JP2018101810A - DEPOSITION METHOD OF SiCN FILM - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a deposition method of an SiCN film which enables an SiCN film to be deposited while maintaining a good deposition rate even when deposition temperature is lowered.SOLUTION: A deposition method of an SiCN film deposits an SiCN film on a processed surface of a processed object. The deposition method of the SiCN film includes: a step (step 1) where an Si material gas containing Si material is supplied to a processing chamber in which the processed object is stored; and a step (step 3) where gas containing a nitriding agent is supplied to the processing chamber after the step (step 1) where the Si material gas is supplied. A 1, 2, 3-triazole-based compound is used as the nitriding agent.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for forming a SiCN film.

As an insulating film of a semiconductor integrated circuit device, a silicon oxide film (SiO ₂ film) and a silicon nitride film (SiN film) are well known. SiN film has a specific dielectric constant than SiO ₂ film is high, and there are advantages such as etching selection ratio can take with respect to SiO ₂ film or a silicon (Si). Thus, SiN film, or used in a portion requiring a higher dielectric constant than SiO ₂ film, and an etching stopper layer for the SiO ₂ film or Si, the hard mask layer in processing the SiO ₂ film or Si It is being used.

  Film forming apparatuses used for manufacturing semiconductor integrated circuit devices are roughly classified into a single wafer type film forming apparatus that processes wafers one by one and a batch type film forming apparatus that processes a plurality of wafers at a time. The batch type film forming apparatus includes a vertical batch type film forming apparatus capable of processing more wafers at a time. The film forming temperature when forming the SiN film using the vertical batch type film forming apparatus is approximately 630 ° C. to 760 ° C.

  Incidentally, miniaturization of semiconductor integrated circuit devices is still progressing. In order to miniaturize a semiconductor integrated circuit device, it is desired to lower the process temperature in the manufacturing process of the semiconductor integrated circuit device.

In order to form the SiN film at a low temperature, a nitriding agent contained in the nitriding gas, for example, ammonia (NH ₃ ) is used as an active nitriding species such as ammonia radicals using plasma. By using such active nitriding species, nitriding of the Si film on the wafer can be promoted even at low temperatures. However, when the Si film is nitrided using a plasma nitriding agent, the chemical resistance of the formed SiN film deteriorates. In particular, it becomes easy to be etched into a diluted hydrofluoric acid solution (hereinafter referred to as a diluted HF solution). Therefore, in Patent Document 1, a method is adopted in which carbon (C) is added to a SiN film to form a silicon carbonitride film (hereinafter referred to as a SiCN film), and chemical resistance is improved as compared with the SiN film.

  In Patent Document 1, a SiC film is formed by nitriding a SiC film using active nitriding species generated using plasma. For this reason, even if the film formation temperature is lowered to a temperature range of less than 630 ° C., a sufficient film formation rate that can be used for actual use can be obtained. However, when there is a fine structure with a step on the surface to be processed, for example, a trench, there is a situation that it is difficult to form a film on the sidewall of the trench bottom. This is partly because active nitridation species such as ammonia radicals are brought into contact with the sidewalls of the trench and deactivated, making it difficult for the active ammonia radicals to reach the bottom of the trench sufficiently.

  Therefore, in Patent Document 2, the SiC film is nitrided without using plasma. Thereby, compared with patent document 1, the advantage that it becomes easy to perform film-forming to a trench bottom part can be acquired.

JP 2006-287194 A JP 2012-23399 A

  However, in Patent Document 2, since the SiC film is nitrided without using plasma, if the film forming temperature is lowered, for example, if the film forming temperature is lowered to a temperature range of less than 630 ° C., it is compared with the case where plasma is used. As a result, there is a situation in which the film formation rate is rapidly reduced.

  The present invention provides a method for forming a SiCN film that can form a SiCN film while maintaining a good film formation rate even when the film formation temperature is lowered.

ただし、前記一般式(１)においてＲ^１、Ｒ^２、Ｒ^３は、水素原子又は置換基を有しても良い炭素原子数１〜８の直鎖状又は分岐状のアルキル基である。 A SiCN film forming method according to an aspect of the present invention is a SiCN film forming method for forming a SiCN film on a processing target surface of a target object, and a processing chamber in which the target target object is accommodated. And a step of supplying a gas containing a nitriding agent into the processing chamber after the step of supplying the Si raw material gas containing Si raw material and the step of supplying the Si raw material gas. The compound of nitrogen and carbon represented by (1) is used.

However, in the said General formula (1), R < ¹ >, R < ² >, R < ³ > is a C1-C8 linear or branched alkyl group which may have a hydrogen atom or a substituent.

  According to the present invention, it is possible to provide a SiCN film forming method capable of forming a SiCN film while maintaining a good film forming rate even when the film forming temperature is lowered.

1 is a flowchart showing an example of a method of forming a SiCN film according to the first embodiment of the present invention. Sectional drawing which shows the state of the to-be-processed object in the sequence shown in FIG. Sectional drawing which shows the state of the to-be-processed object in the sequence shown in FIG. Sectional drawing which shows the state of the to-be-processed object in the sequence shown in FIG. Sectional drawing which shows the state of the to-be-processed object in the sequence shown in FIG. Sectional drawing which shows the state of the to-be-processed object in the sequence shown in FIG. Sectional drawing which shows the state of the to-be-processed object in the sequence shown in FIG. Diagram showing atomic composition of SiCN film The figure which shows the etching rate of a SiN film and a SiCN film The figure which shows the relationship between the film-forming temperature and film-forming rate of a SiN film and a SiCN film The figure which shows the cleavage location of a 1,2,3-triazole type compound 1 is a longitudinal sectional view schematically showing a first example of a film forming apparatus capable of performing the SiCN film forming method according to the first embodiment. 1 is a horizontal sectional view schematically showing a second example of a film forming apparatus capable of performing the SiCN film forming method according to the first embodiment.

  Embodiments of the present invention will be described below with reference to the drawings. Note that common parts are denoted by common reference numerals throughout the drawings.

(First embodiment)
<Film formation method>
FIG. 1 is a flowchart showing an example of a method of forming a SiCN film according to the first embodiment of the present invention, and FIGS. 2A to 2F are cross-sectional views showing states of objects to be processed in the sequence shown in FIG.

First, as shown in FIG. 2A, an object to be processed is prepared. In this example, a silicon wafer (hereinafter referred to as a wafer) 1 was used as the object to be processed. An SiO ₂ film 2 is formed on the wafer 1. In this example, the surface of the SiO ₂ film 2 is the surface to be processed. The SiCN film is formed on the SiO ₂ film 2 that is the surface to be processed. The surface to be processed of the wafer 1 is not limited to the SiO ₂ film 2 but may be any film that can form a SiCN film. Of course, the surface of the wafer 1 itself may be the surface to be processed. Next, the wafer 1 shown in FIG. 2A is accommodated in the processing chamber of the film forming apparatus.

Next, as shown in step 1 and 2B of Figure 1, in the processing chamber by supplying a Si source gas on the SiO ₂ film 2, to form a Si film 3-1 on the SiO ₂ film 2. In this example, hexachlorodisilane (HCD) was used as the Si source gas. Of course, the Si source gas is not limited to HCD.

An example of the processing conditions in Step 1 is as follows.
HCD flow rate: 100sccm
Deposition time: 0.5 min (per cycle)
Deposition temperature: 550 ° C
Deposition pressure: 133.32 Pa (1 Torr)

Next, as shown in Step 2 of FIG. 1, after the processing chamber of the film forming apparatus is evacuated, an inert gas, for example, N ₂ gas is supplied into the processing chamber, and the processing chamber is purged.

  Next, as shown in Step 3 of FIG. 1 and FIG. 2C, a gas containing a carbon-containing nitriding agent is supplied onto the Si film 3-1 to nitride the Si film 3-1 and add carbon (C). To do. As a result, the Si film 3-1 becomes the SiCN film 4-1. As the carbon-containing nitriding agent, a compound of carbon and nitrogen represented by the following general formula (1) is used in this example.

The compound represented by the general formula (1) is a 1,2,3-triazole compound, and R ¹ , R ² and R ³ each have 1 to 8 carbon atoms which may have a hydrogen atom or a substituent. It is a linear or branched alkyl group.

Specific examples of the linear or branched alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, t. -Pentyl group n-hexyl group isohexyl group t-hexyl group n-heptyl group isoheptyl group t-heptyl group n-octyl group isooctyl group t-octyl group. A methyl group, an ethyl group, and an n-propyl group are preferable. More preferred is a methyl group.

The substituent may be a linear or branched monoalkylamino group or dialkylamino group substituted with an alkyl group having 1 to 4 carbon atoms. Specifically, it is a monomethylamino group, a dimethylamino group, a monoethylamino group, a diethylamino group, a monopropylamino group, a monoisopropylamino group, or an ethylmethylamino group. A monomethylamino group and a dimethylamino group are preferable. More preferred is a dimethylamino group.

Further, the substituent may be a linear or branched alkoxy group having 1 to 8 carbon atoms. Specifically, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a hexyloxy group, a heptyloxy group, and an octyloxy group. Preferably, they are a methoxy group, an ethoxy group, and a propoxy group. More preferably, it is a methoxy group.

Examples of specific compounds represented by the general formula (1) include
1H-1,2,3-triazole 1-methyl-1,2,3-triazole 1,4-dimethyl-1,2,3-triazole 1,4,5-trimethyl-1,2,3-triazole 1- Ethyl-1,2,3-triazole 1,4-diethyl-1,2,3-triazole 1,4,5-triethyl-1,2,3-triazole. In addition, you may use these compounds individually or in mixture of 2 or more types.

In this example, 1H-1,2,3-triazole was used as the carbon-containing nitriding agent. An example of the processing conditions in Step 3 is as follows.
Triazole flow rate: 100sccm
Processing time: 0.5 min (per cycle)
Processing temperature: 550 ℃
Processing pressure: 133.32 Pa (1 Torr)

Next, as shown in Step 4 of FIG. 1, after exhausting the processing chamber of the film forming apparatus, an inert gas, for example, N ₂ gas is supplied into the processing chamber, and the processing chamber is purged.

  Next, as shown in step 5 of FIG. 1, it is determined whether or not the number of processes is a set number. If the set number of times has been reached (Yes), the film formation of the SiCN film is terminated.

  If the set number of times has not been reached (No), Steps 1 to 4 are repeated, and as shown in FIG. 2D, a second-layer Si film 3-2 is formed on the SiCN film 4-1, and FIG. As shown, the second Si film 3-2 is nitrided and C is added to form a second SiCN film 4-2.

  Thus, by repeating steps 1 to 4 for the set number of times, as shown in FIG. 2F, the SiCN film 4 having the designed film thickness t is formed.

<Atomic composition of SiCN film>
FIG. 3 shows the atomic composition of the SiCN film. In FIG. 3, in addition to the atomic composition of the SiCN film formed by the film forming method according to the first embodiment, as a reference example, the film forming temperature is 630 ° C., Si source gas is dichlorosilane (DCS), and the nitriding agent is The atomic composition of a SiCN film formed by thermal ALD using NH ₃ and ethylene (C ₂ H ₄ ) as a carbonizing agent is shown.

  As shown in FIG. 3, the atomic composition of the SiCN film according to the reference example is N = 41.9 at%, Si = 47.6 at%, and C = 10.5 at%. According to the reference example, C is added, but the amount of C is less than Si and N. According to the reference example, a SiCN film rich in Si or N is obtained.

  On the other hand, the atomic composition of the SiCN film formed by the film forming method according to the first embodiment is N = 30.5 at%, Si = 30.6 at%, and C = 38.4 at%. A C-rich SiCN film having a larger amount of C than Si or N is formed. Note that a trace amount of chlorine (Cl) of 0.5 at% is detected from the SiCN film formed by the film forming method according to the first embodiment. This Cl is derived from HCD, which is a Si source gas.

  Thus, according to the SiCN film formed by the film forming method according to the first embodiment, a C-rich SiCN film having a larger amount of C than Si or N is formed as compared with the reference example. It is possible. Of course, the amount of C added can be adjusted by adjusting the flow rate of 1H-1,2,3-triazole. That is, according to the film forming method according to the first embodiment, it is possible to obtain the advantage that the amount of C added can be controlled over a wider range than in the reference example. For example, the amount of C added affects the chemical resistance of the SiCN film. The fact that the addition amount of C can be controlled in a wider range means that a SiCN film having a higher chemical resistance can be formed as compared with the reference example.

<Drug resistance of SiCN film>
FIG. 4 is a diagram showing the etching rates of the SiN film and the SiCN film. FIG. 4 shows the ratio of the etching rates of the SiN film and the SiCN film when 0.5% DHF is used as the etchant and the etching rate of the thermal SiO ₂ film is set to a reference value of 1.0 (100%). Has been.

First, the etching rate of the SiN film will be described.
The etching rate with respect to 0.5% DHF of the SiN film formed by the plasma ALD method using DCS as the Si source gas and NH ₃ as the nitriding agent is 0.47 compared to the reference value. (47%), which is approximately half the etching rate of the thermal SiO ₂ film. However, when the deposition temperature is lowered to 450 ° C., the etching rate for 0.5% DHF is 1.21 (121%) compared to the reference value, and the etching rate is faster than that of the thermal SiO ₂ film. . Thus, it cannot be said that the SiN film formed by the plasma ALD method has good chemical resistance, particularly resistance to 0.5% DHF.

Also, according to the SiN film formed by the thermal ALD method using DCS as the Si source gas and NH ₃ as the nitriding agent, the etching rate for 0.5% DHF is compared with the reference value. 0.19 (19%), which can be improved to about 1/5 of the etching rate of the thermal SiO ₂ film. The film formation temperature of the SiN film formed by the thermal ALD method shown in FIG. 4 is 630 ° C., which is higher than the film formation temperature of 450 ° C. to 500 ° C. of the SiN film formed by the plasma ALD method shown in FIG. high. For this reason, it is not a comparison at the same film formation temperature, and it is a general theory, but in order to increase the chemical resistance of the SiN film, it is better that the film formation temperature is higher, and the thermal ALD method than the plasma ALD method. May be considered advantageous. It is certain that FIG. 4 shows that the SiN film formed by the high temperature thermal ALD method at 630 ° C. is less than the SiN film formed by the low temperature plasma ALD method at 450 ° C. to 500 ° C. The resistance to 5% DHF is improved.

Furthermore, according to the SiCN film formed by the thermal ALD method using DCS as the Si source gas and DC ₃ as the Si source gas and NH ₃ as the nitriding agent, and added with C, etching with respect to 0.5% DHF is performed. The rate is 0.03 (3%) compared to the reference value. That is, the SiCN film formed by the thermal ALD method has higher chemical resistance than the SiN film formed by the thermal ALD method.

  Then, according to the SiCN film formed by the film forming method according to the first embodiment, the etching rate with respect to 0.5% DHF is not more than 0.03 (3%), which is below the measurement limit. The result was that it was hardly etched with respect to% DHF. Moreover, the deposition temperature of the SiCN film deposited by the deposition method according to the first embodiment is 550 ° C., which is lower than 630 ° C.

As described above, according to the film forming method according to the first embodiment, the chemical resistance is higher than that of the SiCN film formed by the thermal ALD method using DCS as the Si source gas and NH ₃ as the nitriding agent. A high SiCN film can be obtained.

<Deposition rate of SiCN film>
FIG. 5 is a graph showing the relationship between the deposition temperature and deposition rate of the SiN film and the SiCN film.
As shown in FIG. 5, the plasma ALD method using DCS as the Si source gas and NH ₃ as the nitriding agent ensures a film formation rate of 0.02 nm / min or more even when the film formation temperature is low. This is advantageous for low-temperature film formation.

Further, the thermal ALD method using DCS as the Si source gas and NH ₃ as the nitriding agent has a practical film formation rate of 0.06 to 0.07 nm / min when the film formation temperature is 600 ° C. Can be secured. However, when the film formation temperature is lowered to 550 ° C., the film formation rate is reduced to about 0.01 nm / min. In the thermal ALD method using DCS as the Si source gas and NH ₃ as the nitriding agent, the SiN film can hardly be formed when the film forming temperature is below 500 ° C. However, when HCD is used instead of DCS as the Si source gas, the decrease in film formation rate during low temperature film formation can be improved.

  According to the SiCN film formed by the film forming method according to the first embodiment, when the film forming temperature is 550 ° C., a film forming rate of 0.07 to 0.08 nm / min can be secured. it can. Furthermore, even when the film formation temperature is lowered to 450 ° C., a film formation rate of 0.05 to 0.06 nm / min can be secured. In particular, a favorable film deposition rate in the temperature range of 200 ° C. or higher and 550 ° C. or lower can be obtained that is almost equal to that of the plasma ALD method.

  As described above, according to the film forming method according to the first embodiment, in the low temperature film formation, for example, in the temperature range of 200 ° C. or more and 550 ° C. or less, even if no plasma is used, it is equivalent to the case using plasma. A film forming rate can be secured. One reason for this is as follows.

As shown in FIG. 6, the 1,2,3-triazole compound includes an “N═N—N” bond in the five-membered ring. The portion of “N = N” in this bond has a property of decomposing to become nitrogen (N ₂ , N≡N). For this reason, the 1,2,3-triazole compound has a characteristic of causing cleavage / decomposition at a number of locations, unlike ordinary ring-opening cleavage. That is, in order to generate “N≡N”, an electronically unsaturated state occurs in the compound. Thus, the decomposition product obtained by cleaving / decomposing the 1,2,3-triazole compound is active. For this reason, it is possible to nitride the Si film and add C even when the film formation temperature is low, for example, in a temperature range of 200 ° C. or more and 550 ° C. or less.

  Therefore, according to the SiCN film formation method according to the first embodiment, it is possible to form the SiCN film while maintaining a good film formation rate even when the film formation temperature is lowered. Can be obtained.

  Furthermore, another advantage obtained from the SiCN film forming method according to the first embodiment is that the step of carbonizing the Si film or the SiN film becomes unnecessary. This is because the 1,2,3-triazole-based compound contains N and C atoms, and nitriding and C can be added simultaneously in the same step with one kind of compound. This is an advantageous advantage for improving the throughput.

(Second Embodiment)
The second embodiment relates to an example of a film forming apparatus capable of performing the SiCN film forming method according to the first embodiment.

<Film forming apparatus: first example>
FIG. 7 is a longitudinal sectional view schematically showing a first example of a film forming apparatus capable of performing the SiCN film forming method according to the first embodiment.

  As shown in FIG. 7, the film forming apparatus 100 includes a cylindrical processing chamber 101 having a ceiling with a lower end opened. The entire processing chamber 101 is made of, for example, quartz. A quartz ceiling plate 102 is provided on the ceiling in the processing chamber 101. For example, a manifold 103 formed in a cylindrical shape from stainless steel is connected to a lower end opening of the processing chamber 101 via a seal member 104 such as an O-ring.

  The manifold 103 supports the lower end of the processing chamber 101. From the lower side of the manifold 103, a plurality of, for example, 50 to 100 semiconductor substrates as processing objects, in this example, a quartz wafer boat 105 on which the wafers 1 can be placed in multiple stages are inserted into the processing chamber 101. It is possible. Thereby, the wafer 1 is accommodated in the processing chamber 101. The wafer boat 105 has a plurality of support columns 106, and a plurality of wafers 1 are supported by grooves formed in the support columns 106.

  The wafer boat 105 is placed on a table 108 via a quartz heat insulating cylinder 107. The table 108 is supported on a rotating shaft 110 that opens and closes a lower end opening of the manifold 103 and penetrates a lid portion 109 made of, for example, stainless steel. For example, a magnetic fluid seal 111 is provided in the penetrating portion of the rotating shaft 110 and supports the rotating shaft 110 so as to be rotatable while hermetically sealing. Between the peripheral part of the cover part 109 and the lower end part of the manifold 103, for example, a seal member 112 made of an O-ring is interposed. Thereby, the sealing performance in the processing chamber 101 is maintained. The rotating shaft 110 is attached to the tip of an arm 113 supported by an elevating mechanism (not shown) such as a boat elevator, for example. As a result, the wafer boat 105, the lid portion 109, and the like are integrally moved up and down and inserted into and removed from the processing chamber 101.

  The film forming apparatus 100 includes a processing gas supply mechanism 114 that supplies a gas used for processing in the processing chamber 101, and an inert gas supply mechanism 115 that supplies an inert gas in the processing chamber 101. . The processing gas supply mechanism 114 of this example includes a Si source gas supply source 117a and a 1,2,3-triazole compound gas supply source 117b. The inert gas supply mechanism 115 includes an inert gas supply source 120.

An example of the Si source gas is HCD, and an example of the 1,2,3-triazole-based compound gas is 1H-1,2,3-triazole. An example of the inert gas is N ₂ gas.

  The Si source gas supply source 117a is connected to the dispersion nozzle 123a via the flow rate controller 121a and the on-off valve 122a. Similarly, the 1,2,3-triazole compound gas supply source 117b is connected to the dispersion nozzle 123b via the flow rate controller 121b and the on-off valve 122b.

  The dispersion nozzles 123a and 123b are made of quartz tubes, penetrate the sidewalls of the manifold 103 inward, are bent upward, and extend vertically. A plurality of gas discharge holes 124 are formed at predetermined intervals in vertical portions of the dispersion nozzles 123a and 123b. As a result, each gas is ejected from the gas ejection holes 124 in the horizontal direction into the processing chamber 101 substantially uniformly.

  The inert gas supply source 120 is connected to the nozzle 128 via the flow rate controller 121c and the on-off valve 122c. The nozzle 128 passes through the side wall of the manifold 103 and discharges an inert gas from the tip thereof into the processing chamber 101 in the horizontal direction.

  An exhaust port 129 for exhausting the inside of the processing chamber 101 is provided in a portion of the processing chamber 101 opposite to the dispersion nozzles 123a and 123b. The exhaust port 129 is formed in an elongated shape by scraping the side wall of the processing chamber 101 in the vertical direction. An exhaust port cover member 130 having a U-shaped cross section so as to cover the exhaust port 129 is attached to a portion corresponding to the exhaust port 129 of the processing chamber 101 by welding. The exhaust port cover member 130 extends upward along the side wall of the processing chamber 101, and defines a gas outlet 131 above the processing chamber 101. An exhaust mechanism 132 including a vacuum pump or the like is connected to the gas outlet 131. The exhaust mechanism 132 exhausts the inside of the processing chamber 101 to set the exhaust of the processing gas used for the processing and the pressure in the processing chamber 101 to a processing pressure corresponding to the processing.

  A cylindrical heating device 133 is provided on the outer periphery of the processing chamber 101. The heating device 133 activates the gas supplied into the processing chamber 101 and heats the target object accommodated in the processing chamber 101, in this example, the wafer 1.

  Control of each part of the film forming apparatus 100 is performed by a controller 150 including, for example, a microprocessor (computer). Connected to the controller 150 is a user interface 151 including a touch panel on which an operator inputs commands to manage the film forming apparatus 100, a display for visualizing and displaying the operating status of the film forming apparatus 100, and the like. Yes.

  A storage unit 152 is connected to the controller 150. The storage unit 152 is a control program for realizing various processes executed by the film forming apparatus 100 under the control of the controller 150, and for causing each component of the film forming apparatus 100 to execute processes according to the processing conditions. A program or recipe is stored. The recipe is stored in a storage medium in the storage unit 152, for example. The storage medium may be a hard disk or a semiconductor memory, or a portable medium such as a CD-ROM, DVD, or flash memory. Moreover, you may make it transmit a recipe suitably from another apparatus via a dedicated line, for example. The recipe is read from the storage unit 152 according to an instruction from the user interface 151 as necessary, and the controller 150 executes processing according to the read recipe. A desired process is performed under the control of 150. In this example, under the control of the controller 150, the processing according to the SiCN film forming method according to the first embodiment is sequentially performed.

  The SiCN film forming method according to the first embodiment can be carried out by using a film forming apparatus 100 as shown in FIG.

<Deposition system: second example>
FIG. 8 is a horizontal sectional view schematically showing a second example of a film forming apparatus capable of performing the SiCN film forming method according to the first embodiment.

  The film forming apparatus is not limited to the vertical batch type as shown in FIG. For example, a horizontal batch type as shown in FIG. 8 may be used. FIG. 8 schematically shows a horizontal section of the processing chamber of the horizontal batch type film forming apparatus 200. In FIG. 8, illustration of a processing gas supply mechanism, an inert gas supply mechanism, an exhaust device, a heating device, a controller, and the like is omitted.

  As shown in FIG. 8, the film formation apparatus 200 places, for example, five wafers 1 on the turntable 201 and performs film formation on the five wafers 1. The turntable 201 is rotated clockwise, for example, with the wafer 1 placed thereon. The processing chamber 202 of the film forming apparatus 200 is divided into four processing stages. When the turntable 201 rotates, the wafer 1 rotates around the four processing stages in order.

  The first processing stage PS1 is a stage for performing step 1 shown in FIG. That is, in the processing stage PS1, Si source gas is supplied onto the surface to be processed of the wafer 1. A gas supply pipe 203 that supplies Si source gas is disposed above the processing stage PS1. The gas supply pipe 203 supplies Si raw material gas toward the surface to be processed of the wafer 1 that has been mounted on the turntable 201. An exhaust port 204 is provided on the downstream side of the processing stage PS1.

  The processing stage PS1 is also a loading / unloading stage for loading / unloading the wafer 1 into / from the processing chamber 202. The wafer 1 is carried into and out of the processing chamber 202 via a wafer carry-in / out opening 205. The carry-in / out port 205 is opened and closed by a gate valve 206. The next stage after the processing stage PS1 is the processing stage PS2.

  The processing stage PS2 is a stage that performs Step 2 shown in FIG. The processing stage PS2 is a narrow space, and the wafer 1 passes through the narrow space while being placed on the turntable 201. An inert gas is supplied from the gas supply pipe 207 into the narrow space. The process stage PS3 is followed by the process stage PS3.

  The processing stage PS3 is a stage that performs step 3 shown in FIG. A gas supply pipe 208 is disposed above the processing stage PS3. The gas supply pipe 208 supplies a 1,2,3-trizol-based compound gas toward the surface to be processed of the wafer 1 that has been placed on the turntable 201 and travels. An exhaust port 209 is provided on the downstream side of the processing stage PS3. Next to the processing stage PS3 is the processing stage PS4.

  The processing stage PS4 is a stage that performs step 4 shown in FIG. The processing stage PS4 is a narrow space like the processing stage PS2, and the wafer 1 passes through the narrow space while being placed on the turntable 201. An inert gas is supplied from a gas supply pipe 210 into the narrow space. After the processing stage PS4, the process returns to the first processing stage PS1.

  As described above, in the film forming apparatus 200, when the wafer 1 goes around, the steps 1 to 4 shown in FIG. 1 are completed. While the wafer 1 is placed on the turntable 201, the SiCN film is formed on the surface to be processed of the wafer 1 by rotating the wafer 1 a set number of times.

  The SiCN film forming method according to the first embodiment of the present invention can also be implemented by using a film forming apparatus 200 as shown in FIG.

  As described above, the present invention has been described with some embodiments. However, the present invention is not limited to the above embodiments, and various modifications can be made without departing from the spirit of the present invention.

For example, in the above embodiment, the processing conditions are specifically exemplified, but the processing conditions are not limited to the above specific examples. For example, the gas flow rate and the like are appropriately adjusted according to the volume of the processing chamber.
In addition, the present invention can be variously modified without departing from the gist thereof.

1 ... wafer, ₂ ... SiO 2 film, 3-1,3-2 ... Si film, 4,4-1,4-2 ... SiCN film.

Claims (6)

A SiCN film forming method for forming a SiCN film on a surface to be processed of an object to be processed,
Supplying Si source gas containing Si source into the processing chamber in which the object to be processed is accommodated;
After the step of supplying the Si source gas, a step of supplying a gas containing a nitriding agent into the processing chamber,
A method for forming a SiCN film, wherein a compound of nitrogen and carbon represented by the following general formula (1) is used as the nitriding agent.

However, in the said General formula (1), R < ¹ >, R < ² >, R < ³ > is a C1-C8 linear or branched alkyl group which may have a hydrogen atom or a substituent. The substituent for R ¹ , R ² and R ³ is a monoalkylamino group or a dialkylamino group substituted with a linear or branched alkyl group having 1 to 4 carbon atoms. Item 4. A method for forming a SiCN film according to Item 1. The method for forming a SiCN film according to claim 1, wherein the substituents of R ¹ , R ² , and R ³ are linear or branched alkoxy groups having 1 to 8 carbon atoms. The compound represented by the general formula (1) is
1H-1,2,3-triazole 1-methyl-1,2,3-triazole 1,4-dimethyl-1,2,3-triazole 1,4,5-trimethyl-1,2,3-triazole 1- It is ethyl-1,2,3-triazole 1,4-diethyl-1,2,3-triazole, or 1,4,5-triethyl-1,2,3-triazole. A method for forming the described SiCN film.   5. The method of forming a SiCN film according to claim 1, wherein the step of supplying a gas containing a nitriding agent into the processing chamber is performed without using plasma. 6. 6. The method of forming a SiCN film according to claim 1, wherein a film forming temperature of the SiCN film is 200 ° C. or more and 550 ° C. or less.

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