the present invention. FIG. 23A, FIG. 23B and FIG. 23C are timing charts showing a gas supply method according to a nineteenth embodiment of the present invention, and modifications thereof; and FIGS. 24A, 24B and 24C are diagrams showing the present invention. Twenty embodiments A gas supply and a timing chart of the modification of the method of forming.

The presently preferred embodiments of the present invention, which are incorporated in and constitute a The principle of the invention.

In developing the process of the present invention, the inventors have studied the problems of the conventional techniques of semiconductor processing related to the method of forming a tantalum nitride film. As a result, the inventors have come to the results of the research given below.

A research group comprising the inventors has developed a membrane formation method combining a process gas supply of the ALD or MLD type with a process gas activation by plasma in view of the problems explained in the "Prior Art" (US 2006/205231) A1, etc.). According to this method, NH ₃ or the like is activated by using plasma to promote nitriding processing to achieve high yield while introducing a certain amount of carbon into the SiCN film to improve its chemical resistance to some extent. In this case, the film may have properties exhibiting a lower etching rate and being suitable for the interlayer insulating film, compared to a conventional technique in which the SiCN film is formed at a low temperature.

However, according to a later study, it has been found that the film formation method using plasma as described above is preferable in terms of yield, but has difficulty in increasing the carbon content (addition amount) of the insulating film, resulting in improvement of chemical resistance. Strict restrictions.

In recent years, due to the demand for reducing the line width and film thickness of a semiconductor device, the requirements regarding the handleability of the insulating film have become stricter. Therefore, the film formation method as described above may not satisfy the requirements.

Embodiments of the invention based on the findings given above will now be described with reference to the accompanying drawings. In the following description, constituent elements having substantially the same functions and arrangements are denoted by the same reference numerals, and the description is repeated only when necessary.

1 is a cross-sectional view showing a vertical film forming apparatus according to an embodiment of the present invention. Figure 2 is a cross-sectional plan view showing a portion of the apparatus shown in Figure 1. The film forming apparatus 2 has a process field configured to selectively supply a first process gas containing a dichlorosilane (DCS) gas as a decane gas, and a second containing ammonia (NH ₃ ) gas as a nitriding gas Process gas, and a third process gas containing C ₂ H ₄ gas (ethylene gas) as a hydrocarbon gas. The film forming apparatus 2 is configured to form a SiCN film on a target substrate in a process field, which is a tantalum nitride film containing carbon.

The apparatus 2 includes a process vessel 4 shaped as a cylindrical column having a top plate and an open bottom, wherein the process field 5 is defined to accommodate and process a plurality of semiconductor wafers (target substrates) stacked at a distance from each other in a vertical direction. The entire process container 4 is made of, for example, quartz. The top of the process vessel 4 has a quartz top plate 6 that hermetically seals the top. The bottom of the process vessel 4 is connected to the cylindrical manifold 8 via a sealing member 10 such as an O-ring. Process container It can be formed entirely from a cylindrical quartz column that does not have a separately formed manifold 8.

The manifold 8 is made of, for example, stainless steel and supports the bottom of the process vessel 4. The wafer boat 12 made of quartz is moved up and down through the bottom opening of the manifold 8, so that the boat 12 is loaded into the process vessel 4/the self-service vessel 4 for unloading. A certain number of target substrates or semiconductor wafers W are stacked on the wafer boat 12. For example, in this embodiment, the boat 12 has struts 12A that can support, for example, about 50 to 100 wafers having a diameter of 300 mm that are substantially at a regular distance apart in the vertical direction.

The boat 12 is placed on the table 16 via an insulated cylinder 14 made of quartz. The table 16 is supported by a rotating shaft 20 that penetrates a cover 18 made of, for example, stainless steel and is used to open/close the bottom port of the manifold 8.

A portion of the cover 18 through which the rotary shaft 20 penetrates has, for example, a magnetic fluid seal 22 to rotatably support the rotary shaft 20 in a hermetic seal. A sealing member 24, such as an O-ring, is inserted between the periphery of the cover 18 and the bottom of the manifold 8 such that the interior of the process vessel 4 can remain sealed.

The rotating shaft 20 is attached to the distal end of the arm 26 supported by the lifting mechanism 25 such as a boat lift. The lifting mechanism 25 moves the boat 12 and the lid 18 up and down in unison. The table 16 can be secured to the cover 18 such that the wafer W is processed without rotating the boat 12.

The gas supply zone is connected to the side of the manifold 8 to supply a predetermined process gas to the process plant 5 within the process vessel 4. Specifically, the gas supply zone includes a third process gas supply line 28, a first process gas supply line 30, a second process gas supply line 32, and a purge gas supply line 36. The first process gas supply line 30 is arranged to supply a first process gas containing a decane gas such as a DCS (chlorinated chloroform) gas. The second process gas supply line 32 is arranged to supply a second process gas containing a nitriding gas such as ammonia (NH ₃ ) gas. The third process gas supply line 28 is arranged to supply a third process gas containing a hydrocarbon gas such as C ₂ H ₄ gas (ethylene gas). The purge gas supply line 36 is arranged to supply an inert gas such as N ₂ gas as a purge gas. Each of the first to third process gases is mixed with a suitable amount of carrier gas (such as N ₂ gas) as needed. However, in the following, the carrier gas will not be mentioned for the sake of simplicity of explanation.

More specifically, the third, first, and second process gas supply lines 28, 30, and 32 include gas distribution nozzles 38, 40, and 42, respectively, each of which is formed of a quartz tube that penetrates from the outside. The side walls of the manifold 8 are then turned and extended upward (see Figure 1). The gas distribution nozzles 38, 40, and 42 respectively have a plurality of gas injection holes 38A, 40A, and 42A, each of which is formed on all of the wafers W on the wafer boat 12 at a predetermined distance in the longitudinal direction (vertical direction). Each of the gas injection holes 38A, 40A, and 42A delivers the respective process gases in a horizontal direction almost uniformly to form a gas flow parallel to the wafer W on the wafer boat 12. The purge gas supply line 36 includes a short gas nozzle 46 that penetrates the sidewalls of the manifold 8 from the outside.

The nozzles 38, 40, 42 and 46 are respectively connected to gas sources 28S, 30S of C ₂ H ₄ gas, DCS gas, NH ₃ gas and N ₂ gas via gas supply lines (gas passages) 48, 50, 52 and 56, respectively. , 32S and 36S. Gas supply lines 48, 50, 52, and 56 have switching valves 48A, 50A, 52A, and 56A and flow rate controllers 48B, 50B, 52B, and 56B, such as mass flow controllers, respectively. With this arrangement, C ₂ H ₄ gas, DCS gas, NH ₃ gas, and N ₂ gas can be supplied at a controlled flow rate. Gas supply lines (gas passages) 48, 50, and 52 are further connected to a gas source of N ₂ gas (not shown).

A nozzle receiving groove 60 is formed at a side wall of the process vessel 4 to extend in a vertical direction. The nozzle receiving recess 60 has a vertically longer and thinner opening 64 formed by cutting a predetermined width of the side wall of the process vessel 4 in the vertical direction. The opening 64 is covered with a quartz cover 66 that is hermetically attached to the outer surface of the process vessel 4. The cover 66 has a vertically longer and thinner shape having a concave cross section such that its self-contained container 4 projects outward.

Therefore, the nozzle receiving groove 60 is formed such that the side wall of the self-made process container 4 protrudes outward and is connected to the inside of the process container 4 on the other side. In other words, the nozzle receiving groove 60 The interior space communicates with the process field 5 within the process vessel 4 via the opening 64. The opening 64 has a vertical length sufficient to cover all of the wafers W on the wafer boat 12 in the vertical direction.

The gas distribution nozzles 38, 40, and 42 are outwardly curved in the radial direction of the process vessel 4 at a position lower than the lowest wafer W on the wafer boat 12. Next, the gas distribution nozzles 38, 40, and 42 extend vertically side by side at the deepest position in the nozzle receiving groove 60 (the farthest position from the center of the process vessel 4). The gas injection holes 38A, 40A, and 42A of the gas distribution nozzles 38, 40, and 42 are formed at positions between the wafers W on the wafer boat 12 to substantially uniformly deliver the respective gases in the horizontal direction, respectively, to form a wafer. W parallel gas flow. Gas is injected inwardly from gas injection holes 38A, 40A, and 42A of gas distribution nozzles 38, 40, and 42 and supplied to wafer W on wafer boat 12 via opening 64. When an inert gas containing N ₂ gas is ejected from the gas distribution nozzles 38, 40, and 42, the gas is supplied in the same manner to form a gas flow parallel to the wafer W.

On the other hand, on the side of the process vessel 4 opposite to the nozzle receiving recess 60, a longer and thinner discharge opening 62 for evacuating the internal atmosphere is formed by cutting the side walls of the process vessel 4. As shown in FIG. 1, the vent 62 has a vertical length sufficient to cover all of the wafers W on the wafer boat 12 in the vertical direction. The discharge port 62 is covered with a discharge port covering member 68 made of quartz having a U-shaped cross section and attached by welding. The vent cover member 68 extends upwardly along the sidewall of the process vessel 4 and has a gas outlet 70 at the top of the process vessel 4. The gas outlet 70 is connected to a vacuum discharge system 73 including a vacuum pump or the like. The vacuum discharge system 73 has a discharge passage 77 connected to the gas outlet 70, and a valve unit (opening degree adjustment valve) 78, a vacuum pump 79, and the like are placed on the discharge passage 77 in this order from the upstream side.

The process vessel 4 is surrounded by a casing 71. The casing 71 has a heater 72 on the inner surface for heating the atmosphere in the process vessel 4 and the wafer W. For example, the heater 72 is formed of carbon wire that does not cause contamination and has good characteristics for increasing and decreasing temperature. A thermocouple (not shown) is placed in the process vessel 4 near the discharge port 62 to control the heater 72.

The operation of the film forming apparatus 2 constructed as described above is generally performed by a control unit such as a computer 74 to control. The computer program operating the device 2 is stored in a storage area 76 containing storage media such as a flexible disk, a CD (Compact Disc), a hard disk and/or a flash memory. The start/stop of the supply of the respective gases, the gas flow rate, the processing temperature, and the processing pressure are controlled in accordance with an instruction from the control unit 74.

Next, an explanation will be given of a film formation method (so-called ALD or MLD film formation) performed in the apparatus shown in Fig. 1. In this film formation method, an insulating film of SiCN (germanium carbonitride) is formed on a semiconductor wafer by ALD or MLD. To achieve this, a first process gas containing a dichlorosilane (DCS) gas as a decane gas, a second process gas containing ammonia (NH ₃ ) gas as a nitriding gas, and a C ₂ H ₄ gas (ethylene gas) A third process gas as a hydrocarbon gas is selectively supplied to the process field 5 containing the wafer W. Specifically, the film formation process is performed with the following operations.

First, a wafer boat 12 having a 300 mm diameter wafer supporting a certain number (for example, 50 to 100) at room temperature is loaded into a process vessel 4 heated at a predetermined temperature, and the process is hermetically sealed. Container 4. Next, the interior of the process vessel 4 is vented to a vacuum and maintained at a predetermined processing pressure, and the wafer temperature is increased to a processing temperature for film formation. At this point, the device is in a waiting state until the temperature becomes stable. Next, while rotating the boat 12, the first to third process gases are supplied from the respective gas distribution nozzles 40, 42 and 38 intermittently or continuously at a controlled flow rate.

The first process gas containing the DCS gas, the second process gas containing the NH ₃ gas, and the third process gas containing the C ₂ H ₄ gas are supplied from the gas injection holes 40A, 42A, and 38A of the gas distribution nozzles 40, 42 and 38, respectively. To form a gas stream parallel to the wafer W on the wafer boat 12. When DCS gas, NH ₃ gas, and C ₂ H ₄ gas are supplied, molecules of DCS gas, NH ₃ gas, and C ₂ H ₄ gas, and molecules and atoms of decomposition products generated by the decomposition thereof are adsorbed on the wafer W. These gas molecules and/or decomposition components react with each other on the wafer W by using the heat of the heater 72, thereby forming a unit film of SiCN on the wafer W. This cycle for forming a unit film is repeated several times, and the SiCN film formed by the respective batches is laminated, thereby achieving the SiCN film having the target thickness.

For example, when each cycle is arranged to supply the first and third process gases prior to supplying the second process gas, the DCS and C ₂ H ₄ first react with each other on the wafer surface and form an adsorption on the wafer W. A thin SiC film on it. Next, when the second process gas is supplied, NH ₃ reacts with the SiC film adsorbed on the wafer W to form a unit film of SiCN. Alternatively, for example, when each cycle is arranged to supply the first and second process gases prior to supplying the third process gas, the DCS and NH ₃ first react with each other on the wafer surface and form an adsorption on the wafer W. Thin SiN film. Next, when the third process gas is supplied, C ₂ H ₄ reacts with the SiN film adsorbed on the wafer W to form a unit film of SiCN.

Next, an explanation will be given of the gas supply timing according to an embodiment of the present invention. For convenience understood that in all the drawings showing the timing chart, as (for example) shown in FIG. 3A, the first process gas is represented by the DCS, the second process gas is represented by NH _3, and the third process gas from the C ₂ H ₄ indicates. Additionally, in these figures, reference numerals 80 and 82 respectively indicate the steps of performing and stopping the supply of the first process gas. Reference numerals 84 and 86 denote the steps of performing and stopping the supply of the second process gas, respectively. Reference numerals 88 and 90 denote the steps of performing and stopping the supply of the third process gas, respectively.

<First Embodiment>

Fig. 3A is a timing chart showing the gas supply of the film formation method according to the first embodiment of the present invention. As shown in FIG. 3A, the film forming method according to this embodiment is arranged to alternately repeat the first to fourth time periods T1 to T4. The period including the first to fourth periods T1 to T4 is repeated several times, and the SiCN film formed by the respective batches is laminated, thereby achieving the SiCN film having the target thickness.

Specifically, the first time period T1 is arranged to supply the supply of the first and third process gases to the process field 5 when the supply of the second process gas to the process field 5 is stopped. The second time period T2 is arranged to stop supplying the first, second and third process gases to the process field 5. The third time period T3 is arranged to stop supplying the first and third process gases to the process field 5, The supply of the second process gas to the process plant 5 is performed. The fourth time period T4 is arranged to stop supplying the first, second and third process gases to the process field 5.

In this embodiment, the first process gas supply step 80, the second process gas supply step 84, and the third process gas supply step 88 are set to have the same or close to each other. The first and third process gas supply steps 80 and 88 are performed synchronously (to completely overlap each other), and thus the first and third process gas stop steps 82 and 90 are performed synchronously (to completely overlap each other). The second process gas supply step 84 is performed substantially in the middle of the first and third process gas stop steps 82 and 90. The first and third process gas supply steps 80 and 88 are performed substantially in the middle of the second process gas stop step 86.

The second and fourth time periods T2 and T4 are used as the purification steps P1 and P2, respectively, to remove residual gases in the process vessel 4. The term "purification" means to discharge the inside of the process vessel 4 to a vacuum while supplying an inert gas such as N ₂ gas into the process vessel 4, or to make the process vessel 4 while stopping the supply of all the gases. The interior is vented to a vacuum to remove residual gases within the process vessel 4. In this regard, the second and fourth time periods T2 and T4 can be arranged such that the first half of the time period utilizes only the discharge to the vacuum and the second half of the time period utilizes both the discharge to the vacuum and the supply of the inert gas. In addition, the first and third time periods T1 and T3 may be arranged to stop discharging the process vessel 4 to a vacuum while supplying the first to third process gases. However, when the supply of the respective first to third process gases is performed as the process container 4 is discharged to the vacuum, the inside of the process vessel 4 may be continuously discharged to the vacuum throughout all of the first to fourth time periods T1 to T4.

For example, in FIG. 3, the first time period T1 is set to about 4 seconds, the second time period T2 is set to about 5 seconds, the third time period T3 is set to about 6 seconds, and the fourth time period T4 is set to about 5 seconds. Generally, the film thickness obtained by one cycle of the first to fourth time periods T1 to T4 is about 0.048 to 0.13 nm. Therefore, for example, when the target film thickness is 70 nm, the cycle is repeated about 600 times. However, such equivalents of the number and thickness are merely examples and thus are not limiting.

As mentioned above, the first and third process gases will be converted outside of the process field 5 a period T1 in which the first and third process gases are simultaneously supplied in the case of plasma (ie, without converting it into a radical), and a second process gas is converted into a plasma outside the process field 5 (ie, The period T3 in which the second process gas is exclusively supplied without being converted into a radical is alternately performed, and the periods T2 and T4 at which the supply of the process gas is stopped (purification steps P1 and P2) are respectively inserted therebetween. In this case, although the film formation temperature is set to be lower than, for example, a conventional film formation temperature of about 760 ° C, a larger amount of carbon may be introduced into the formed SiCN film so as to be lowered and performed on the film surface. The film etching rate associated with dilute hydrofluoric acid used in cleaning or etching processes. Therefore, the film is not excessively etched by cleaning, and thus the cleaning process is performed with a highly controllable film thickness. In addition, the film may sufficiently function as an etching stopper film or an interlayer insulating film.

Further, as described above, the periods T2 and T4 of the supply of the process gas between the periods T1 and T2 during which the process gas is supplied are used not only as the purification steps P1 and P2 but also as the period of the quality of the reconstituted film. The surface of the SiCN film formed directly before each of these periods is recombined during this period, thereby improving the film quality. Therefore, the etching rate of the SiCN film is further reduced. The effect of recombination processing at the atomic level is considered as follows. Specifically, when a SiCN film containing carbon atoms is formed, some of the Cl atoms derived from the DCS gas are not desorbed but are bonded to the uppermost surface of the film in an activated state. During the period T2 and T4 during which the supply of the DCS gas is stopped, the C atom or the N atom derived from the C ₂ H ₄ or NH ₃ gas replaces the Cl atom on the uppermost surface of the film, and the Cl component in the film is reduced, thereby reducing the Cl component in the film. Reduce the etch rate. In particular, when a C ₂ H ₄ gas is used, the number of C atoms introduced into the film is increased, thereby further reducing the etching rate.

The processing conditions for the film formation process are as follows. The flow rate of the DCS gas is set to be in the range of 500 to 5,000 sccm, for example, at 1,000 sccm (1 slm). The flow rate of the NH ₃ gas is set to be in the range of 100 to 10,000 sccm, for example, at 1,000 sccm. The flow rate of the C ₂ H ₄ gas is set to be in the range of 100 to 5,000 sccm, for example, at 500 sccm. The flow rate of the C ₂ H ₄ gas is set to not exceed three times the flow rate of the DCS gas. This is attributed to the fact that if the flow rate of the C ₂ H ₄ gas used as the hydrocarbon gas is too high, the film quality is undesirably drastically lowered.

The processing temperature is lower than that of general CVD processing, and is set to be in the range of 300 to 700 ° C, and preferably in the range of 550 to 650 ° C, such as 630 ° C. If the processing temperature is lower than 300 ° C, substantially no film is deposited because almost no reaction is caused. If the processing temperature is higher than 700 ° C, a low quality CVD film is deposited, and an existing film such as a metal film is subjected to thermal damage.

The processing pressure is set to be in the range of 13 Pa (0.1 Torr) to 1,330 Pa (10 Torr), and preferably in the range of 40 Pa (0.3 Torr) to 266 Pa (2 Torr). For example, the processing pressure is set to 1 Torr during the first period (adsorption step) T1 and set to 10 Torr during the third period (nitridation step) T3. If the processing pressure is lower than 13 Pa, the film formation rate becomes lower than the practical level. On the other hand, if the processing pressure exceeds 1,330 Pa, the reaction mode is converted from the adsorption reaction to the gas phase reaction, which then spreads over the wafer W. This is not the case because the uniformity and planar uniformity between the substrates of the film deteriorates, and the number of particles attributed to the gas phase reaction suddenly increases.

The timing diagram shown in Figure 3A includes two purification steps P1 and P2, but it may be omitted partially or completely. Fig. 3B shows a timing chart of Modification 1 of the first embodiment, in which the first purification step P1 in Fig. 3A is omitted. In this case, one cycle is formed by the periods T1, T3, and T4. Specifically, the first and third process gas supply steps 80 and 88 are directly followed by the second process gas supply step 84 without the purge step interposed therebetween, and then the purification step P2 is performed.

Fig. 3C shows a timing chart of Modification 2 of the first embodiment, in which the two purification steps P1 and P2 in Fig. 3A are omitted. In this case, one cycle is formed by the periods T1 and T3. Specifically, one cycle is completed such that the first and third process gas supply steps 80 and 88 are directly followed by the second process gas supply step 84 without the purge step interposed therebetween. In addition, although not shown in the drawings, Modification 3 of the first embodiment is arranged such that only FIG. 3A is omitted. Finally, the purification step P2. According to the film formation method in which the purification step is partially or completely omitted, the treatment rate is increased more, thereby improving the yield.

To control the carbon content of the thus formed SiCN film, the length of the third process gas supply step 88, that is, the C ₂ H ₄ adsorption time; and/or the length of the second process gas supply step 84, that is, nitridation, may be adjusted. time.

<Checking the SiCN film>

As a current example, the film formation method according to the first embodiment is used while adjusting the lengths of the second and/or third process gas supply steps 84 and/or 88 to form a SiCN film having a different value of carbon concentration (content). As a comparative example CE1, a SiN film was formed without supplying a C ₂ H ₄ gas. As a comparative example CE2, a SiN film (film formation method according to the disclosure of US 2007/167028 A1) was formed by using plasma. Each of the thus formed films was etched with dilute hydrofluoric acid DHF (200:1).

4 is a graph showing the relationship between the carbon content of the SiCN film obtained by experiment and the etching rate. As shown in FIG. 4, Comparative Example CE1 (SiN film not containing carbon) provided an extremely high etching rate of 0.6 nm/min. Comparative Example CE2 (by using a plasma formed SiCN film) had a carbon concentration of up to about 3.5% and provided a significant etch rate of 0.35 nm/min.

On the other hand, in the case of the film formation method according to the first embodiment, the carbon concentration in the SiCN film is greatly increased and can be controlled in the range of 15.2% to 28.5% by the condition adjustment. As a representative of the SiCN film formed by the film formation method according to the first embodiment, FIG. 4 shows a first current example PE1 having a carbon concentration of 15.2%, a second current example PE2 having a carbon concentration of 26.2%, and having Data relating to the third current example PE3 of 28.5% carbon concentration. The first, second, and third current instances PE1, PE2, and PE3 provide an etch rate in the range of 0.22 to 0.1 nm/min, which is sufficiently lower than the etch rates of the control examples CE1 and CE2.

<Second embodiment>

Fig. 5A is a timing chart showing a gas supply of a film formation method according to a second embodiment of the present invention. As shown in FIG. 5A, the film formation method according to this embodiment is arranged such that the supply of the first process gas (DCS supply) is performed at the same timing as the first embodiment shown in FIG. 3A, and the second The supply of the process gas (NH ₃ supply) and the supply of the third process gas (C ₂ H ₄ supply) are performed at timings interchangeable with each other as compared with the method shown in FIG. 3A.

Specifically, the first time period T1 is arranged to supply the first and second process gases to the process field 5 when the supply of the third process gas to the process field 5 is stopped (the first and second process gas supply steps) 80 and 84). The second time period T2 is arranged to stop supplying the first, second and third process gases to the process field 5 (purification step P1). The third time period T3 is arranged to supply the third process gas to the process field 5 (the third process gas supply step 88) while the supply of the first and second process gases to the process field 5 is stopped. The fourth time period T2 is arranged to stop supplying the first, second and third process gases to the process field 5 (purification step P2).

This embodiment can also provide the same effect as the first embodiment, that is, although the film formation temperature is set lower, a larger amount of carbon may be introduced into the formed SiCN film. Therefore, the etching rate of the SiCN film is lowered, and thus the cleaning process is performed with a highly controllable film thickness. In addition, the SiCN film can sufficiently serve as an insulating film for a specific purpose such as an etching stopper film or an interlayer insulating film.

The timing diagram shown in Figure 5A includes two purification steps P1 and P2, but it may be omitted partially or completely. Fig. 5B shows a timing chart of Modification 1 of the second embodiment, in which the first purification step P1 in Fig. 5A is omitted. In this case, one cycle is formed by the periods T1, T3, and T4. Specifically, the first and second process gas supply steps 80 and 84 are directly followed by the third process gas supply step 88 without the purge step interposed therebetween, and then the purification step P2 is performed.

Fig. 5C shows a timing chart of Modification 2 of the second embodiment, in which the two purification steps P1 and P2 in Fig. 5A are omitted. In this case, one cycle is formed by the periods T1 and T3. Specifically, one cycle is completed to make the first and second process gas supply steps 80 and 84 straight after A third process gas supply step 88 is followed and no purge step is inserted therebetween. Further, although not shown in the drawings, Modification 3 of the second embodiment is arranged such that only the last purification step P2 in Fig. 5A is omitted. According to the film formation method in which the purification step is partially or completely omitted, the treatment rate is increased more, thereby improving the yield.

<Third embodiment>

Fig. 6A is a timing chart showing a gas supply of a film formation method according to a third embodiment of the present invention. As shown in FIG. 6A, the film forming method according to this embodiment is arranged to alternately repeat the first to sixth time periods T1 to T6. The period including the first to sixth periods T1 to T6 is repeated several times, and the SiCN film formed by the respective batches is laminated, thereby achieving the SiCN film having the target thickness.

Specifically, the first time period T1 is arranged to supply the supply of the first process gas to the process field 5 (the first process gas supply step 80) while the supply of the second and third process gases to the process field 5 is stopped. The second time period T2 is arranged to stop supplying the first, second and third process gases to the process field 5 (purification step P1). The third time period T3 is arranged to supply the third process gas to the process field 5 (the third process gas supply step 88) while the supply of the first and second process gases to the process field 5 is stopped. The fourth time period T4 is arranged to stop supplying the first, second and third process gases to the process field 5 (purification step P2). The fifth time period T5 is arranged to supply supply of the second process gas to the process field 5 (the second process gas supply step 84) while the supply of the first and third process gases to the process field 5 is stopped. The sixth time period T6 is arranged to stop supplying the first, second, and third process gases to the process field 5 (purification step P3).

For example, the first to fourth time periods T1 to T4 are set to have the same length as the same period of the first embodiment, and the fifth time period T5 is set to about 6 seconds, and the sixth time period T6 is set to About 5 seconds. This embodiment can also provide the same effect as the first embodiment, that is, although the film formation temperature is set lower, a larger amount of carbon can be introduced into the formed SiCN film.

The timing diagram shown in Figure 6A includes three purification steps P1, P2, and P3, but it may be omitted partially or completely. Fig. 6B shows a timing chart of Modification 1 of the third embodiment, in which the second purification step P2 in Fig. 6A is omitted. In this case, one cycle is formed by the periods T1, T2, T3, T5, and T6. Specifically, the third process gas supply step 88 is followed by a second process gas supply step 84 without a purge step interposed therebetween.

Fig. 6C shows a timing chart of Modification 2 of the third embodiment, in which the first and second purification steps P1 and P2 in Fig. 6A are omitted. In this case, one cycle is formed by the periods T1, T3, T5, and T6.

Fig. 6D shows a timing chart of Modification 3 of the third embodiment, in which the first to third purification steps P1 to P3 in Fig. 6A are omitted. In this case, one cycle is formed by the periods T1, T3, and T5.

<Fourth embodiment>

Fig. 7A is a timing chart showing a gas supply of a film formation method according to a fourth embodiment of the present invention. As shown in FIG. 7A, the film formation method according to this embodiment is arranged to be the same as the film formation method of the third embodiment shown in FIG. 6A except that the supply of the second process gas (NH ₃ supply) is not only in the It is executed in the five time period T5 and is performed in the first time period T1. In other words, the second process gas supply step 84 is performed twice (multiple times) in one cycle. The number of these multiples can be further increased.

This embodiment can also provide the same effect as in the first embodiment, that is, although the film formation temperature is set lower, a larger amount of carbon can be introduced into the formed SiCN film.

The timing diagram shown in Figure 7A includes three purification steps P1, P2, and P3, but it may be omitted partially or completely. Fig. 7B shows a timing chart of Modification 1 of the fourth embodiment, in which the second purification step P2 in Fig. 7A is omitted. In this case, one cycle is formed by the periods T1, T2, T3, T5, and T6. Specifically, the third process gas supply step 88 is followed by a second process gas supply step 84 without a purge step interposed therebetween.

7C shows a timing chart of Modification 2 of the fourth embodiment, in which the first of FIG. 7A is omitted. And second purification steps P1 and P2. In this case, one cycle is formed by the periods T1, T3, T5, and T6.

Fig. 7D shows a timing chart of Modification 3 of the fourth embodiment, in which the first to third purification steps P1 to P3 in Fig. 7A are omitted. In this case, one cycle is formed by the periods T1, T3, and T5.

<Fifth Embodiment>

Fig. 8A is a timing chart showing the gas supply of the film formation method according to the fifth embodiment of the present invention. As shown in FIG. 8A, the film formation method according to this embodiment is arranged to be the same as the film formation method of the third embodiment shown in FIG. 6A except that the supply of the third process gas (C ₂ H ₄ supply) is not only It is executed in the third time period T3 and is performed outside in the first time period T1. In other words, the third process gas supply step 88 is performed twice (multiple times) in one cycle. The number of these multiples can be further increased.

This embodiment can also provide the same effect as the first embodiment, that is, although the film formation temperature is set lower, a larger amount of carbon can be introduced into the formed SiCN film.

The timing diagram shown in Figure 8A includes three purification steps P1, P2, and P3, but it may be omitted partially or completely. Fig. 8B shows a timing chart of Modification 1 of the fifth embodiment, in which the second purification step P2 in Fig. 8A is omitted. In this case, one cycle is formed by the periods T1, T2, T3, T5, and T6. Specifically, the third process gas supply step 88 is followed by a second process gas supply step 84 without a purge step interposed therebetween.

Fig. 8C shows a timing chart of Modification 2 of the fifth embodiment, in which the first and second purification steps P1 and P2 in Fig. 8A are omitted. In this case, one cycle is formed by the periods T1, T3, T5, and T6. The two periods of the third process gas supply step 88 are continuous and thus become a total longer than the first process gas supply step 80.

Fig. 8D shows a timing chart of Modification 3 of the fifth embodiment, in which the first to third purification steps P1 to P3 in Fig. 8A are omitted. In this case, one cycle is formed by the periods T1, T3, and T5.

<Sixth embodiment>

Fig. 9A is a timing chart showing gas supply of a film forming method according to a sixth embodiment of the present invention. As shown in FIG. 9A, the film formation method according to this embodiment is arranged to be the same as the film formation method of the third embodiment shown in FIG. 6A except that the supply of the second process gas (NH ₃ supply) is not only in the The fifth period T5 is performed and executed in the first period T1, and the supply of the third process gas (C ₂ H ₄ supply) is performed not only in the third period T3 but also in the first period T1. In other words, each of the second process gas supply step 84 and the third process gas supply step 88 is performed twice (multiple times) in one cycle. The number of these multiples can be further increased.

This embodiment can also provide the same effect as the first embodiment, that is, although the film formation temperature is set lower, a larger amount of carbon can be introduced into the formed SiCN film.

The timing diagram shown in Figure 9A includes three purification steps P1, P2, and P3, but it may be omitted partially or completely. Fig. 9B shows a timing chart of Modification 1 of the sixth embodiment, in which the second purification step P2 in Fig. 9A is omitted. In this case, one cycle is formed by the periods T1, T2, T3, T5, and T6. Specifically, the third process gas supply step 88 is followed by a second process gas supply step 84 without a purge step interposed therebetween.

Fig. 9C shows a timing chart of Modification 2 of the sixth embodiment, in which the first and second purification steps P1 and P2 in Fig. 9A are omitted. In this case, one cycle is formed by the periods T1, T3, T5, and T6.

Fig. 9D shows a timing chart of Modification 3 of the sixth embodiment, in which the first to third purification steps P1 to P3 in Fig. 9A are omitted. In this case, one cycle is formed by the periods T1, T3, and T5.

<Seventh embodiment>

Fig. 10A is a timing chart showing the gas supply of the film formation method according to the seventh embodiment of the present invention. As shown in FIG. 10A, the film formation method according to this embodiment is arranged to be the same as the film formation method of the first embodiment shown in FIG. 3A except that the supply of the second process gas (NH ₃ supply) is not only in the The third period T3 is performed and performed in the first period T1, and the supply of the third process gas (C ₂ H ₄ supply) is performed not only in the first period T1 but also in the third period T3. In other words, each of the second process gas supply step 84 and the third process gas supply step 88 is performed twice (multiple times) in one cycle. The number of these multiples can be further increased.

This embodiment can also provide the same effect as the first embodiment, that is, although the film formation temperature is set lower, a larger amount of carbon can be introduced into the formed SiCN film.

The timing diagram shown in Figure 10A includes two purification steps P1 and P2, but it may be omitted partially or completely. Fig. 10B shows a timing chart of Modification 1 of the seventh embodiment, in which the first purification step P1 in Fig. 10A is omitted. In this case, one cycle is formed by the periods T1, T3, and T4. Specifically, the first, second, and third process gas supply steps 80, 84, and 88 performed together are directly followed by the second and third process gas supply steps 84 and 88 performed together without the purification step being inserted therebetween, and Purification step P2 is then performed.

Fig. 10C shows a timing chart of Modification 2 of the seventh embodiment, in which the two purification steps P1 and P2 in Fig. 10A are omitted. In this case, one cycle is formed by the periods T1 and T3. Specifically, this embodiment is arranged to alternately execute and stop the supply of the first process gas (DCS) while continuously supplying the supply of the second process gas (NH ₃ ) and the third process gas (C ₂ H ₄ ) ). Further, although not shown in the drawings, Modification 3 of the seventh embodiment is arranged such that only the last purification step P2 in Fig. 10A is omitted.

<Eighth Embodiment>

Fig. 11A is a timing chart showing the gas supply of the film formation method according to the eighth embodiment of the present invention. As shown in FIG. 11A, the film formation method according to this embodiment is arranged to be the same as the film formation method of the second embodiment shown in FIG. 5A except that the supply of the second process gas (NH ₃ supply) is not only in the It is executed in a period T1 and is performed in the third period T3. In other words, the second process gas supply step 84 is performed twice (multiple times) in one cycle. The number of these multiples can be further increased.

This embodiment can also provide the same effect as the first embodiment, that is, although the film formation temperature is set lower, a larger amount of carbon can be introduced into the formed SiCN film.

The timing diagram shown in Figure 11A includes two purification steps P1 and P2, but it may be omitted partially or completely. Fig. 11B shows a timing chart of Modification 1 of the eighth embodiment, in which the first purification step P1 in Fig. 11A is omitted. In this case, one cycle is formed by the periods T1, T3, and T4. Specifically, the first and second process gas supply steps 80 and 84 performed together are directly followed by the second and third process gas supply steps 84 and 88 performed together without the purification step interposed therebetween, and then the purification step P2 is performed. .

Fig. 11C shows a timing chart of Modification 2 of the eighth embodiment, in which the two purification steps P1 and P2 in Fig. 11A are omitted. In this case, one cycle is formed by the periods T1 and T3. Specifically, this embodiment is arranged to alternately execute and stop the first process gas (DCS) and the third process gas (C ₂ H ₄ ) while continuously supplying the supply of the second process gas (NH ₃ ) The supply of each. Further, although not shown in the drawings, Modification 3 of the eighth embodiment is arranged such that only the last purification step P2 in Fig. 11A is omitted.

<Ninth embodiment>

Fig. 12A is a timing chart showing the gas supply of the film formation method according to the ninth embodiment of the present invention. As shown in FIG. 12A, the film formation method according to this embodiment is arranged to be the same as the film formation method of the first embodiment shown in FIG. 3A except that the supply of the third process gas (C ₂ H ₄ supply) is The third time period T3 is not performed in the first time period T1.

This embodiment can also provide the same effect as the first embodiment, that is, although the film formation temperature is set lower, a larger amount of carbon can be introduced into the formed SiCN film.

The timing diagram shown in Figure 12A includes two purification steps P1 and P2, but it may be omitted partially or completely. Fig. 12B shows a timing chart of Modification 1 of the ninth embodiment, in which the first purification step P1 in Fig. 12A is omitted. In this case, one cycle is formed by the periods T1, T3, and T4. Specifically, the first process gas supply step 80 is directly followed by the second and third process gas supply steps 84 and 88 performed together without the purification step being inserted therebetween, and The purification step P2 is performed.

Fig. 12C shows a timing chart of Modification 2 of the ninth embodiment, in which the two purification steps P1 and P2 in Fig. 12A are omitted. In this case, one cycle is formed by the periods T1 and T3. Specifically, one cycle is completed such that the first process gas supply step 80 is followed directly by the second and third process gas supply steps 84 and 88 performed together without the purge step interposed therebetween. Further, although not shown in the drawings, Modification 3 of the ninth embodiment is arranged such that only the last purification step P2 in Fig. 12A is omitted.

<Tenth embodiment>

Fig. 13A is a timing chart showing the gas supply of the film formation method according to the tenth embodiment of the present invention. As shown in FIG. 13A, the film formation method according to this embodiment is arranged to be the same as the film formation method of the first embodiment shown in FIG. 3A except that the supply of the third process gas (C ₂ H ₄ supply) is not only It is executed in the first time period T1 and is performed in the third time period T3. In other words, the third process gas supply step 88 is performed twice (multiple times) in one cycle. The number of these multiples can be further increased.

This embodiment can also provide the same effect as the first embodiment, that is, although the film formation temperature is set lower, a larger amount of carbon can be introduced into the formed SiCN film.

The timing diagram shown in Figure 13A includes two purification steps P1 and P2, but it may be omitted partially or completely. Fig. 13B shows a timing chart of Modification 1 of the tenth embodiment, in which the first purification step P1 in Fig. 13A is omitted. In this case, one cycle is formed by the periods T1, T3, and T4. Specifically, the first and third process gas supply steps 80 and 88 performed together are directly followed by the second and third process gas supply steps 84 and 88 performed together without the purification step interposed therebetween, and then the purification step P2 is performed. .

Fig. 13C shows a timing chart of Modification 2 of the tenth embodiment, in which the two purification steps P1 and P2 in Fig. 13A are omitted. In this case, one cycle is formed by the periods T1 and T3. Specifically, this embodiment is arranged to alternately execute and stop the first process gas (DCS) and the second process gas (NH ₃ ) while continuously supplying the third process gas (C ₂ H ₄ ). The supply of each. Further, although not shown in the drawings, Modification 3 of the tenth embodiment is arranged such that only the last purification step P2 in Fig. 13A is omitted.

<Modification of film forming device>

Figure 14 is a structural view showing a portion of a gas supply line used in a film forming apparatus according to a modification. As shown in FIG. 14, the gas passage 48 of the third process gas supply line 28 has a self-flow rate controller 48B and an on-off valve 48A downstream of the storage tank 48C having a certain volume and a second switching valve 48D in the following order. The gas passage 50 of the first process gas supply line 30 has a self-flow rate controller 50B and an on-off valve 50A downstream of the storage tank 50C and the second switching valve 50D having a certain volume in the following order. Each of the storage tanks 48C and 50C has a volume of, for example, about 200 to 5,000 milliliters.

According to this modification, the film forming method may be arranged to store the process gas to be subsequently supplied to the process field 5 in the storage tank 48C or 50C when the supply of the process gas to the process field 5 is stopped, and then in the next supply The gas thus stored in the storage tank 48C or 50C is supplied to the process plant 5 immediately in the step. In this case, a larger amount of process gas can be supplied to the process field 5 in a shorter time, thereby reducing the adsorption time. The switching between the start and stop of supplying the process gas to the process field 5 is performed by the second on-off valve 48D or 50D being opened/closed, and switching between the start and stop of the process gas stored in the storage tank 48C or 50C. It is performed by the opening/closing of the upstream switching valve 48A or 50A. The opening/closing of the second switching valve 48D or 50D is controlled by the control portion 74 (see Fig. 1). The upstream switching valve 48A or 50A may be set in a normally open state, or may be set to an open state only when the gas is stored in the storage tank 48C or 50C.

In this modification, both the gas path 48 of the third process gas supply line 28 and the gas path 50 of the first process gas supply line 30 have storage tanks 48C and 50C and switching valves 48D and 50D, respectively. However, only one of the gas passages has a storage tank. Whether or not the storage tanks 48C and 50C are placed can be determined in accordance with the manner in which the process gas is supplied. When one of the storage tanks 48C and 50C is omitted, the film formation side according to each of the following embodiments is changed. The method is such that the storage process of the corresponding process gas is not performed.

<Eleventh Embodiment>

Fig. 15A is a timing chart showing the gas supply of the film formation method according to the eleventh embodiment of the present invention. As shown in FIG. 15A, the film forming method according to this embodiment is arranged to alternately repeat the first to fourth periods T1 to T4 as in the first embodiment shown in FIG. 3A. The period including the first to fourth periods T1 to T4 is repeated several times, and the SiCN film formed by the respective batches is laminated, thereby achieving the SiCN film having the target thickness.

Specifically, the first time period T1 is arranged to perform supplying the first and third process gases (DCS and C ₂ H ₄ ) to the process when the supply of the second process gas (NH ₃ ) to the process field 5 is stopped. Field 5 (first and third process gas supply steps 80 and 88). The second time period T2 is arranged to stop supplying the first, second and third process gases to the process field 5 (purification step P1). The third time period T3 is arranged to supply supply of the second process gas to the process field 5 (the second process gas supply step 84) while the supply of the first and third process gases to the process field 5 is stopped. The fourth time period T4 is arranged to stop supplying the first, second and third process gases to the process field 5 (purification step P2).

In addition, in the first process gas stop step 82 of stopping the supply of the first process gas to the process field 5, a first process gas storage step 94 of storing the first process gas in the storage tank 50C is performed. Similarly, in the third process gas stop step 90 of stopping the supply of the third process gas to the process field 5, a third process gas storage step 96 of storing the third process gas in the storage tank 48C is performed.

In the timing diagram shown in FIG. 15A, the first and third process gas storage steps 94 and 96 are performed during the third time period T3, but may be any of the first and third process gas stop steps 82 and 90, respectively. Steps 94 and 96 are performed in the sequence. In particular, each of the first and third process gas storage steps 94 and 96 can be set at any location and can have any length within the second to fourth time periods T2 to T4. For the first cycle, the respective process gases are preferably stored in the storage tanks 50C and 48C in advance. These conditions are the twelfth to the following Common to the twenty embodiments.

As described above, the film forming method is arranged to store the first and third process gases each having an amount to be subsequently supplied to the process field 5 when the supply of the first and third process gases to the process field 5 is stopped. The gas thus stored in the storage tanks 50C and 48C is supplied to the process plant 5 in the storage tanks 50C and 48C, and then immediately in the next supply step. In this case, a larger amount of process gas can be supplied to the process field 5 in a shorter time, thereby reducing the adsorption time (the length of the period T1) and improving the yield. In addition, when the first and third process gases are supplied to the process field 5, the opening of the pressure regulating valve (the valve unit 78 in FIG. 1) on the discharge passage may be set to be smaller to increase the process container 4 The amount of gas.

Fig. 15B shows a timing chart of Modification 1 of the eleventh embodiment, in which the first purification step P1 in Fig. 15A is omitted. In this case, one cycle is formed by the periods T1, T3, and T4. The first and third process gas storage steps 94 and 96 are performed during the fourth time period T4.

Fig. 15C shows a timing chart of Modification 2 of the eleventh embodiment, in which the two purification steps P1 and P2 in Fig. 15A are omitted. In this case, one cycle is formed by the periods T1 and T3. The first and third process gas storage steps 94 and 96 are performed during the fourth time period T3.

<Twelfth Embodiment>

Fig. 16A is a timing chart showing the gas supply of the film formation method according to the twelfth embodiment of the present invention. As shown in FIG. 16A, the film formation method according to this embodiment is arranged such that the supply of the first process gas (DCS supply) is performed at the same timing as the eleventh embodiment shown in FIG. 15A, and The supply of the two process gases (NH ₃ supply) and the supply of the third process gas (C ₂ H ₄ supply) are performed at timings interchangeable with each other as compared with the method shown in FIG. 15A. Additionally, when the third process gas storage step 96 is performed in the second time period T2, the first process gas storage step 94 is not performed.

Fig. 16B shows a timing chart of Modification 1 of the twelfth embodiment, in which the first purification step P1 in Fig. 16A is omitted. In this case, one cycle is formed by the periods T1, T3, and T4. A third process gas storage step 96 is performed during the first time period T1.

Fig. 16C shows a timing chart of Modification 2 of the twelfth embodiment, in which the two purification steps P1 and P2 in Fig. 16A are omitted. In this case, one cycle is formed by the periods T1 and T3. A third process gas storage step 96 is performed during the first time period T1.

This embodiment can also provide the same effects as the eleventh embodiment. Additionally, this embodiment can also be arranged to utilize the first process gas storage step 94 as described in the eleventh embodiment.

<Thirteenth Embodiment>

Fig. 17A is a timing chart showing the gas supply of the film formation method according to the thirteenth embodiment of the present invention. As shown in Fig. 17A, the film forming method according to this embodiment is arranged to alternately repeat the first to sixth periods T1 to T6 as in the third embodiment shown in Fig. 6A. The period including the first to sixth periods T1 to T6 is repeated several times, and the SiCN film formed by the respective batches is laminated, thereby achieving the SiCN film having the target thickness.

Specifically, the first time period T1 is arranged to supply the supply of the first process gas to the process field 5 (the first process gas supply step 80) while the supply of the second and third process gases to the process field 5 is stopped. The second time period T2 is arranged to stop supplying the first, second and third process gases to the process field 5 (purification step P1). The third time period T3 is arranged to supply the third process gas to the process field 5 (the third process gas supply step 88) while the supply of the first and second process gases to the process field 5 is stopped. The fourth time period T4 is arranged to stop supplying the first, second and third process gases to the process field 5 (purification step P2). The fifth time period T5 is arranged to supply supply of the second process gas to the process field 5 (the second process gas supply step 84) while the supply of the first and third process gases to the process field 5 is stopped. The sixth time period T6 is arranged to stop supplying the first, second, and third process gases to the process field 5 (purification step P3).

In addition, in the first process gas stop step 82 of stopping the supply of the first process gas to the process field 5, a first process gas storage step 94 of storing the first process gas in the storage tank 50C is performed. Similarly, when the third process gas is stopped from being supplied to the process field 5 In the three process gas stop step 90, a third process gas storage step 96 of storing the third process gas in the storage tank 48C is performed.

In the timing diagram shown in FIG. 17A, the first and third process gas storage steps 94 and 96 are performed during the fourth time period T4, but may be any of the first and third process gas stop steps 82 and 90, respectively. Steps 94 and 96 are performed in the sequence. In particular, each of the first and third process gas storage steps 94 and 96 can be set at any location and can have any length within the second to sixth time periods T2 to T6.

Fig. 17B shows a timing chart of Modification 1 of the thirteenth embodiment, in which the second purification step P2 in Fig. 17A is omitted. In this case, one cycle is formed by the periods T1, T2, T3, T5, and T6. The first and third process gas storage steps 94 and 96 are performed during the fifth time period T5.

Fig. 17C shows a timing chart of Modification 2 of the thirteenth embodiment, in which the first and second purification steps P1 and P2 in Fig. 17A are omitted. In this case, one cycle is formed by the periods T1, T3, T5, and T6. The first and third process gas storage steps 94 and 96 are performed during the sixth time period T6.

Fig. 17D shows a timing chart of Modification 3 of the thirteenth embodiment, in which the first to third purification steps P1 to P3 in Fig. 17A are omitted. In this case, one cycle is formed by the periods T1, T3, and T5. The first and third process gas storage steps 94 and 96 are performed during the fifth time period T5.

This embodiment can also provide the same effects as the eleventh embodiment.

<Fourteenth Embodiment>

Fig. 18A is a timing chart showing the gas supply of the film formation method according to the fourteenth embodiment of the present invention. As shown in Fig. 18A, the film formation method according to this embodiment is arranged to be the same as the film formation method of the thirteenth embodiment shown in Fig. 17A except that the supply of the second process gas (NH ₃ supply) is not only Executed in the fifth time period T5 and performed in the first time period T1, and the third process gas storage step 96 is not performed in the second time period T2 except that the first process gas storage step 94 is not performed.

Fig. 18B shows a timing chart of Modification 1 of the fourteenth embodiment, in which the second purification step P2 in Fig. 18A is omitted. In this case, one cycle is formed by the periods T1, T2, T3, T5, and T6. A third process gas storage step 96 is performed during the second time period T2.

Fig. 18C shows a timing chart of Modification 2 of the fourteenth embodiment, in which the first and second purification steps P1 and P2 in Fig. 18A are omitted. In this case, one cycle is formed by the periods T1, T3, T5, and T6. A third process gas storage step 96 is performed during the first time period T1.

Fig. 18D shows a timing chart of Modification 3 of the fourteenth embodiment, in which the first to third purification steps P1 to P3 in Fig. 18A are omitted. In this case, one cycle is formed by the periods T1, T3, and T5. A third process gas storage step 96 is performed during the first time period T1.

This embodiment can also provide the same effects as the eleventh embodiment. Additionally, this embodiment can also be arranged to utilize the first process gas storage step 94 as described in the eleventh embodiment.

<Fifteenth Embodiment>

Fig. 19A is a timing chart showing the gas supply of the film formation method according to the fifteenth embodiment of the present invention. As shown in FIG. 19A, the film formation method according to this embodiment is arranged to be the same as the film formation method of the thirteenth embodiment shown in FIG. 17A except for the supply of the third process gas (C ₂ H ₄ supply). Not only performed in the third time period T3 but also in the first time period T1, and the first process gas is executed in the fifth time period T5 when the third process gas storage step 96 is performed in the second and fifth time periods T2 and T5 Store outside of step 94. In this case, the second time period T2 needs to include a third process gas storage step 96 to prepare for the third process gas supply step 88 directly thereafter.

Fig. 19B shows a timing chart of Modification 1 of the fifteenth embodiment, in which the second purification step P2 in Fig. 19A is omitted. In this case, one cycle is formed by the periods T1, T2, T3, T5, and T6. When the third process gas storage step 96 is performed in the second and fifth time periods T2 and T5, the first process gas storage step 94 is performed in the fifth time period T5.

Fig. 19C shows a timing chart of Modification 2 of the fifteenth embodiment, in which the first and second purification steps P1 and P2 in Fig. 19A are omitted. In this case, one cycle is formed by the periods T1, T3, T5, and T6. The first and third process gas storage steps 94 and 96 are performed only during the fifth time period T5.

Fig. 19D shows a timing chart of Modification 3 of the fifteenth embodiment, in which the first to third purification steps P1 to P3 in Fig. 19A are omitted. In this case, one cycle is formed by the periods T1, T3, and T5. The first and third process gas storage steps 94 and 96 are performed only during the fifth time period T5.

This embodiment can also provide the same effects as the eleventh embodiment.

<Sixteenth embodiment>

Fig. 20A is a timing chart showing the gas supply of the film formation method according to the sixteenth embodiment of the present invention. As shown in FIG. 20A, the film formation method according to this embodiment is arranged to be the same as the film formation method of the thirteenth embodiment shown in FIG. 17A except that the supply of the second process gas (NH ₃ supply) is not only Executed in the fifth time period T5 and executed in the first time period T1, the supply of the third process gas (C ₂ H ₄ supply) is performed not only in the third time period T3 but also in the first time period T1, and in the second time The execution of the third process gas storage step 96 in the fifth time period T2 and T5 does not perform the first process gas storage step 94. In this case, the second time period T2 needs to include a third process gas storage step 96 to prepare for the third process gas supply step 88 directly thereafter.

Fig. 20B shows a timing chart of Modification 1 of the sixteenth embodiment, in which the second purification step P2 in Fig. 20A is omitted. In this case, one cycle is formed by the periods T1, T2, T3, T5, and T6. A third process gas storage step 96 is performed in the second and sixth time periods T2 and T6.

Fig. 20C shows a timing chart of Modification 2 of the sixteenth embodiment, in which the first and second purification steps P1 and P2 in Fig. 20A are omitted. In this case, one cycle is formed by the periods T1, T3, T5, and T6. Executing a third process gas reservoir in the fifth and sixth time periods T5 and T6 Save step 96.

Fig. 20D shows a timing chart of Modification 3 of the sixteenth embodiment, in which the first to third purification steps P1 to P3 in Fig. 20A are omitted. In this case, one cycle is formed by the periods T1, T3, and T5. The third process gas storage step 96 is performed only in the fifth time period T5.

This embodiment can also provide the same effects as the eleventh embodiment. Additionally, this embodiment can also be arranged to utilize the first process gas storage step 94 as described in the eleventh embodiment.

<Seventeenth Embodiment>

Fig. 21A is a timing chart showing the gas supply of the film forming method according to the seventeenth embodiment of the present invention. As shown in Fig. 21A, the film formation method according to this embodiment is arranged to be the same as the film formation method of the eleventh embodiment shown in Fig. 15A except that the supply of the second process gas (NH ₃ supply) is not only Executed in the third time period T3 and executed in the first time period T1, the supply of the third process gas (C ₂ H ₄ supply) is performed not only in the first time period T1 but also in the third time period T3, and in the second The execution of the third process gas storage step 96 in the fourth time period T2 and T4 is performed outside of the first process gas storage step 94 in the fourth time period T4. In this case, the second time period T2 needs to include a third process gas storage step 96 to prepare for the third process gas supply step 88 directly thereafter.

Fig. 21B shows a timing chart of Modification 1 of the seventeenth embodiment, in which the first purification step P1 in Fig. 21A is omitted. In this case, one cycle is formed by the periods T1, T3, and T4. The first and third process gas storage steps 94 and 96 are performed only in the fourth time period T4.

Fig. 21C shows a timing chart of Modification 2 of the seventeenth embodiment, in which the two purification steps P1 and P2 in Fig. 21A are omitted. In this case, one cycle is formed by the periods T1 and T3. Specifically, this embodiment is arranged to alternately execute and stop the first process gas (DCS) while continuously supplying the supply of the second process gas (NH ₃ ) and the third process gas (C ₂ H ₄ ). Supply. Therefore, only the first process gas storage step 94 is performed in the third time period T3.

This embodiment can also provide the same effects as the eleventh embodiment.

<Eighteenth Embodiment>

Fig. 22A is a timing chart showing the gas supply of the film formation method according to the eighteenth embodiment of the present invention. As shown in Fig. 22A, the film formation method according to this embodiment is arranged to be the same as the film formation method of the twelfth embodiment shown in Fig. 16A except that the supply of the second process gas (NH ₃ supply) is not only Executed in the first time period T1 and performed in the third time period T3. When the third process gas storage step 96 is performed in the second time period T2, the first process gas storage step 94 is not performed.

Fig. 22B shows a timing chart of Modification 1 of the eighteenth embodiment, in which the first purification step P1 in Fig. 22A is omitted. In this case, one cycle is formed by the periods T1, T3, and T4. A third process gas storage step 96 is performed during the first time period T1.

Fig. 22C shows a timing chart of Modification 2 of the eighteenth embodiment, in which the two purification steps P1 and P2 in Fig. 22A are omitted. In this case, one cycle is formed by the periods T1 and T3. A third process gas storage step 96 is performed during the first time period T1.

This embodiment can also provide the same effects as the eleventh embodiment. Additionally, this embodiment can also be arranged to utilize the first process gas storage step 94 as described in the eleventh embodiment.

<Nineteenth Embodiment>

Fig. 23A is a timing chart showing the gas supply of the film formation method according to the nineteenth embodiment of the present invention. As shown in FIG. 23A, the film formation method according to this embodiment is arranged to be the same as the film formation method of the eleventh embodiment shown in FIG. 15A except for the supply of the third process gas (C ₂ H ₄ supply). Execution is performed in the third time period T3 instead of in the first time period T1, and is not performed outside the first process gas storage step 94 when the third process gas storage step 96 is performed in the second time period T2.

Fig. 23B shows a timing chart of Modification 1 of the nineteenth embodiment, in which the first purification step P1 in Fig. 23A is omitted. In this case, one cycle is formed by the periods T1, T3, and T4. A third process gas storage step 96 is performed during the first time period T1.

Figure 23C shows a timing chart of Modification 2 of the nineteenth embodiment, in which the two purification steps P1 and P2 in Figure 23A are omitted. In this case, one cycle is formed by the periods T1 and T3. A third process gas storage step 96 is performed during the first time period T1.

This embodiment can also provide the same effects as the eleventh embodiment. Additionally, this embodiment can also be arranged to utilize the first process gas storage step 94 as described in the eleventh embodiment.

<Twentieth Embodiment>

Fig. 24A is a timing chart showing the gas supply of the film formation method according to the twentieth embodiment of the present invention. As shown in Fig. 24A, the film formation method according to this embodiment is arranged to be the same as the film formation method of the eleventh embodiment shown in Fig. 15A except for the supply of the third process gas (C ₂ H ₄ supply) Not only performed in the first time period T1 but also in the third time period T3, and the first process gas is executed in the fourth time period T4 when the third process gas storage step 96 is performed in the second and fourth time periods T2 and T4 Store outside of step 94. In this case, the second time period T2 needs to include a third process gas storage step 96 to prepare for the third process gas supply step 88 directly thereafter.

Fig. 24B shows a timing chart of Modification 1 of the twentieth embodiment, in which the first purification step P1 in Fig. 24A is omitted. In this case, one cycle is formed by the periods T1, T3, and T4. The first and third process gas storage steps 94 and 96 are performed only in the fourth time period T4.

Fig. 24C shows a timing chart of Modification 2 of the twentieth embodiment, in which the two purification steps P1 and P2 in Fig. 24A are omitted. In this case, one cycle is formed by the periods T1 and T3. Specifically, this embodiment is arranged to alternately execute and stop the first process gas (DCS) and the second process gas (NH ₃ ) while continuously supplying the supply of the third process gas (C ₂ H ₄ ) The supply of each. Therefore, the first process gas storage step 94 is performed only in the third time period T3.

This embodiment can also provide the same effects as the eleventh embodiment.

<The case common to the first to twentieth embodiments>

The above embodiment is exemplified by the case of forming a SiCN film, but the film may be additionally doped with an impurity such as B (boron). The above embodiment is exemplified by the case where each cycle is arranged to supply the first process gas (DCS) first, but each cycle may be arranged to first supply the second process gas (NH ₃ ) or the third process gas (C _{2 )} H ₄ ).

The apparatus shown in Figures 1 and 2 includes nozzle receiving recesses 60 formed in the side walls of process vessel 4 to accommodate nozzles 38, 40 and 42. However, the nozzle receiving recess 60 may be omitted when a space sufficient to accommodate the nozzle exists between the process vessel 4 and the edge of the wafer.

The film forming apparatus shown in Figs. 1 and 2 has a single tube type, but a double tube type film forming apparatus including a concentric inner tube and an outer tube can be used. The flow of gas within the process vessel is not limited to lateral flow. For example, the present invention is applicable to a film forming apparatus having a vertical process vessel in which gas is supplied from one end in a vertical direction and discharged from the other end to form a vertical flow. The apparatus shown in Figures 1 and 2 is a batch type membrane forming apparatus for processing a plurality of wafers together. Alternatively, the present invention is applicable to a film forming apparatus of a single substrate type for processing wafers one by one.

In the above embodiment, the first process gas contains DCS gas as a decane gas. In this aspect, the decane gas may be one or more gases selected from the group consisting of: dichlorosilane (DCS), hexachlorodioxane (HCD), monodecane (SiH ₄ ), dioxane (Si ₂ Cl ₆ ), hexamethyldiazepine (HMDS), tetrachlorodecane (TCS), dioxane amine (DSA), tridecylamine (TSA), bis-tert-butylamino decane (BTBAS) and diisopropyl Amino decane (DIPAS).

In the above embodiment, the second process gas contains NH ₃ gas as the nitriding gas. In this aspect, the nitriding gas may be one or more gases selected from the group consisting of ammonia (NH ₃ ), nitrogen (N ₂ ), nitrous oxide (N ₂ O), and nitrogen oxide (NO).

In the above embodiment, the third process gas contains ethylene gas as a hydrocarbon gas. In this aspect, the hydrocarbon gas may be one or more selected from the group consisting of: Gas: acetylene, ethylene, methane, ethane, propane and butane.

The target substrate is not limited to a semiconductor wafer, and it may be another substrate such as an LCD substrate or a glass substrate.

Those skilled in the art will readily appreciate additional advantages and modifications. Therefore, the invention in its broader aspects is not intended to Accordingly, various modifications may be made without departing from the spirit and scope of the inventions.

80‧‧‧Steps for supplying the first process gas

82‧‧‧Steps to stop supplying the first process gas

84‧‧‧Steps for supplying the second process gas

86‧‧‧Steps to stop supplying the second process gas

88‧‧‧Steps for supplying a third process gas

90‧‧‧Steps to stop supplying third process gas

P1‧‧‧ purification steps

P2‧‧‧ purification steps

First time of T1‧‧

T2‧‧‧ second period

T3‧‧‧ third period

T4‧‧‧ fourth period

Claims (13)

A method for forming a SiCN film having a carbon concentration of 15.2 to 28.5% on a target substrate in a process field, the process field system sequentially supplying a first process gas containing a helium source gas in a pulse wave manner, a second process gas containing ammonia gas and a third process gas containing ethylene gas, the method being arranged to perform a plurality of cycles to laminate the films respectively formed by the cycles, thereby forming the SiCN film having a predetermined thickness Each of the periods includes: performing a first step of supplying the first process gas to the process field; performing a second step of supplying the second process gas to the process field; performing the supply of the third process gas to a third step of the process field; and a fourth step of stopping the supply of the first process gas to the process field; the flow rate of the helium source gas in a unit cycle is in the range of 500 to 5,000 sccm, and the flow rate of the ammonia gas In the range of 100 to 10,000 sccm, the flow rate of the ethylene gas is in the range of 100 to 5,000 sccm, and the flow rate of the ethylene gas is not more than three times the flow rate of the helium source gas; The cycle is arranged to not convert any one of the first process gas, the second process gas, and the third process gas into a plasma outside the process field during its supply, and in the first step, During the second step, the third step and the fourth step, the process field is heated to a process temperature of 300-700 ° C, and the process pressure is set to 13 Pa (0.1 Torr) to 1,330 Pa (10 Torr) per unit cycle. In the range, the helium source gas, the ammonia gas and the ethylene gas react with each other, and the third step is performed at least in part between the first step and the second step; and wherein the pulse wave supply per unit period The source gas, the ammonia gas, and the ethylene gas are each supplied once in a supply period of a single digit number of seconds, and the supply of the B The pulsation period of the olefin gas is longer than the period of the pulse wave supplying the yttrium gas, and the thickness of each film formed per unit period is about 0.048 to 0.13 nm. The method of claim 1, wherein the third step does not overlap with the second step. The method of claim 1, wherein the third step overlaps with the first step. The method of any one of claims 1 to 3, wherein the third step is longer than the first step. The method of any one of clauses 1 to 3, wherein the first step does not overlap with the second step. The method of any one of claims 1 to 3, wherein the periods are each included in the process site when the supply of the first process gas, the second process gas, and the third process gas to the process plant are stopped. One step of exhausting gas. The method of any one of claims 1 to 3, wherein the periods are each included in the performing the fourth step, storing the first process gas to be subsequently supplied to the process field in a storage tank In the step, the storage tank is disposed between the first rate controller and the processing farm. An apparatus for forming a SiCN film on a target substrate, the apparatus comprising: a process container having a frame to form a process field for accommodating the target substrate; and a support member configured to support the target substrate in the process field a heater, the frame is configured to heat the target substrate in the process field; an exhaust system, the frame constitutes a gas discharged from the process field; and a first process gas supply line, the frame structure thereof will contain a first process gas of the source gas is supplied to the process field; a second process gas supply line is configured to supply a second process gas containing ammonia gas to the process field; and a third process gas supply line a tie frame constituting a third process gas containing ethylene gas to the process plant; and A control unit, the cradle constitutes an operation for controlling the device, wherein the control portion is preset to perform a method for forming a SiCN film on the target substrate in the process field, the method being performed by performing a plurality of cycles Stacking the films respectively formed by the cycles, thereby forming the SiCN film having a predetermined thickness of about 0.048 to 0.13 nm, each of the cycles including performing the first step of supplying the first process gas to the process field, and performing a second step of supplying the second process gas to the process field, performing a third step of supplying the third process gas to the process field, and stopping a fourth step of supplying the first process gas to the process field, wherein The cycles are each arranged to not convert any of the first process gas, the second process gas, and the third process gas into a plasma outside of the process field during its supply, and at the first During the step, the second step, the third step and the fourth step, the process field is heated to a process temperature of 300-700 ° C, and the process pressure is set to 13 Pa (0.1 Torr) to 1,330 Pa (10 Torr) per unit cycle. Scope of Internally, the helium source gas, the ammonia gas, and the ethylene gas react with each other, and the third step is performed at least in part between the first step and the second step; and wherein the pulse wave is supplied per unit period, The source gas, the ammonia gas, and the ethylene gas injected by the source gas are each supplied once in a supply period of a single digit number of seconds, and a period of a pulse wave supplying the ethylene gas is shorter than a period of a pulse wave supplying the source gas. long. The device of claim 8, wherein the third step does not overlap with the second step. The apparatus of claim 8, wherein the third step overlaps the first step. The apparatus of any one of clauses 8 to 10, wherein the periods each comprise a fifth step of discontinuing supply of the second process gas to the process field. The apparatus of any one of clauses 8 to 10, wherein the periods each comprise a cessation of supply The third process gas is to the sixth step of the process field. The apparatus of any one of claims 8 to 10, wherein the first process gas supply line includes a storage tank disposed between the first rate controller and the process field, and the cycles are each included in the execution of the fourth At the time of the step, the first process gas to be supplied to the process field is subsequently stored in the storage tank.