JP2003179054A - Method of forming insulation film and apparatus of forming the insulation film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of forming an insulation film having a low content of N-H bond. <P>SOLUTION: Hexamethyldisilazane gas, ammonia gas, and Argon gas are supplied into a chamber 12 in a vacuum, and a thin film of SiCN is formed with a thickness of about 1 to 10 nm on a surface of a wafer W. Subsequently, a pressure is reduced and the wafer W is heated while Argon gas is supplied. The annealing treatment excites the N-H bond in the thin film and dissociation removes H from the film. The formation of the thin film and the annealing treatment are repeated so as to form an SiCN film with a predetermined thickness. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming an insulating film, and more particularly to a method for forming an insulating film having a low NH bond content and an apparatus therefor.

[0002]

2. Description of the Related Art In recent years, miniaturization of semiconductor devices has progressed, and the design rule has reached 0.13 μm. 0.
In the 13 μm generation, the wiring performance is dominant with respect to the semiconductor device performance, and the wiring delay greatly influences the operation speed of the device. Therefore, in order to manufacture a high-speed circuit, it is necessary to suppress the wiring delay as much as possible.

In order to reduce the wiring delay, the wiring material is shifting from aluminum alloy to copper. Copper has low specific resistance and high electromigration resistance, and is suitably used for high-speed circuit construction. However, unlike aluminum alloys, it is difficult to form a wiring pattern by chemical etching with copper. Therefore, a so-called damascene method is adopted as a method for forming copper wiring.

Hereinafter, the damascene method will be described with reference to FIGS.
This will be described with reference to (e). First, as shown in FIG. 8A, a hard mask 102 such as a silicon nitride film is formed on an interlayer insulating film 101 such as a silicon oxide film. Subsequently, as shown in FIG. 8B, an opening 103 is formed in the hard mask 102 by photolithography and etching.
To form. At this time, etching is performed on the hard mask 10.
2 is etched, but the interlayer insulating film 101 is not etched.

Then, the interlayer insulating film 101 is etched using the hard mask 102 having the opening 103 as a mask. As a result, the trench hole 104 as shown in FIG. 8C is formed. Furthermore, trench hole 1
After forming a barrier metal film 105 such as TiN on the entire surface including the inner wall of 04, the inside of the trench hole 104 is filled with the wiring metal 106 by plating, as shown in FIG. 8D. Finally, the unnecessary metal film is removed by chemical mechanical polishing (CMP) to form a copper wiring layer 107 as shown in FIG. 8 (e).

In recent years, a SiCN-based film has been developed as the hard mask 102 used in the damascene method.
The SiCN-based film is composed mainly of silicon (Si), carbon (C), and nitrogen (N). The SiCN film is
For example, it is formed using hexamethyldisilazane and ammonia as starting materials. The SiCN-based film has advantages such as a relatively low relative dielectric constant and a high barrier property against copper.

[0007]

However, when the damascene method is performed using the hard mask 102 made of the SiCN-based film, the resist is not exposed according to the mask pattern when performing lithography for forming the opening 103. Is often recognized. Such a phenomenon is called resist poisoning.

It has been confirmed that resist poisoning in the case of using a SiCN-based film is more likely to occur as the number of nitrogen-hydrogen bonds (N—H bonds) in the film increases. It is considered that this is because the N—H bond in the film is desorbed as ammonia (NH ₃ ) in the heat treatment in the lithography process. Therefore, SiCN with a small number of NH bonds in the film
Obtaining a system film is necessary to form a wiring pattern with high accuracy.

However, conventionally, there is no method capable of forming a SiCN-based film having a low N--H bond content in the film, and a highly reliable semiconductor is obtained when the SiCN-based film is used as a hard mask. There was a risk that the device could not be manufactured.

In view of the above circumstances, it is an object of the present invention to provide a method for forming an insulating film and an apparatus therefor capable of suppressing the occurrence of resist poisoning. Further, the present invention is
It is an object of the present invention to provide a method for forming an insulating film that can be suitably used for forming a buried wiring layer.

[0011]

In order to achieve the above object, a method of forming an insulating film according to the present invention is a method of forming an insulating film containing hydrogen, which is composed mainly of silicon, carbon and nitrogen, and which is bonded to the nitrogen. A thin film forming step of forming a thin film; and a hydrogen removing step of exciting nitrogen hydrogen bonds contained in the thin film to dissociate the nitrogen hydrogen bonds to remove hydrogen from the nitrogen hydrogen bonds. To do.

According to the above structure, it is possible to form an insulating film having a low nitrogen-hydrogen bond content in the film. As a result, ammonia (N
It is possible to suppress the occurrence of so-called resist poisoning, which is the deterioration of the resist pattern due to the generation of H ₃ ). Therefore, the insulating film functioning as a hard mask used for forming the embedded wiring layer can be formed with high reliability.

In the above structure, it is preferable that at least the nitrogen-containing compound and the silicon compound containing carbon, nitrogen and hydrogen are reacted with each other in the thin film forming step to form the insulating film.

In the above structure, the hydrogen removing step is
At least a step of heating the thin film under a reduced pressure atmosphere,
Any one of a step of heating the thin film under a diluting gas flow and a step of exposing the thin film to plasma of an inert gas may be included.

In the above structure, it is desirable that the thin film forming step and the hydrogen removing step are alternately repeated to laminate the thin films to form the insulating film having a predetermined thickness.

In the above structure, it is desirable that the thin film is formed to a thickness of 1 nm to 50 nm in the thin film forming step.

In order to achieve the above object, an apparatus for forming an insulating film according to the present invention comprises a chamber, a raw material supply section for supplying a raw material for forming an insulating film to the chamber, and a predetermined pressure reduction degree in the chamber. A vacuum evacuation unit that maintains the object to be processed, a heating unit that places the object to be processed and heats it to a predetermined temperature, a plasma generation unit that generates plasma to contact the object to be processed in the chamber, the raw material supply unit, and By controlling the evacuation unit, the heating unit, the plasma generation unit, to form a thin film of an insulating film containing hydrogen, which is composed mainly of silicon and nitrogen and is bonded to the nitrogen, on the object to be processed, Any one of a step of heating the thin film under a reduced pressure atmosphere, a step of heating the thin film under a diluting gas flow, and a step of exposing the thin film to plasma of an inert gas, or alone. In combination with extent, by exciting nitrogen hydrogen bonds contained in the thin film, and a control unit for removing hydrogen from the nitrogen hydrogen bonds by dissociating the nitrogen hydrogen bonds, characterized in that.

In the above structure, the control section alternately repeats the step of forming a thin film and the step of removing hydrogen from the nitrogen-hydrogen bonds of the thin film to stack the thin films and form an insulating film having a predetermined thickness. Can be formed.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION A method for forming an insulating film according to this embodiment will be described below with reference to the drawings. According to the insulating film forming method of the present embodiment, silicon (S
A film composed of i), carbon (C), and nitrogen (N) as main components (hereinafter, SiCN-based film) is formed. SiCN
The system film functions as a hard mask for forming a buried wiring layer in the interlayer insulating film by using the damascene method or the dual damascene method.

FIG. 1 shows a structural example of an apparatus for carrying out the method for forming an insulating film according to this embodiment. The processing apparatus according to the present embodiment is configured as a so-called parallel plate type plasma CVD apparatus having vertically opposed electrodes, and a SiCN-based film C is formed on the surface of a semiconductor wafer (hereinafter, wafer W).
The film is formed by VD.

Referring to FIG. 1, the processing apparatus 11 has a cylindrical chamber 12. The chamber 12 is made of a conductive material such as aluminum that has been anodized (anodized). Further, the chamber 12 is grounded.

An exhaust port 13 is provided at the bottom of the chamber 12. An exhaust device 14 including a vacuum pump such as a turbo molecular pump is connected to the exhaust port 13. The exhaust device 14 exhausts the inside of the chamber 12 to a predetermined pressure. A gate valve 15 is provided on the side wall of the chamber 12. With the gate valve 15 open,
The wafer W is carried in and out from the outside of the chamber 12.

A substantially columnar susceptor support 16 is provided on the bottom of the chamber 12. A susceptor 17 as a mounting table for the wafer W is provided on the susceptor support 16. The susceptor 17 has a function as a lower electrode, and the susceptor support 16 and the susceptor 17 are insulated by an insulator 18 such as ceramic.

A lower coolant channel 19 is provided inside the susceptor support 16. A coolant circulates in the lower coolant channel 19. By circulating the coolant through the lower coolant channel 19, the susceptor 17 and the wafer W are controlled to a desired temperature.

A semiconductor wafer W is mounted on the susceptor support 16.
Lift pins 20 are provided for delivering and receiving, and the lift pins 20 can be lifted and lowered by a cylinder (not shown). Further, the susceptor 17 is formed in a disc shape having a convex upper center portion, and an electrostatic chuck (not shown) having substantially the same shape as the wafer W is provided thereon. The wafer W placed on the susceptor 17 is electrostatically attracted by applying a DC voltage.

A first high frequency power supply 21 is connected to a susceptor 17 functioning as a lower electrode via a first matching box 22. The first high frequency power source 21 is 0.1 to 13
It has a frequency in the range of MHz. By applying the frequency in the above range to the first high-frequency power source 21, effects such as reduction of damage to the object to be processed can be obtained.

Above the susceptor 17, the susceptor 1
A shower head 23 is provided so as to oppose in parallel with 7. An electrode plate 25 made of aluminum or the like having a large number of gas holes 24 is provided on the surface of the shower head 23 facing the susceptor 17. The shower head 23 is supported on the ceiling portion of the chamber 12 by the electrode support 26. Inside the shower head 23,
An upper coolant channel 27 is provided. Upper refrigerant channel 27
Refrigerant circulates in the shower head 23, and the shower head 23 is controlled to a desired temperature.

Further, a gas introducing pipe 28 is connected to the shower head 23. The gas introduction pipe 28 includes a hexamethyldisilazane (HMDS) gas source 29, an ammonia (NH ₃ ) gas source 30, and an argon (Ar) gas source 31.
And are connected via a mass flow controller, a valve, and the like (not shown).

The processing gas from each of the gas sources 29 to 31 is mixed and supplied to a hollow portion (not shown) formed inside the shower head 23 through the gas introduction pipe 28. The gas supplied into the shower head 23 is diffused in the hollow portion and is supplied to the surface of the wafer W from the gas holes 24 of the shower head 23.

A second high frequency power supply 32 is connected to the shower head 23, and a second matching unit 33 is interposed in the power supply line. The second high frequency power source 32 is
The shower head 2 has a frequency in the range of up to 150 MHz, and by applying such a high frequency.
3 functions as an upper electrode, and forms a high density plasma in the chamber 12 in a preferable dissociated state.

The controller 34 controls the overall operation of the processing apparatus 11 including the film formation processing on the wafer W. In addition,
Detailed operation of the controller 34 is omitted for easy understanding.

A method for forming an insulating film using the processing apparatus 11 will be described below. FIG. 2 shows a timing chart of the manufacturing method of the present embodiment. Note that the timing diagram shown in FIG. 2 is an example, and any configuration may be used as long as it has the same effect.

First, an unprocessed wafer W having an insulating film on its surface is carried into the chamber 12 via the gate valve 15 which is held by a transfer arm (not shown) and is open. The transfer arm transfers the wafer W to the lift pins 20 in the raised position and withdraws from the chamber 12. After that, the wafer W is placed on the susceptor 17 by lowering the lift pins 20. The wafer W is fixed on the susceptor 17 by an electrostatic chuck.

Next, the controller 34 controls the exhaust device 1
4, the inside of the chamber 12 is, for example, 1.3 × 10
^-2 Pa (1 x ^10-4 Torr). At the same time, the controller 34 changes the temperature of the susceptor 17 to 40
The temperature is set to 0 ° C. or lower, for example, 350 ° C.

Thereafter, the HMDs are fed from the respective gas sources 29 to 31.
S, NH ₃ and Ar gases are supplied to the chamber 1 at a predetermined flow rate.
2 is supplied. The mixed gas of the processing gas is uniformly discharged from the gas holes 24 of the shower head 23 toward the wafer W. The supply of HMDS, NH ₃ and Ar is performed, for example, at a flow rate ratio (each sccm) of HMDS / NH ₃ / Ar = 30/10/100.

After that, from the second high frequency power source 32, for example, high frequency power of 60 MHz is applied to the upper electrode (shower head 23). As a result, a high frequency electric field is generated between the upper electrode and the lower electrode (susceptor 17), and plasma of the mixed gas is generated. On the other hand, the first high frequency power source 21
Then, for example, a high frequency power of 2 MHz is applied to the lower electrode. As a result, the ions in the plasma are drawn toward the susceptor 17 side, and the plasma density near the surface of the wafer W is increased. By applying high-frequency power to the upper and lower electrodes 23 and 17, plasma of the processing gas is generated, and a chemical reaction on the surface of the wafer W by the plasma forms a SiCN-based film on the surface of the wafer W. .

Here, the controller 34 controls the upper and lower electrodes 2
High frequency power is applied to the wafers 3 and 17 for several seconds, and the wafer W
On the surface, for example, a thin film of a SiCN-based film having a thickness of 1 nm to 5 nm (10Å to 50Å) is formed. After a predetermined time from the start of the application of the high frequency power, the controller 34 stops the application of the high frequency power to the upper electrode and the lower electrode and stops the introduction of the HMDS and NH ₃ from the HMDS gas source 29 and the NH ₃ gas source 30. To do. With that, the film forming process is completed. At this time, Ar is flowing in the chamber 12.

The controller 34 purges the chamber 12 with Ar gas for a predetermined time to remove the remaining HMDS and NH ₃ from the chamber 12. At this time, the controller 34 changes the temperature of the susceptor 17 to 45
The temperature is set to 0 ° C. or lower, for example, 400 ° C., and the pressure is set to, for example, 1.3 × 10 ⁻³ Pa (1 × 10 ⁻⁵ T).
orr).

The controller 34 is provided with 40 of the susceptor 17.
Annealing is performed by heating at 0 ° C. for a predetermined time. In the annealing step, the N—H bond existing in the SiCN-based film formed on the surface of the wafer W is excited, whereby the N—H bond is dissociated and hydrogen (H) is desorbed. The released H is H
₂ etc. are exhausted outside the chamber 12 as exhaust gas. Here, the formed SiCN-based film has a thickness of 1 n.
It is a thin film of several atomic layers with a thickness of about m to 5 nm. Therefore, desorption of H easily occurs even on the surface other than the film surface, and SiCN
Removal of N—H bonds from the system membrane is sufficient.

Here, the fact that the absorption peak of N—H bond near 1200 cm ^−1, which was present in the thin film just after the film formation, disappeared completely after annealing, for example, FT
It is confirmed by IR (Fourier transform infrared spectroscopy). Therefore, it can be seen that the N—H bond is surely removed from the formed thin film.

The controller 34 performs the above annealing treatment for a sufficient time to remove H from the N--H bonds in the film. After a predetermined time, the controller 34 lowers the temperature of the susceptor 17 to the temperature (350 ° C.) at the time of film formation while flowing Ar into the chamber 12, and the pressure is 1.3 × 10 5.
^-2 Pa (1 x ^10-4 Torr).

After that, the controller 34 starts the film formation of the above-mentioned SiCN-based film again. That is,
The controller 34 controls the HMDS and NH from the gas source.
Supply of ₃ is started. Next, high frequency power is applied to the upper electrode and the lower electrode. By performing the film forming process for a predetermined time in the same manner as above, a thin film of a SiCN-based film having a thickness of 1 nm to 5 nm is newly formed on the already formed thin film.

After the film forming process, the controller 34 stops applying the high frequency power to the upper electrode and the lower electrode,
Stop the supply of MDS and NH ₃ . Next, the temperature of the susceptor 17 is set to 400 ° C., the pressure inside the chamber 12 is set to 1.3 × 10 ⁻³ Pa (1 × 10 ⁻⁵ Torr), and the inside of the chamber 12 is purged with Ar gas.

The controller 34 again returns to the susceptor 17
Is held at 400 ° C. for a predetermined time, and an annealing process is performed. As a result, H of N—H bond in the SiCN-based film, in particular, the newly formed film is released. In this way, the NH bond is removed from the newly formed SiCN-based film.

Thereafter, the controller 34 sets the susceptor 17
Is lowered to 350 ° C., and the pressure in the chamber 12 is set to 1.3 × 10 ⁻² Pa (1 × 10 ⁻⁴ Torr). In this way, the controller 34 repeats the film forming process, the annealing process, and the purging between the processes. The controller 34 is an S formed by stacking thin films.
The total thickness of the iCN-based film is a predetermined value, for example, 500
The above processes are repeated the number of times reaching nm (5000Å).

After repeating the above processes a predetermined number of times, the controller 34 stops the heating of the susceptor 17 and returns the pressure inside the chamber 12 to about the pressure outside the chamber 12. After that, the electrostatic chuck is released and the lift pin 20 rises. Next, the gate valve 15 is opened, and the transfer arm enters the chamber 12. The wafer W is carried out of the chamber 12 by the transfer arm.

Thus, the process of forming the SiCN-based film using the processing apparatus 11 is completed, and the insulating film 40 as shown in FIG.
As a result, the SiCN-based film 41 is formed thereon.
The wafer W is then subjected to patterning of the SiCN-based film 41 and then etching of the insulating film 40 using the patterned SiCN-based film 41 as a hard mask. For example, the embedded wiring as shown in FIGS. Layer 42 is formed.

4 to 6, the wiring layer 42 is provided via a barrier layer 42a. Here, the wiring layer 42 shown in FIG. 4 is an example formed by using a damascene method.
The wiring layer 42 shown in FIGS. 5 and 6 is formed by using the dual damascene method to form the trench hole 43 and the via hole 4
4 and 4 are formed. In addition, the wiring layer 42 shown in FIG.
Is formed by using one hard mask (SiCN-based film 41), and the wiring layer 42 shown in FIG. 6 is formed by using two hard masks.

As described above, according to the present invention, S
The iCN film is formed by laminating thin films having a thickness of several nm. During the film forming process of the thin film, the N—H bond in the thin film (particularly the film surface) is removed by thermal annealing. As a result, a SiCN-based film having a low N—H bond content in the film is finally formed.

[0050] By forming a small SiCN-based film of NH bond content, it can be suppressed occurrence of NH ₃ at the time of heating in a lithographic process. FIG. 7 shows the result of gas analysis of NH ₃ generated under the resist processing conditions in a thin film in which the amount of N—H bonds remaining in the film was changed by changing the annealing time. As shown in FIG. 7, the NH bond existing in the film and the generated NH ₃ intensity show a positive correlation, and the NH ₃ intensity generated also decreases as the NH bond decreases. From this, by using an insulating film formed by adequately removing N—H bonds from a thin film by appropriate annealing treatment, it is possible to reduce alteration of resist (so-called resist poisoning), and to improve reliability. High-performance lithography process (patterning)
It turns out that is possible. Therefore, a highly reliable wiring layer forming process (especially damascene process) using the SiCN-based film as a hard mask becomes possible. The resist poisoning can be quantified by, for example, taking an SEM (scanning electron microscope) photograph of the surface of the patterned substrate and measuring the distance between the patterned lines of the image. This is because when resist poisoning occurs, the line edge is scraped, the depth of focus of the microscope does not match, and the line edge is in a so-called defocused state, so that the measurement interval becomes smaller than the design interval.

The present invention is not limited to the above embodiment,
Various modifications and applications are possible. Hereinafter, modifications of the above-described embodiment applicable to the present invention will be described.

In the above embodiment, the SiCN-based film is made of H
MDS and NH ₃ were formed as source gas compounds. However, the raw material compound may be any compound as long as it is a compound containing Si, C, and N, and a SiCN-based film is formed alone or by a reaction in which these are appropriately combined.

For example, three kinds containing Si, C and N respectively
It is also possible to use the source gas compound of
SiH as contained compound_FourAs C-containing compound_Two
H_Four, CH_Four, C_TwoH₆, C_ThreeH₈, C_TwoH_Two, N
N as a containing compound_Two, NF _Three, N_TwoO, N_TwoO_Four, N
O, N_ThreeH₈Etc. may be appropriately combined.

A raw material compound containing Si and C, and N
It is also possible to form a film by mixing two kinds of raw material compounds containing
Yes. In this case, the above-mentioned N-containing compound is used.
Alkylsilane, a compound containing Si and C
Use organic silanes such as lucoxysilane
Can be combined with. As an alkyl silane, for example
For example, methylsilane (SiH_Three(CH_Three)), Dimethyl
Run (SiH_Two(CH _Three)_Two), Trimethylsilane (S
iH (CH_Three)_Three), Tetramethylsilane (Si (CH
_Three)_Four) And methylated silanes.
As silane, for example, trimethoxymethylsilane
(Si (CH_Three) (OCH_Three)_Three) Methoxylation
Silane may be mentioned. On the contrary, Si and N
So that the source gas containing C and the source gas containing C are mixed.
Good. In this case, the C-containing compound is the above
The compound containing Si and N selected from
For example, disilazane (SiH_Three-NH-SiH_Three) Is used
Then, these may be combined appropriately.

Further, HM containing all of Si, C and N
It is also possible to use compounds other than DS as source gas
is there. Examples of such compounds include a silazane bond (-S
It is possible to use an organic silazane compound having i-N-).
it can. When an organic silazane compound is used, for example,
The film can be formed by thermal polymerization by the plasma CVD method.
It Examples of usable organic silazane compounds include:
Triethylsilazane (SiEt_ThreeNH_Two), Tripropy
Lucilazane (SiPr_ThreeNH_Two), Triphenylsilaza
(SiPh_ThreeNH_Two), Tetramethyldisilazane (S
iMe_TwoH-NH-SiMe_TwoH), hexaethyldishes
Razan (SiEt_Three-NH-SiEt_Three), Hexafe
Nildisilazane (SiPh_Three-NH-SiPh_Three), F
Ptamethyldisilazane (SiMe_Three-NMe-SiMe
_Three), Dipropyl-tetramethyldisilazane (SiPr
Me_Two-NH-SiPrMe_Two), Di-n-butyl-te
Tramethyldisilazane (SiBuMe_Two-NH-SiB
uMe_Two), Di-n-octyl-tetramethyldisilazaza
(SiOcMe_Two-NH-SiOcMe_Two), Jivini
Le-tetramethyldisilazane (CH_Two= CH-SiMe
_Two-NH-SiMe _Two-CH = CH_Two) Chained chilli
Zan compound, triethyl-trimethylcyclotrisilaza
((SiEtH-NMe)_Three), 1, 1, 3, 3,
5,5-hexamethylcyclotrisilazane (HMCT
S) and 1,2,3,4,5,6-hexamethylcycloto
Hexamethylcyclotri containing isomers such as lisilazane
Silazane ((SiMe_Two-NH)_Three), Hexaethyl
Clotrisilazane ((SiEt_Two-NH)_Three), Hexa
Phenylcyclotrisilazane ((SiPh_Two-N
H)_Three), Octamethylcyclotetrasilazane ((Si
Me_Two-NH)_Four), Octaethylcyclotetrasilaza
((SiEt_Two-NH)_Four), Tetraethyl-tetra
Methylcyclotetrasilazane ((SiHEt-NMe)
_Four), Cyanopropylmethylcyclosilazane (SiMe
NC (CH_Two)_Three-NH), tetraphenyldimethyldi
Silazane (SiMePh_Two-NH-SiMePh_Two),
Diphenyl-tetramethyldisilazane ((SiMe_TwoP
h)_Two-NH), trivinyl-trimethylcyclotrishi
Razan ((CH_Two= CH-SiMe-NH)_Three), Tet
Labinyl-tetramethylcyclotetrasilazane (CH_Two
= CH-SiMe-NH)_FourCyclic silazane compounds such as
Is mentioned. In the above formula, Me is a methyl group (CH_Three),
Et is an ethyl group (C_TwoH₅), Pr is a propyl group (C_Three
H₇) And Oc are n-octyl groups (n-C₈H₁₇), P
h is a phenyl group (C₆H₅) Is shown.

Further, in the above example, the source gas containing Si, C and N may be one each, but the present invention is not limited to this. For example, in addition to organosilane and N ₂ , C ₂ H ₂ may be used. It is also possible to use a gas added with or a gas added with N ₂ in addition to the organic silazane.

In the above embodiment, a parallel plate type plasma CVD apparatus is used for the film forming process. However, the present invention is not limited to this, and plasma processing of ECR type, ICP type, TCP type, helicon type or the like may be used. Moreover, not only plasma CVD but thermal CVD may be used. Further, so-called ALD (Atomic Layer Deposition) or ALE (Atomic Layer Epitaxy) for adsorbing the reactants atomic layer by atomic layer to form a film at the atomic layer level may be applied.

In the above embodiment, the N—H bond removal treatment is performed by exciting the N—H bond by heating under reduced pressure. However, the method of exciting the N—H bond is not limited to this. For example, plasma annealing may be used. In this case, the thin film of the SiCN-based film may be exposed to the plasma of an inert gas such as Ar, He, Ne, Xe, N ₂ . By using the plasma annealing, not only the desorption of H from the N—H bond but also the N—H bond can be removed by activating the N—H bond by extracting H by an active species such as Ar ion.

In the above embodiment, the SiCN film is used as a hard mask for etching. However, the film is not limited to this, and may be used as a film for other purposes such as a barrier layer provided on the wiring layer to suppress diffusion of the wiring material.

In the above-mentioned embodiment, the SiCN-based film has been described as an example. However, the present invention is not limited to this, and the present invention can be applied to an insulating film containing an N—H bond, such as a SiN-based film containing at least nitrogen and hydrogen.

Further, the processing apparatus 11 of the above embodiment may be combined with an etcher or the like. In this case, a clustering system including the processing device 11 or an inline system can be used.

[0062]

As described above, according to the present invention,
Provided are a method and an apparatus for forming an insulating film capable of suppressing the occurrence of resist poisoning.

[Brief description of drawings]

FIG. 1 is a diagram showing a configuration of a processing apparatus according to an embodiment of the present invention.

FIG. 2 is a timing chart of an insulating film forming method according to an embodiment of the present invention.

FIG. 3 is a diagram showing a configuration of a resultant product formed by the insulating film forming method according to the embodiment of the present invention.

FIG. 4 is a diagram in which a wiring layer is formed on a resultant formed by the insulating film forming method according to the embodiment of the present invention.

FIG. 5 is a diagram in which a wiring layer is formed on a resultant product formed by the insulating film forming method according to the embodiment of the present invention.

FIG. 6 is a diagram in which a wiring layer is formed on a resultant product formed by the insulating film forming method according to the embodiment of the present invention.

FIG. 7 shows N of a thin film formed by changing annealing conditions.
It is a diagram showing a relationship between detected intensity of the NH ₃ gas during -H binding amount and the resist process.

FIG. 8 is a diagram showing a step of forming a wiring layer using a damascene method.

[Explanation of symbols]

11 Processing Device 12 Chamber 13 Exhaust Port 14 Exhaust Device 15 Gate Valve 16 Susceptor Support 17 Susceptor 18 Insulator 19 Lower Refrigerant Flow Path 20 Lift Pin 21 First High Frequency Power Supply 22 First Matcher 23 Shower Head 24 Gas Hole 25 Electrode Plate 26 Electrode Support 27 Upper Refrigerant Flow Path 28 Gas Inlet Tube 29 HMDS Gas Source 30 NH ₃ Gas Source 31 Ar Gas Source 32 Second High Frequency Power Supply 33 Second Matching Machine 34 Controller

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 4K030 AA06 AA09 AA13 BA29 BA41                       CA04 CA12 DA09 FA03 JA01                       KA41 LA02                 5F033 QQ28 SS01 SS03 SS15                 5F045 AA08 AB31 AB33 AC08 AC12                       AC16 AD07 AE11 BB14 BB16                       DC64 DP03 DQ10 EB02 EF05                       EH05 EH14 EH19 HA16 HA23                 5F058 BA20 BC08 BC10 BC20 BF07                       BF27 BF30 BF37 BF39 BF80                       BJ02

Claims (7)

[Claims] 1. A thin film forming step of forming a thin film of an insulating film which is composed mainly of silicon, carbon and nitrogen and which contains hydrogen bonded to the nitrogen, and a nitrogen hydrogen bond contained in the thin film is excited, A hydrogen removing step of dissociating the nitrogen-hydrogen bonds to remove hydrogen from the nitrogen-hydrogen bonds, the method comprising: forming an insulating film. 2. The insulating film is formed by reacting at least a nitrogen-containing compound with a silicon compound containing carbon, nitrogen and hydrogen in the thin film forming step. Method of forming insulating film. 3. The hydrogen removing step comprises at least a step of heating the thin film under a reduced pressure atmosphere, a step of heating the thin film under a diluting gas flow, and a step of exposing the thin film to plasma of an inert gas. Including any one step,
The method according to claim 1, wherein the insulating film is formed. 4. The thin film forming step and the hydrogen removing step are alternately repeated to stack the thin films to form the insulating film having a predetermined thickness.
The method for forming an insulating film according to claim 1. 5. The thin film is formed to a thickness of 1 nm in the thin film forming step.
The method for forming an insulating film according to claim 1, wherein the insulating film is formed with a thickness of ˜50 nm. 6. A chamber, a raw material supply unit for supplying a raw material for forming an insulating film to the chamber, a vacuum exhaust unit for maintaining the inside of the chamber at a predetermined pressure reduction degree, and an object to be processed placed thereon. A heating unit for heating to a predetermined temperature, a plasma generation unit for generating a plasma to be brought into contact with the object to be processed in the chamber, a raw material supply unit, the vacuum exhaust unit, the heating unit, and the plasma generation unit are controlled. The object to be processed is formed with a thin film of an insulating film containing hydrogen which is composed mainly of silicon and nitrogen and which is bonded to the nitrogen, and at least a step of heating the thin film under a reduced pressure atmosphere, under a diluting gas flow. One of the steps of heating the thin film and exposing the thin film to plasma of an inert gas is used alone or in combination with other steps to excite nitrogen-hydrogen bonds contained in the thin film. , Forming apparatus of the insulating film, characterized in that it comprises a control unit for removing hydrogen from the nitrogen hydrogen bonds by dissociating the nitrogen hydrogen bonds. 7. The control unit alternately repeats a step of forming a thin film and a step of removing hydrogen from nitrogen-hydrogen bonds of the thin film to stack the thin films to form an insulating film having a predetermined thickness. The insulating film forming apparatus according to claim 6, wherein.