JP2000106357A - Manufacture of semiconductor device and method for forming insulating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent an organic insulating film from being oxidized, even when the organic insulating film is etched. SOLUTION: On a semiconductor substrate 100, a first metallic wiring 101, a silicon nitride film 102, a first organic film 103 whose main component is an organic component, a silicon oxide film 104, a second organic film 105A which with its main component being an organic component, is patterned, and a mask pattern 108 comprising a titanium nitride film is formed, and then the silicon oxide film 104 is etched to form a patterned silicon oxide film 104A. Then a patterned second organic film 105A and the first organic film 103 are dry-etched using H2O plasma, respectively, so that a wiring groove 111 is formed on the patterned second organic film 105A, while a patterned first organic film 103A comprising a contact hole 110 is formed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for forming an organic insulating film mainly containing an organic component on a substrate, and a method for manufacturing a semiconductor device for patterning an organic insulating film mainly containing an organic component. .

[0002]

2. Description of the Related Art With the progress of high integration of semiconductor integrated circuits,
An increase in wiring delay time caused by an increase in capacitance between wirings, which is a parasitic capacitance between metal wirings, hinders performance enhancement of a semiconductor integrated circuit. The wiring delay time is a so-called RC delay which is proportional to the product of the resistance of the metal wiring and the capacitance between the wirings.

Therefore, in order to reduce the wiring delay time, it is necessary to reduce the resistance of the metal wiring or reduce the capacitance between the wirings.

As a method of reducing the capacitance between wirings, it is conceivable to reduce the relative dielectric constant of an interlayer insulating film formed between metal wirings, and a material different from a conventional silicon oxide film is used as the interlayer insulating film. The use of is considered.

In a semiconductor integrated circuit having a minimum processing size of 0.25 μm, a fluorine-added silicon oxide film obtained by adding fluorine to a silicon oxide film is being used as an insulating film. The relative dielectric constant of the fluorine-added silicon oxide film is
Since it is about 3.3 to 3.9, which is smaller than 4.2 to 4.5 of the conventional silicon oxide film, it is reported that it is effective in reducing the capacitance between wirings and, in turn, the wiring delay time. ing.

However, it is clear that the miniaturization of the semiconductor integrated circuit is further advanced, and the minimum processing size is 0.1%.
In a semiconductor integrated circuit of 3 μm or less, the relative dielectric constant is 2.50.
It is considered that the use of the following insulating films is indispensable for realizing a practical processing speed.

Therefore, a low dielectric constant SOG is used as an insulating film having a relative dielectric constant much smaller than that of a fluorine-added silicon oxide film.
(Spin-on-glass) films, organic films, and porous films have been studied. When examining currently known insulating films from the viewpoint of material properties, organic films are promising because of their low dielectric constants.

[0008] Among organic films, a perfluorocarbon polymer has a fluorine-carbon bond and is a material having the lowest relative dielectric constant. The relative dielectric constant of the perfluorocarbon polymer is at least about 1.9.

As a typical method for forming perfluorocarbon, a method using plasma CVD has been reported. Plasma CVD using perfluorocarbon as material
Is generally called an amorphous fluorocarbon (a-CF) film in many cases.

[0010]

As described above,
As an insulating film having a small relative dielectric constant, an organic insulating film containing an organic component as a main component has been proposed, but the organic insulating film has various problems as described below.

First, when the organic insulating film is etched using oxygen plasma, there is a problem that the organic insulating film is deteriorated by the oxygen plasma. That is, the organic insulating film is oxidized by active oxygen radicals generated in the plasma to generate an unstable carbonyl compound, and the generated carbonyl compound is thermally decomposed by a heat treatment performed later. When the carbonyl compound is thermally decomposed, low-molecular gas such as carbon dioxide is generated, and the generated low-molecular gas impedes the formation of a barrier metal layer deposited in a concave portion of the organic insulating film, or the organic insulating film has a low molecular weight. A silicon oxide film or a metal film deposited on the film is separated from the organic insulating film.

Second, when the organic insulating film is deposited by the CVD method, radicals are generated on the surface of the organic insulating film,
Since the generated radicals react with oxygen, the organic insulating film is oxidized. When the organic insulating film is oxidized, the polymer constituting the organic insulating film is cut off, and low-molecular gas such as toluene, phenol or carbon dioxide is generated, and the generated low-molecular gas is deposited on the concave portions of the organic insulating film. This causes problems such as hindering the formation of a barrier metal layer to be formed, and peeling off a silicon oxide film or a metal film deposited on the organic insulating film from the organic insulating film.

Third, when the organic insulating film is etched in an oxidizing atmosphere to pattern the organic insulating film, a portion of the organic insulating film exposed by the etching is oxidized. When the organic insulating film is oxidized, as described above, the polymer that forms the organic insulating film is cut and low-molecular gas is generated, and the generated low-molecular gas is deposited on the recesses and the like of the organic insulating film. There are problems in that the formation of a layer is hindered, and a silicon oxide film, a metal film, or the like deposited on the organic insulating film is separated from the organic insulating film.

Fourth, when an organic insulating film is deposited on a base film made of a silicon oxide film or a metal film, if the base film is hydrophilic, water is adsorbed on the surface of the base film. There is a problem that the action of water deteriorates the adhesion between the organic insulating film and the base film. In particular, when the organic insulating film is fluorine-
When it has a carbon bond, the adhesion to the underlying film is significantly reduced.

Fifth, when a silicon oxide film serving as, for example, an etching mask or an etching stopper is formed on the organic insulating film, a portion of the organic insulating film that is in contact with the silicon oxide film is oxidized. When the organic insulating film is oxidized, as described above, the polymer that forms the organic insulating film is cut and low-molecular gas is generated, and the generated low-molecular gas is deposited on the recesses and the like of the organic insulating film. There are problems in that the formation of a layer is hindered, and a silicon oxide film, a metal film, or the like deposited on the organic insulating film is separated from the organic insulating film.

Sixth, when an organic insulating film is deposited by a coating method, it is necessary to perform heat treatment such as baking and baking on the organic insulating film. The organic insulating film is oxidized. When the organic insulating film is oxidized, as described above, the polymer that forms the organic insulating film is cut and low-molecular gas is generated, and the generated low-molecular gas is deposited on the recesses and the like of the organic insulating film. There are problems in that the formation of a layer is hindered, and a silicon oxide film, a metal film, or the like deposited on the organic insulating film is separated from the organic insulating film.

In view of the above, a first object of the present invention is to prevent the organic insulating film from being oxidized even when the organic insulating film is etched. Nevertheless, the second object is to prevent the organic insulating film from being oxidized, and even though the organic insulating film is etched in an oxidizing atmosphere, a portion of the organic insulating film exposed by the etching is removed. The third object is to prevent oxidation, and the fourth object is to improve the adhesion between the organic insulating film and the underlying film. When forming a silicon oxide film on the organic insulating film, A fifth object of the present invention is to prevent a portion of the insulating film in contact with the silicon oxide film from being oxidized. In a case where the organic insulating film is deposited by a coating method, a heat treatment step for the organic insulating film is performed. There are, an organic insulating film is a sixth object of that to avoid oxidation.

[0018]

In order to achieve the first object, a first method of manufacturing a semiconductor device according to the present invention comprises:
The method includes a step of depositing an organic insulating film mainly containing an organic component on a substrate, and a step of patterning the organic insulating film by etching the organic insulating film with H ₂ O plasma.

According to the first method for manufacturing a semiconductor device, an organic insulating film mainly composed of an organic component deposited on a substrate is etched by H ₂ O plasma.
Since the density of active O radicals is very low in H ₂ O plasma as compared with O ₂ plasma, OH radicals mainly act on etching of the organic insulating film. Since OH radicals are much less oxidizable than O radicals, it is considered that etching of the organic insulating film proceeds by abstraction of hydrogen by OH. For this reason, the situation where a carbonyl compound is generated by oxidation of the organic insulating film is avoided.

In order to achieve the first object, a second method for manufacturing a semiconductor device according to the present invention comprises the steps of: depositing an organic insulating film mainly containing an organic component on a substrate; On the other hand, etching by CO plasma,
Patterning the organic insulating film.

According to the second method of manufacturing a semiconductor device, an organic insulating film mainly composed of an organic component deposited on a substrate is etched by CO plasma.
Since the density of active O radicals is very low in O plasma as compared with O ₂ plasma, CO radicals mainly act on etching of the organic insulating film.
Since the CO radical is much less oxidizable than the O radical, it is considered that the etching of the organic insulating film proceeds by extracting hydrogen with CO. For this reason,
A situation in which a carbonyl compound is generated by oxidation of the organic insulating film is avoided.

In order to achieve the second object, a first method for forming an insulating film according to the present invention comprises a step of depositing an organic insulating film containing an organic component as a main component on a substrate by a CVD method. And a heat treatment step of performing a heat treatment on the organic insulating film in a hydrogen atmosphere.

According to the first method for forming an insulating film, CVD
Since the organic insulating film formed by the thermal treatment is subjected to a heat treatment in a hydrogen atmosphere, the radicals in the organic insulating film react with hydrogen to cause —CF ₂ H Is generated, so that the organic insulating film is stable against oxidation by oxygen.

In the first method for forming an insulating film, the CVD method in the insulating film deposition step is a plasma CVD method,
The heat treatment step preferably includes a step of performing a heat treatment on the organic insulating film in a hydrogen atmosphere without exposing the deposited organic insulating film to an oxidizing atmosphere.

In order to achieve the second object, a second method of forming an insulating film according to the present invention comprises an insulating film depositing step of depositing an organic insulating film mainly containing an organic component on a substrate by a CVD method. And a plasma processing step of performing hydrogen plasma processing on the organic insulating film.

According to the second method for forming an insulating film, CVD
Since hydrogen plasma treatment is performed on the organic insulating film formed by the method, radicals in the organic insulating film react with hydrogen radicals to form -CF ₂ H Is generated, so that the organic insulating film is stable against oxidation by oxygen.

In the second method for forming an insulating film, the CVD method in the insulating film deposition step is a plasma CVD method,
The plasma treatment step preferably includes a step of performing a hydrogen plasma treatment on the organic insulating film without exposing the deposited organic insulating film to an oxidizing atmosphere.

In order to achieve the second object, a third method of forming an insulating film according to the present invention comprises a step of depositing an organic insulating film containing an organic component as a main component on a substrate by a CVD method. And an ion implantation step of performing a heat treatment after implanting hydrogen ions into the organic insulating film.

According to the third method for forming an insulating film, CVD
After hydrogen ions are implanted into the organic insulating film formed by the CVD method, heat treatment is performed, so that the radicals in the organic insulating film react with hydrogen so that -CF ₂ H Is generated, so
The organic insulating film is stable against oxidation by oxygen.

In the third method for forming an insulating film, the CVD method in the insulating film deposition step is a plasma CVD method,
The ion implantation step preferably includes a step of implanting hydrogen ions into the organic insulating film without exposing the deposited organic insulating film to an oxidizing atmosphere.

In order to achieve the third object, a fourth method for forming an insulating film according to the present invention comprises the steps of: depositing an organic insulating film mainly containing an organic component on a substrate; On the other hand, the method includes a step of patterning the organic insulating film by performing etching in an oxygen atmosphere, and a step of performing a heat treatment on the patterned organic insulating film in a hydrogen atmosphere.

According to the fourth method of forming an insulating film, the organic insulating film is etched in an oxygen atmosphere and then heat-treated in a hydrogen atmosphere. Is reduced by hydrogen to CH ₂ , so that even if a heat treatment is performed on the organic insulating film in a later step, it is possible to avoid a situation in which the carbonyl compound is thermally decomposed to generate a low-molecular gas.

In order to achieve the third object, a fifth method for forming an insulating film according to the present invention comprises the steps of: depositing an organic insulating film mainly containing an organic component on a substrate; On the other hand, the method includes a step of patterning the organic insulating film by performing etching in an oxygen atmosphere, and a step of performing a hydrogen plasma treatment on the patterned organic insulating film.

According to the fifth method of forming an insulating film, the organic insulating film is etched in an oxygen atmosphere and then subjected to a hydrogen plasma treatment, so that the carbonyl groups generated in the organic insulating film are hydrogen. Reduced by C
Since it becomes H ₂ , even when a heat treatment is performed on the organic insulating film in a later step, it is possible to avoid a situation in which the carbonyl compound is thermally decomposed and a low-molecular gas is generated.

In order to achieve the third object, a sixth method of forming an insulating film according to the present invention comprises the steps of: depositing an organic insulating film mainly containing an organic component on a substrate; On the other hand, the method includes a step of patterning the organic insulating film by performing etching in an oxygen atmosphere, and a step of performing a heat treatment after implanting hydrogen ions into the patterned organic insulating film.

According to the sixth method for forming an insulating film, the organic insulating film is etched in an oxygen atmosphere, hydrogen ions are implanted, and then heat treatment is performed. The reduced carbonyl group is reduced by hydrogen to CH ₂ , so that even if a heat treatment is performed on the organic insulating film in a later step, it is possible to avoid a situation in which the carbonyl compound is thermally decomposed and a low-molecular gas is generated. Can be.

In order to achieve the fourth object, a seventh method of forming an insulating film according to the present invention comprises the steps of: performing a heat treatment in a hydrogen atmosphere on a base film formed on a substrate; Depositing an organic insulating film containing an organic component as a main component on the base film subjected to the heat treatment in the inside.

According to the seventh method of forming the insulating film, the heat treatment is performed on the underlying film in a hydrogen atmosphere, so that the silanol groups constituting the underlying film are reduced by hydrogen.
The surface of the underlayer changes to hydrophobic because it becomes SiH or the oxide of the metal forming the underlayer changes to a metal hydride.

In order to achieve the fourth object, an eighth method for forming an insulating film according to the present invention comprises the steps of: performing a hydrogen plasma treatment on a base film formed on a substrate; Depositing an organic insulating film containing an organic component as a main component on the performed base film.

According to the eighth method for forming an insulating film, since hydrogen plasma treatment is performed on the underlying film, the silanol groups constituting the underlying film are reduced to -SiH by hydrogen, or the underlying film is formed. Since the metal oxide changes to a metal hydride, the surface of the base film changes to hydrophobic.

To achieve the fourth object, a ninth method for forming an insulating film according to the present invention comprises the steps of: implanting carbon ions into a base film formed on a substrate; Depositing an organic insulating film containing an organic component as a main component on the base film thus formed.

According to the ninth method for forming an insulating film, since carbon ions are implanted into the base film, the bond between the atoms forming the base film and the hydroxyl groups changes to the bond between the atoms forming the base film and the carbon atoms. Therefore, the affinity with the organic insulating film increases, and the surface of the underlying film changes to hydrophobic.

In order to achieve the fourth object, a tenth method of forming an insulating film according to the present invention is a step of performing a heat treatment after implanting hydrogen ions into a base film formed on a substrate. And a step of depositing an organic insulating film containing an organic component as a main component on the base film subjected to the heat treatment after the hydrogen ion implantation.

According to the tenth method for forming an insulating film, heat treatment is performed after hydrogen ions are implanted into the underlying film, so that the silanol groups forming the underlying film are reduced by hydrogen to -SiH, Since the metal oxide that forms the base film changes to a metal hydride, the surface of the base film changes to hydrophobic.

In order to achieve the fifth object, an eleventh method of forming an insulating film according to the present invention comprises the steps of: depositing an organic film containing an organic component as a main component on a substrate; ,
Depositing an organic component-containing silicon oxide film by a plasma CVD method using an alkoxysilane as a raw material and in the absence of an oxidizing agent to form an organic film and an insulating film composed of the organic component-containing silicon oxide film. I have.

According to the eleventh method for forming an insulating film, since a plasma CVD method is performed on an organic insulating film using alkoxysilane as a raw material, a polymerization reaction occurs even in the absence of an oxidizing agent. Therefore, since the organic component-containing silicon oxide film can be formed by plasma CVD performed in the absence of an oxidizing agent, oxidation of the organic insulating film can be prevented.

In order to achieve the fifth object, a twelfth method for forming an insulating film according to the present invention comprises the steps of: depositing an organic film mainly containing an organic component on a substrate; ,
Depositing an organic component-containing silicon oxide film by a plasma CVD method using alkoxysilane and silane as raw materials and in the absence of an oxidizing agent to form an organic film and an insulating film composed of the organic component-containing silicon oxide film. Have.

According to the twelfth method for forming an insulating film, a plasma CVD method is performed on an organic insulating film using alkoxysilane and silane as raw materials, so that a polymerization reaction occurs even in the absence of an oxidizing agent. Therefore, since the organic component-containing silicon oxide film can be formed by plasma CVD performed in the absence of an oxidizing agent, oxidation of the organic insulating film can be prevented.

In order to achieve the sixth object, a thirteenth method of forming an insulating film according to the present invention comprises the steps of applying a material containing an organic component as a main component on a substrate to form a coating film;
Baking and baking the applied film in a reducing atmosphere to form an organic insulating film made of the applied film.

According to the thirteenth method for forming an insulating film, a coating film formed by applying a material containing an organic component as a main component is baked and baked in a reducing atmosphere. Since the organic insulating film made of a film is formed, oxidation of the organic insulating film can be suppressed.

[0051]

(First Embodiment) A first embodiment of the present invention.
As an embodiment of the present invention, there is provided a method of manufacturing a semiconductor device including a step of performing etching using H ₂ O plasma on an organic insulating film containing an organic component as a main component, for example, an organic insulating film having a poly (allyl ether) structure. , FIG.
(A)-(c), FIGS. 2 (a)-(c) and FIGS. 3 (a)-
This will be described with reference to FIG.

First, as shown in FIG. 1A, a first metal wiring 101 formed on a semiconductor substrate 100 is
After a silicon nitride film 102 having a thickness of, for example, 50 nm for protecting the first metal wiring 101 is formed in an etching process performed later, the silicon nitride film 102 is formed.
A first organic film 103 having a thickness of, for example, 300 nm and containing an organic component as a main component is deposited thereon. Next, for example, plasma CVD is performed on the first organic film 103.
After depositing a silicon oxide film 104 having a thickness of, for example, 100 nm by a method, a second organic film 105 having a thickness of, for example, 300 nm and containing an organic component as a main component is deposited on the silicon oxide film 104. Thereafter, a titanium nitride film 106 having a thickness of, for example, 50 nm is deposited on the second organic film 105.

The method for depositing the first and second organic films 103 and 105 is not particularly limited. For example, an organic film having a poly (allyl ether) structure is formed by a coating method. That is, after an organic film having a poly (allyl ether) structure is applied to a thickness of 300 nm, baking by a hot plate is performed under nitrogen atmosphere for 15 minutes.
After performing for 1 minute at a temperature of 0 ° C. and for 1 minute at a temperature of 250 ° C., baking is performed at a temperature of 400 ° C. for 60 minutes while flowing a nitrogen gas under reduced pressure in an electric furnace.

Next, as shown in FIG. 1B, a first resist pattern 107 having an opening for forming a wiring groove is formed on the titanium nitride film 106 by a lithography process. Dry etching is performed on the titanium nitride film 106 using the resist pattern 107 as a mask to form a mask pattern 108 made of the titanium nitride film 106 as shown in FIG.

Next, without removing the first resist pattern 107, a second resist pattern 109 having a contact hole forming opening is formed on the second organic film 105 by a lithography process. The second organic film 105 is subjected to dry etching using H ₂ O plasma to form a patterned _second electrode having an opening for forming a contact hole as shown in FIG.
Is formed. In this case, since the second organic film 105 and the first resist pattern 107 and the second resist pattern 109 both contain an organic component as a main component, the etching rate for the second organic film 105, Second resist patterns 107 and 109
The first resist pattern 107 and the second resist pattern 109 are removed by the dry etching process on the second organic film 105 because the etching rate is substantially equal to the etching rate for the second organic film 105.

Next, the patterned second organic film 10
5A is used as a mask and the silicon oxide film 104 is dry-etched using a fluorocarbon-based etching gas to form a patterned silicon having an opening for forming a contact hole as shown in FIG. An oxide film 104A is formed.

Next, H ₂ O is applied to the second organic film 105A patterned using the mask pattern 108 as a mask and to the first organic film 103 using the patterned silicon oxide film 104A as a mask. By performing dry etching using plasma, a wiring groove 111 is formed in the patterned second organic film 105A as shown in FIG.
A patterned first organic film 103A having 0 is formed.

Next, the patterned silicon oxide film 1
By performing dry etching on the silicon nitride film 102 using the mask 04A as a mask, as shown in FIG.
A patterned silicon nitride film 102A is formed, and a first metal wiring 101 is formed in a contact hole 110A.
Exposure to

Next, as shown in FIG. 3B, for example, 50 nm is formed on the wall surfaces of the contact hole 110 and the wiring groove 111.
After depositing an adhesion layer 112 made of titanium nitride having a thickness of m, a metal film 113 is deposited over the entire surface so as to fill the contact holes 110 and the wiring grooves 111. The composition of the metal film 113 is not particularly limited, and copper, aluminum, gold, silver, nickel, cobalt, tungsten, an alloy thereof, or the like can be used.

Next, as shown in FIG. 3C, the second organic film 105A is deposited on the patterned second organic film 105A.
Adhesion layer 112, metal film 113 and mask pattern 108
Is removed by, for example, a CMP method to form a second metal wiring 114 made of a metal film 113 and a contact 115 made of a metal film 113 connecting the first metal wiring 101 and the second metal wiring 114.

Incidentally, in the etching process for the first organic film 103 and the second organic film 105, conventionally, reactive ion etching using oxygen as an etching gas was performed. And high reactivity, the film quality is deteriorated by oxygen during etching. In other words, the organic film is oxidized by the active oxygen radicals generated in the plasma to generate an unstable carbonyl compound, and the generated carbonyl compound is thermally decomposed by a heat treatment in a later step, so that degassing occurs. was there.

On the other hand, as in the first embodiment,
The H ₂ O plasma method H ₂ O is used as the etching gas, the first organic layer 103 and the second organic film 105
Is etched, in the H ₂ O plasma, O
_{2. Since} the density of active O radicals is much lower than in the plasma, OH radicals mainly act on the etching of the first and second organic films 103 and 105. Therefore, the etching rate is slower than the case of using an O ₂ plasma, is sufficiently practical speed was about 2/3 of the case of using an O ₂ plasma.

Since the OH radical has a much lower oxidizing property than the O radical, the first and second organic films 103, 10
It is considered that the etching of No. 5 proceeds by extracting hydrogen with OH. That is, OH radicals react with H atoms bonded to C atoms constituting the polymer of the organic film to generate H ₂ O, and the generated H ₂ O
Is removed from the C atom, so that a dangling bond is formed at the C atom. Another OH radical is bonded to the dangling bond of the C atom, and a low molecular compound consisting of an alcohol or an aldehyde compound is generated. It is considered that the etching proceeds.

Therefore, the first and second organic films 103, 1
It is possible to greatly reduce the situation where low-molecular gas is generated by oxidization of 05 to produce a carbonyl compound.

When the first and second organic films 103 and 105 were etched with H ₂ O plasma, a desired groove shape having anisotropy could be formed in the organic films.

When the organic film after etching was evaluated by infrared spectrum (FTIR), the absorption peak based on the carbonyl group was below the observation limit.

Second Embodiment As a second embodiment of the present invention, an organic insulating film containing an organic component as a main component, for example, an organic insulating film having a poly (allyl ether) structure is etched by CO plasma. A method for manufacturing a semiconductor device including the steps of performing the steps will be described.

The second embodiment is different from the first embodiment only in the etching process for the first and second organic films 103 and 105. That is, the etching process for the first and second organic films 103 and 105 is performed by a CO plasma method using CO as an etching gas.

When the CO plasma method using CO as an etching gas is performed as in the second embodiment, the CO plasma is more active than the O ₂ plasma.
Since the radical density is very low, CO radicals mainly act on the etching of the first and second organic films 103 and 105. Therefore, the etching rate is O
_Although it is slower than the case where _two plasmas are used, it is about 1/2 of the case where O2 plasma is used, which is a sufficiently practical speed.

Since the CO radical is much less oxidizable than the O radical, the first and second organic films 103, 10
It is considered that the etching of No. 5 proceeds by extracting hydrogen with CO. That is, the CO radical is bonded to the C atom constituting the polymer of the organic film to generate a low molecular compound composed of an alcohol or an aldehyde compound, and the generated low molecular compound is eliminated from the polymer of the organic film, It is considered that the etching of the organic film proceeds.

Therefore, the first and second organic films 103, 1
It is possible to greatly reduce the situation where low-molecular gas is generated by oxidization of 05 to produce a carbonyl compound.

According to the second embodiment, the bond between C and O in the CO radical forms the bond between H and O in the OH radical.
Is stronger than that of the first embodiment,
The degree to which O radicals contribute to etching is low. For this reason, although the etching rate is slightly inferior, the phenomenon of generating low-molecular gas is more unlikely to occur.

When the first and second organic films 103 and 105 were etched with CO plasma, a desired anisotropic groove shape could be formed in the organic films.

When the organic film after etching was evaluated by infrared spectrum (FTIR), the absorption peak based on the carbonyl group was below the observation limit.

(Third Embodiment) As a third embodiment of the present invention, an organic insulating film mainly composed of an organic component, for example, an amorphous fluorocarbon film formed by a plasma CVD method is heat-treated in a hydrogen atmosphere. A method of forming an organic insulating film will be described.

After an organic insulating film such as an amorphous fluorocarbon film is deposited on a semiconductor substrate by a plasma CVD method, the deposited amorphous fluorocarbon film is exposed to, for example, 400 ° C. in a hydrogen atmosphere without being exposed to an oxygen atmosphere. Is performed at a temperature of about 60 minutes.

In an organic insulating film such as an amorphous fluorocarbon film formed by a plasma CVD method,
Immediately after film formation, radicals are present in the organic insulating film. The reason is that the fluorocarbon, which is the raw material of the amorphous fluorocarbon film, is dissociated into CF ₂ radicals in the plasma, and the dissociated CF ₂ radicals are polymerized to form a polymer. _This is because it is terminated by _two radical groups.

As described above, radicals are present in the organic insulating film immediately after being formed by the plasma CVD method, and when the organic insulating film is exposed to an oxidizing atmosphere, radicals and oxygen react with each other. The insulating film is oxidized, and a low-molecular gas such as toluene, phenol, or carbon dioxide is generated from the organic insulating film in a heat treatment performed thereafter.

However, in the third embodiment, the heat treatment is performed on the organic insulating film immediately after being formed by the plasma CVD method in a hydrogen atmosphere without exposing it to an oxygen atmosphere. As shown in the formula, the radical in the organic insulating film reacts with hydrogen to form -CF
₂ H Is generated, so that the organic insulating film is stable against oxidation by oxygen.

-CF_Two ^*+ H_Two→ −CF_TwoH + H^*  Therefore, according to the third embodiment, the organic insulating film has a low
It becomes difficult to generate gas from the child.

(Fourth Embodiment) As a fourth embodiment of the present invention, an organic insulating film containing an organic component as a main component, for example, an amorphous fluorocarbon film formed by a plasma CVD method is treated with hydrogen plasma. A method for forming an organic insulating film will be described.

After an organic insulating film, for example, an amorphous fluorocarbon film is deposited on a semiconductor substrate by a plasma CVD method, the deposited amorphous fluorocarbon film is exposed to, for example, 5
Hydrogen plasma treatment is performed under the conditions of a vacuum of rr and a substrate temperature of 50 ° C.

According to the fourth embodiment, plasma CVD
The hydrogen plasma treatment is performed on the organic insulating film immediately after being formed by the method without exposing the organic insulating film to an oxygen atmosphere. Therefore, as shown in the following chemical reaction formula, radicals in the organic insulating film and hydrogen radicals are generated. React to -CF ₂ H Is generated, so that the organic insulating film is stable against oxidation by oxygen.

-CF_Two ^*+ H^* → −CF_TwoH  Therefore, according to the fourth embodiment, the organic insulating film has a low
It becomes difficult to generate gas from the child.

In the third embodiment, high energy is required for the reaction between —CF ₂ ^* and a hydrogen molecule (H ₂ ), but in the fourth embodiment, —CF ₂ ^* and hydrogen Radical (H ^* ) Reacts with low energy, so that radicals can be reduced at a lower temperature and in a shorter time than in the third embodiment.

However, since the reaction between the hydrogen radical and the unsaturated bond of the polymer proceeds, the relative permittivity may increase depending on the conditions of the plasma treatment.

(Fifth Embodiment) As a fifth embodiment of the present invention, hydrogen ions are implanted into an organic insulating film mainly composed of an organic component, for example, an amorphous fluorocarbon film formed by a plasma CVD method. A method for forming an organic insulating film to be subjected to heat treatment later will be described.

After an organic insulating film such as an amorphous fluorocarbon film is deposited on a semiconductor substrate by a plasma CVD method, hydrogen ions are implanted into the deposited amorphous fluorocarbon film without exposing the film to an oxygen atmosphere. For example, heat treatment is performed at a temperature of 400 ° C. for about 60 minutes.

According to the fifth embodiment, plasma CVD
Since the heat treatment is performed after hydrogen ions are implanted into the organic insulating film immediately after being formed by the method without exposing the organic insulating film to an oxygen atmosphere, the radicals in the organic insulating film react with hydrogen to generate —CF ₂ H Is generated, so that the organic insulating film is stable against oxidation by oxygen.

In particular, according to the fifth embodiment, since hydrogen ions are implanted into the organic insulating film, hydrogen atoms diffuse into the organic insulating film, so that the generation of radicals can be suppressed more reliably.

Further, since it becomes possible to implant hydrogen ions in an amount corresponding to the concentration of radicals present in the organic insulating film, there is no possibility that excessive hydrogen will cause deterioration of the organic insulating film.

However, the device may be damaged due to the charge-up due to the implantation of hydrogen ions.

Sixth Embodiment As a sixth embodiment of the present invention, an organic insulating film containing an organic component as a main component, for example, an organic insulating film having a poly (allyl ether) structure, is oxidized in an oxidizing atmosphere. A method of forming an organic insulating film by performing a heat treatment in a hydrogen atmosphere on a portion of the organic insulating film exposed by the etching after the etching is described.

As a method of forming the organic insulating film, an organic film having a poly (allyl ether) structure is used in the same manner as the first and second organic films 103 and 105 in the first embodiment.
After coating to a thickness of 00 nm, baking by a hot plate was performed in a nitrogen atmosphere at a temperature of 150 ° C. for 1 minute and at a temperature of 250 ° C. for 1 minute, respectively, and then, in an electric furnace under reduced pressure. Baking is performed at 400 ° C. for 60 minutes while flowing nitrogen gas.

Next, unlike the first embodiment, the organic insulating film is etched by a reactive ion etching method using oxygen as an etching gas, and then, in an atmosphere of hydrogen, at a temperature of 400 ° C., for example. For about 60 minutes.

When the organic insulating film is subjected to etching using oxygen as an etching gas, the organic insulating film has high reactivity to oxygen, so that the quality of the film is deteriorated by the oxygen during the etching. That is, the organic insulating film is oxidized by the active oxygen radicals generated in the plasma to generate an unstable carbonyl compound, and the generated carbonyl compound is thermally decomposed by a heat treatment in a later step, so that a low-molecular gas is generated. Might be.

However, in the sixth embodiment, after the organic insulating film is etched using oxygen as an etching gas and then heat-treated in a hydrogen atmosphere, the carbonyl formed in the organic insulating film is formed. Group (> C
ＯO) is reduced by hydrogen to CH ₂ . Therefore, even when a heat treatment is performed on the organic insulating film in a later step, a situation in which the carbonyl compound is thermally decomposed to generate a low-molecular gas can be avoided.

When the organic insulating film after the etching was evaluated by infrared spectrum (FTIR), it was confirmed that the carbonyl group was reduced.

(Seventh Embodiment) As a seventh embodiment of the present invention, an organic insulating film containing an organic component as a main component, for example, an organic insulating film having a poly (allyl ether) structure, is oxidized in an oxidizing atmosphere. A method of forming an organic insulating film in which a portion of the organic insulating film exposed by the etching after the etching is processed by hydrogen plasma will be described.

An organic insulating film is formed by forming an organic film having a poly (allyl ether) structure in the same manner as the first and second organic films 103 and 105 in the first embodiment.
After coating to a thickness of 00 nm, baking by a hot plate was performed in a nitrogen atmosphere at a temperature of 150 ° C. for 1 minute and at a temperature of 250 ° C. for 1 minute, respectively, and then, in an electric furnace under reduced pressure. Baking is performed at 400 ° C. for 60 minutes while flowing nitrogen gas.

Next, unlike the first embodiment, the organic insulating film is etched by a reactive ion etching method using oxygen as an etching gas.
Hydrogen plasma treatment is performed under the conditions of a vacuum of Torr and a substrate temperature of 50 ° C.

According to the seventh embodiment, the organic insulating film is etched using oxygen as an etching gas and then subjected to the hydrogen plasma treatment, so that the carbonyl groups (> C ＯO) is reduced by hydrogen to CH ₂ . Therefore, even when a heat treatment is performed on the organic insulating film in a later step, a situation in which the carbonyl compound is thermally decomposed to generate a low-molecular gas can be avoided.

When the organic insulating film after the etching was evaluated by infrared spectrum (FTIR), it was confirmed that the carbonyl group was reduced.

(Eighth Embodiment) As an eighth embodiment of the present invention, an organic insulating film containing an organic component as a main component, for example, an organic insulating film having a poly (allyl ether) structure, is oxidized in an oxidizing atmosphere. A method of forming an organic insulating film in which heat treatment is performed after hydrogen ions are implanted into a portion of the organic insulating film exposed by the etching after the etching is described.

An organic insulating film is formed by forming an organic film having a poly (allyl ether) structure in the same manner as the first and second organic films 103 and 105 in the first embodiment.
After being applied to a thickness of 00 nm, baking by a hot plate was performed in a nitrogen atmosphere at a temperature of 150 ° C. for 1 minute and at a temperature of 250 ° C. for 1 minute. Baking is performed at 400 ° C. for 60 minutes while flowing nitrogen gas.

Next, unlike the first embodiment, the organic insulating film is etched by a reactive ion etching method using oxygen as an etching gas, and then hydrogen ions are implanted. Is performed at a temperature of about 60 minutes.

According to the eighth embodiment, after the organic insulating film is etched using oxygen as an etching gas, hydrogen ions are implanted, and then heat treatment is performed. Carbonyl group (> C =
O) is the CH ₂ being reduced by hydrogen. Therefore, even when a heat treatment is performed on the organic insulating film in a later step, a situation in which the carbonyl compound is thermally decomposed to generate a low-molecular gas can be avoided.

When the organic insulating film after the etching was evaluated by infrared spectrum (FTIR), it was confirmed that the carbonyl group was reduced.

(Ninth Embodiment) As a ninth embodiment of the present invention, after performing a heat treatment on a surface of a semiconductor substrate in a hydrogen atmosphere, an organic insulating film mainly containing an organic component is deposited. A method for forming an organic insulating film will be described.

After a silicon oxide film is deposited on the semiconductor substrate by, eg, plasma CVD, the silicon oxide film is subjected to a heat treatment in a hydrogen atmosphere at a temperature of, for example, 400 ° C. for about 60 minutes. Thereafter, an organic insulating film mainly containing an organic component is deposited on the silicon oxide film by a coating method or a plasma CVD method.

Since a silanol group is present on the surface of the silicon oxide film immediately after the film formation and the surface of the silicon oxide film is made hydrophilic by the silanol group, an organic insulating film is deposited on the silicon oxide film. In this case, especially when the organic insulating film is deposited by a coating method, the adhesion between the organic insulating film and the silicon oxide film is impaired.

However, in the ninth embodiment, the silicon oxide film is subjected to a heat treatment in a hydrogen atmosphere, and then the organic insulating film is deposited on the silicon oxide film. The adhesion to the film is improved. That is, when the silicon oxide film is subjected to a heat treatment in a hydrogen atmosphere, the silanol groups (—SiOH) present on the surface of the silicon oxide film are reduced to —SiH by hydrogen, so that the surface of the silicon oxide film becomes hydrophobic. Therefore, the adhesion between the organic insulating film and the silicon oxide film is improved.

When the silicon oxide film is subjected to a heat treatment in a hydrogen atmosphere, even silanol and moisture in the silicon oxide film can be removed, so that the adhesion between the organic insulating film and the silicon oxide film is greatly improved. Can be.

When an organic insulating film is deposited on a silicon oxide film subjected to a heat treatment in a hydrogen atmosphere by a plasma CVD method, -SiH existing on the surface of the silicon oxide film reacts with organic radicals. Therefore, the adhesion between the organic insulating film and the silicon oxide film is further improved.

In the ninth embodiment, the case where the adhesion between the silicon oxide film and the organic insulating film is improved has been described. Alternatively, for example, the organic insulating film may be formed on a metal film made of an aluminum alloy or the like. Also in the case of depositing a film, if the organic insulating film is deposited after performing a heat treatment on the surface of the metal film in a hydrogen atmosphere, the adhesion between the organic insulating film and the metal film is improved. The reason is that when a heat treatment is performed on the surface of the metal film in a hydrogen atmosphere, a metal oxide (Me-O)
Is changed to a metal hydride (Me-H), and the surface of the metal film is changed to hydrophobic.

(Tenth Embodiment) As a tenth embodiment of the present invention, after performing a hydrogen plasma treatment on a surface of a semiconductor substrate, an organic insulating film mainly containing an organic component is deposited. A method for forming a film will be described.

After depositing a silicon oxide film on the semiconductor substrate by, for example, a plasma CVD method, the silicon oxide film is subjected to hydrogen plasma processing under the conditions of, for example, a vacuum of 5 Torr and a substrate temperature of 50 ° C. After a while
An organic insulating film containing an organic component as a main component is deposited on the silicon oxide film by a coating method or a plasma CVD method.

According to the tenth embodiment, since the organic insulating film is deposited on the silicon oxide film after the silicon oxide film is subjected to the hydrogen plasma treatment, the adhesion between the organic insulating film and the silicon oxide film is improved. Is improved. That is, when a hydrogen plasma treatment is performed on the silicon oxide film, silanol groups (-SiO
H) is reduced by hydrogen to -SiH, so that the surface of the silicon oxide film changes to hydrophobic, so that the adhesion between the organic insulating film and the silicon oxide film is improved.

In the tenth embodiment, since the surface of the silicon oxide film is subjected to the hydrogen plasma treatment, the surface of the silicon oxide film can be made hydrophobic in a short time.

When an organic insulating film is deposited on the silicon oxide film subjected to the hydrogen plasma treatment by the plasma CVD method, -SiH existing on the surface of the silicon oxide film is used.
Reacts with the organic radical to form a Si—C bond, so that the adhesion between the organic insulating film and the silicon oxide film is further improved.

In the tenth embodiment, the case where the adhesion between the silicon oxide film and the organic insulating film is improved has been described. Alternatively, for example, the organic insulating film is formed on a metal film made of an aluminum alloy or the like. Also in the case of depositing a film, if the organic insulating film is deposited after performing hydrogen plasma treatment on the surface of the metal film, the adhesion between the organic insulating film and the metal film is improved. The reason is that when a hydrogen plasma treatment is performed on the surface of the metal film, the metal oxide (Me-O) changes to a metal hydride (Me-H), so that the surface of the metal film becomes hydrophobic. To change.

(Eleventh Embodiment) As an eleventh embodiment of the present invention, a heat treatment is performed after carbon ions are implanted into the surface of a semiconductor substrate, and thereafter, an organic insulating material mainly containing an organic component is used. A method for forming an organic insulating film for depositing a film will be described.

A silicon oxide film is deposited on a semiconductor substrate by, for example, a plasma CVD method. After carbon ions are implanted into the silicon oxide film, a heat treatment is performed at a temperature of, for example, 400 ° C. for about 60 minutes, and then, on the silicon oxide film, by a coating method or a plasma CVD method,
An organic insulating film containing an organic component as a main component is deposited.

According to the eleventh embodiment, heat treatment is performed after carbon ions are implanted into the silicon oxide film, and thereafter, an organic insulating film is deposited on the silicon oxide film. The adhesion with the oxide film is improved. That is, when carbon ions are implanted into the silicon oxide film, the silanol groups (—SiOH) present on the surface of the silicon oxide film are changed to —SiC, so that the affinity with the organic insulating film increases and the silicon Since the surface of the oxide film changes to hydrophobic, the adhesion between the organic insulating film and the silicon oxide film is improved.

When an organic insulating film is deposited on a silicon oxide film into which carbon ions have been implanted by a plasma CVD method, Si—C-bonded carbon existing on the surface of the silicon oxide film and an organic material that is a raw material of polymer are used. Since the radicals react, the adhesion between the organic insulating film and the silicon oxide film is further improved.

In the eleventh embodiment, the heat treatment is performed after the carbon ions are implanted. However, when the carbon ions are implanted into the silicon oxide film, the subsequent heat treatment is not necessarily required.

(Twelfth Embodiment) As a twelfth embodiment of the present invention, heat treatment is performed after hydrogen ions are implanted into the surface of a semiconductor substrate, and thereafter, an organic insulating material mainly containing an organic component is used. A method for forming an organic insulating film for depositing a film will be described.

A silicon oxide film is deposited on a semiconductor substrate by, for example, a plasma CVD method. After hydrogen ions are implanted into the silicon oxide film, a heat treatment is performed for about 60 minutes at a temperature of, for example, 400 ° C., and then, on the silicon oxide film, by a coating method or a plasma CVD method,
An organic insulating film containing an organic component as a main component is deposited.

According to the twelfth embodiment, heat treatment is performed after hydrogen ions are implanted into a silicon oxide film, and then an organic insulating film is deposited on the silicon oxide film. The adhesion with the oxide film is improved. That is, when heat treatment is performed after hydrogen ions are implanted into the silicon oxide film, silanol groups (—SiOH) present on the surface of the silicon oxide film are reduced to —SiH by hydrogen, so that the silicon oxide film Since the surface changes to hydrophobic, the adhesion between the organic insulating film and the silicon oxide film is improved.

In the twelfth embodiment, since hydrogen ions are implanted into the surface of the silicon oxide film, a Si—H bond can be formed only on the very surface of the silicon oxide film.
The stress generated in the silicon oxide film can be suppressed as compared with the first embodiment, but the eleventh embodiment is slightly better in terms of improving the adhesion.

When an organic insulating film is deposited by a plasma CVD method on a silicon oxide film which has been subjected to a heat treatment after hydrogen ions have been implanted, -SiH and organic radicals existing on the surface of the silicon oxide film are removed. Reacts with Si-C
Since the bond is formed, the adhesion between the organic insulating film and the silicon oxide film is further improved.

In the twelfth embodiment, the case where the adhesion between the silicon oxide film and the organic insulating film is improved has been described. Alternatively, the organic insulating film may be formed on a metal film made of, for example, an aluminum alloy. Also when depositing a film, heat treatment is performed after hydrogen ions are implanted into the surface of the metal film, and then, when an organic insulating film is deposited, the adhesion between the organic insulating film and the metal film is improved. The reason is that when heat treatment is performed after hydrogen ions are implanted into the surface of the metal film, the metal oxide (Me-O) becomes a metal hydride (Me-O).
-H) because the surface of the metal film changes to hydrophobic.

(Thirteenth Embodiment) As a thirteenth embodiment of the present invention, an organic insulating film containing an organic component as a main component is formed by plasma CVD using an alkoxysilane as a raw material in the absence of an oxidizing agent. A method for forming an insulating film for forming a silicon oxide film will be described.

On a semiconductor substrate, a coating method or a plasma CV
After an organic insulating film containing an organic component as a main component is deposited by the method D, an alkoxysilane, for example, phenyltrimethoxysilane is used as a source gas and no oxidizing agent is present on the organic insulating film using a plasma CVD apparatus. An organic component-containing silicon oxide film is formed below. As an example of the film forming conditions of the organic component-containing silicon oxide film, RF power: 500
W, pressure: 5 torr, flow rate of phenyltrimethoxysilane: 1 ml / min, flow rate of Ar: 5000 scc
m, substrate temperature: 400 ° C. The film formation rate when forming a film under these conditions was 100 nm / min.

According to the thirteenth embodiment, since the plasma CVD method using alkoxysilane, for example, phenyltrimethoxysilane as a source gas is performed, a polymerization reaction occurs even in the absence of an oxidizing agent. Therefore, an organic component-containing silicon oxide film can be formed by plasma CVD performed in the absence of an oxidizing agent, so that oxidation of the organic insulating film can be prevented. Therefore, a situation in which a low-molecular gas is generated from the organic insulating film is avoided. Can be.

After the silicon oxide film was deposited, the organic insulating film was observed by FTIR. As a result, no oxidation of the organic insulating film was observed.

(Fourteenth Embodiment) As a fourteenth embodiment of the present invention, on an organic insulating film containing an organic component as a main component, an alkoxysilane and silane are used as raw materials in the absence of an oxidizing agent. A method for forming an insulating film for forming a silicon oxide film by plasma CVD will be described.

On a semiconductor substrate, a coating method or a plasma CV
After an organic insulating film containing an organic component as a main component is deposited by a method D, an alkoxysilane such as phenyltrimethoxysilane and silane is used as a source gas and oxidized on the organic insulating film using a plasma CVD apparatus. A silicon oxide film is formed in the absence of an agent. As an example of the conditions for forming the silicon oxide film, RF power: 500 W, pressure: 5 torr
r, flow rate of phenyltrimethoxysilane: 1 ml / mi
n, flow rate of silane: 500 sccm, flow rate of Ar: 50
00 sccm, substrate temperature: 400 ° C. The film forming speed when forming a film under these conditions is 300 nm / m
was in.

According to the fourteenth embodiment, since a plasma CVD method is performed using alkoxysilane and silane as raw material gases, a polymerization reaction occurs even in the absence of an oxidizing agent. Therefore, since the silicon oxide film can be formed by plasma CVD performed in the absence of an oxidizing agent, the oxidation of the organic insulating film can be prevented, and the situation where low-molecular gas is generated from the organic insulating film can be avoided.

After the silicon oxide film was deposited, the organic insulating film was observed by FTIR. As a result, no oxidation of the organic insulating film was observed.

According to the fourteenth embodiment, although the water content in the silicon oxide film is slightly increased as compared with the thirteenth embodiment, the film forming speed is greatly improved.

(Fifteenth Embodiment) As a fifteenth embodiment of the present invention, a baking step and a baking step in forming an organic insulating film mainly containing an organic component by a coating method are performed in a reducing atmosphere. A method for forming an organic insulating film will be described.

For example, after an organic film having a poly (allyl ether) structure is applied to a thickness of 300 nm, the applied organic film is exposed to a reducing atmosphere composed of a mixed gas of nitrogen gas and hydrogen gas. An organic insulating film is formed by performing heat treatment and performing baking and baking. The conditions of the heat treatment include, for example, the flow rate of nitrogen gas at a temperature of about 400 ° C. under normal pressure: 2
It is kept under an atmosphere of 000 sccm and a flow rate of hydrogen gas: 200 sccm for 30 minutes.

Conventionally, a heat treatment is performed on an organic film by keeping the inside of an electric furnace or a hot plate under an atmosphere of an inert gas at normal or reduced pressure and at a temperature of about 400 ° C. However, since it is difficult to maintain the inside of the electric furnace or the hot plate in a completely inert gas atmosphere, a small amount of oxygen is mixed into the electric furnace or the hot plate. 40
In an atmosphere in which the organic film is held at a temperature of about 0 ° C., the organic film is easily oxidized even if a small amount of oxygen is mixed.

On the other hand, in the fifteenth embodiment, since the baking and baking are performed by performing the heat treatment by holding the organic film in a reducing atmosphere, it is possible to suppress the oxidation of the organic insulating film. it can.

When the organic insulating film formed by the method of the fifteenth embodiment was observed by FTIR, no oxidation of the organic insulating film was observed.

[0147]

According to the first method of manufacturing a semiconductor device of the present invention, the organic insulating film is etched by H ₂ O plasma, so that the carbonyl compound is generated by oxidation of the organic insulating film. Since a situation in which a low molecular gas such as carbon dioxide is generated by thermal decomposition of the compound is avoided, a silicon oxide film or a metal film is favorably deposited on the organic insulating film after the etching.

According to the second method of manufacturing a semiconductor device of the present invention, since the organic insulating film is etched by CO plasma, the carbonyl compound is generated by oxidation of the organic insulating film, and the carbonyl compound is thermally decomposed. As a result, a situation in which a low molecular gas such as carbon dioxide is generated is avoided, so that a silicon oxide film, a metal film, or the like is satisfactorily deposited on the etched organic insulating film.

In particular, according to the second method for manufacturing a semiconductor device, the bond between C and O in the CO radical is stronger than the bond between H and O in the OH radical. Since the degree to which the O radicals contribute to the etching is lower than that of the above, the situation where the carbonyl compound is generated by the oxidation of the organic insulating film can be further reduced.

According to the first method for forming an insulating film of the present invention, the organic insulating film formed by the CVD method is subjected to a heat treatment in a hydrogen atmosphere, so that the radicals in the organic insulating film react with hydrogen. -CF ₂ H Is generated, so that the organic insulating film is stable against oxidation by oxygen. Therefore, a situation in which a low-molecular gas is generated due to oxidation of the organic insulating film is avoided, so that a silicon oxide film, a metal film, or the like is favorably deposited on the organic insulating film formed by the CVD method.

In the first method for forming an insulating film, when a heat treatment is performed in a hydrogen atmosphere without exposing the deposited organic insulating film to an oxidizing atmosphere, radicals of a carbon compound formed by a plasma CVD method, oxygen, Can be reliably prevented from oxidizing the organic insulating film due to the reaction.

According to the second method of forming an insulating film of the present invention, since hydrogen plasma treatment is performed on the organic insulating film formed by the CVD method, the radicals in the organic insulating film react with hydrogen radicals. -CF ₂ H Is generated, so that the organic insulating film is stable against oxidation by oxygen. Therefore, a situation in which a low-molecular gas is generated due to oxidation of the organic insulating film is avoided, so that a silicon oxide film, a metal film, or the like is favorably deposited on the organic insulating film formed by the CVD method.

In particular, according to the method of forming the second insulating film,
Since the radicals in the organic insulating film react with the hydrogen radicals, the reaction occurs at low energy, so that the radicals in the organic insulating film are reduced at a lower temperature and in a shorter time than in the first method for forming the insulating film. be able to.

In the second method for forming an insulating film, when hydrogen plasma heat treatment is performed without exposing the deposited organic insulating film to an oxidizing atmosphere, radicals of carbon compounds formed by the plasma CVD method react with oxygen. As a result, the situation where the organic insulating film is oxidized can be reliably avoided.

According to the third method for forming an insulating film of the present invention, since heat treatment is performed after hydrogen ions are implanted into the organic insulating film formed by the CVD method, radicals and hydrogen in the organic insulating film are converted. React to -CF ₂ H Is generated, so that the organic insulating film is stable against oxidation by oxygen. Therefore, a situation in which a low-molecular gas is generated due to oxidation of the organic insulating film is avoided, so that a silicon oxide film, a metal film, or the like is favorably deposited on the organic insulating film formed by the CVD method.

In particular, according to the third insulating film forming method,
Since hydrogen ions are implanted into the organic insulating film, hydrogen atoms diffuse into the organic insulating film, so that generation of radicals in the organic insulating film can be suppressed more reliably.

In the third method of forming an insulating film, when hydrogen ions are implanted without exposing the deposited organic insulating film to an oxidizing atmosphere, radicals and oxygen of a carbon compound formed by a plasma CVD method are generated. The situation where the organic insulating film is oxidized due to the reaction can be reliably avoided.

According to the fourth method for forming an insulating film, the organic insulating film is etched in an oxygen atmosphere and then heat-treated in a hydrogen atmosphere. However, since it is possible to avoid a situation in which the carbonyl compound is thermally decomposed to generate a low-molecular gas, a silicon oxide film or a metal film can be favorably deposited on the organic insulating film etched in an oxygen atmosphere. it can.

According to the fifth method for forming an insulating film, the organic insulating film is etched in an oxygen atmosphere and then subjected to a hydrogen plasma treatment. Since a situation in which a carbonyl compound is thermally decomposed to generate a low-molecular gas can be avoided, a silicon oxide film or a metal film can be favorably deposited on the organic insulating film etched in an oxygen atmosphere.

According to the sixth method for forming an insulating film, the organic insulating film is etched in an oxygen atmosphere, hydrogen ions are implanted, and then heat treatment is performed. Even if heat treatment is performed, a situation in which a carbonyl compound is thermally decomposed to generate a low-molecular gas can be avoided, so that a silicon oxide film or a metal film is favorably formed on an organic insulating film etched in an oxygen atmosphere. Can be deposited.

According to the seventh method for forming an insulating film, the surface of the underlying film is made hydrophobic by performing a heat treatment on the underlying film in a hydrogen atmosphere, and then the organic insulating film is formed on the underlying film. The deposition improves the adhesion between the base film and the organic insulating film.

According to the eighth method of forming an insulating film, the surface of the underlying film is made hydrophobic by performing a hydrogen plasma treatment on the underlying film, and then an organic insulating film is deposited on the underlying film. Therefore, the adhesion between the base film and the organic insulating film is improved.

According to the ninth method for forming an insulating film, carbon ions are implanted into the base film to increase the affinity of the base film with the organic insulating film or change the surface of the base film to hydrophobic. Since the organic insulating film is deposited on the base film, the adhesion between the base film and the organic insulating film is improved.

According to the tenth method for forming an insulating film, hydrogen ions are implanted into a base film, heat treatment is performed to change the surface of the base film to hydrophobic, and then the base film is Since the organic insulating film is deposited on the substrate, the adhesion between the base film and the organic insulating film is improved.

According to the eleventh method of forming an insulating film, an organic component-containing silicon oxide film is deposited on an organic insulating film by a plasma CVD method using alkoxysilane as a raw material and in the absence of an oxidizing agent. Since oxidation of the organic insulating film can be prevented, generation of low-molecular gas due to oxidation of the organic insulating film can be reliably prevented.

According to the twelfth method for forming an insulating film, an organic component-containing silicon oxide film is deposited on an organic insulating film by a plasma CVD method using alkoxysilane and silane as raw materials and in the absence of an oxidizing agent. Therefore, oxidation of the organic insulating film can be prevented, so that generation of low-molecular gas due to oxidation of the organic insulating film can be reliably prevented.

According to the thirteenth insulating film forming method, an organic insulating film is formed by performing baking and baking in a reducing atmosphere on a coating film made of a material containing an organic component as a main component. Since oxidation of the organic insulating film can be prevented, generation of low-molecular gas due to oxidation of the organic insulating film can be reliably prevented.

[Brief description of the drawings]

FIGS. 1A to 1C are cross-sectional views showing steps of a method for manufacturing a semiconductor device according to first and second embodiments of the present invention.

FIGS. 2A to 2C are cross-sectional views showing steps of a method for manufacturing a semiconductor device according to first and second embodiments of the present invention.

FIGS. 3A to 3C are cross-sectional views illustrating steps of a method for manufacturing a semiconductor device according to first and second embodiments of the present invention.

[Explanation of symbols]

 Reference Signs List 100 semiconductor substrate 101 first metal film 102 silicon nitride film 102A patterned silicon nitride film 103 first organic film 103A patterned first organic film 104 silicon oxide film 104A patterned silicon oxide film 105 Second organic film 105A Patterned second organic film 106 Titanium nitride film 107 First resist pattern 108 Mask pattern 109 Second resist pattern 110 Contact hole 111 Wiring groove 112 Adhesion layer 113 Metal film 114 Second Metal wiring 115 contacts

Claims (18)

[Claims] 1. A step of depositing an organic insulating film containing an organic component as a main component on a substrate, and a step of patterning the organic insulating film by etching the organic insulating film with H ₂ O plasma. And a method for manufacturing a semiconductor device. 2. A step of depositing an organic insulating film containing an organic component as a main component on a substrate, and a step of patterning the organic insulating film by etching the organic insulating film with CO plasma. A method for manufacturing a semiconductor device, comprising: 3. An insulating film depositing step of depositing an organic insulating film mainly containing an organic component on a substrate by a CVD method, and a heat treatment step of performing a heat treatment on the organic insulating film in a hydrogen atmosphere. A method of forming an insulating film. 4. The CVD method in the insulating film deposition step is a plasma CVD method. In the heat treatment step, a hydrogen atmosphere is applied to the organic insulating film without exposing the deposited organic insulating film to an oxidizing atmosphere. 4. The method for forming an insulating film according to claim 3, further comprising a step of performing a heat treatment therein. 5. An insulating film depositing step of depositing an organic insulating film mainly containing an organic component on a substrate by a CVD method, and a plasma processing step of performing a hydrogen plasma treatment on the organic insulating film. A method for forming an insulating film. 6. The CVD method in the insulating film deposition step is a plasma CVD method. In the plasma processing step, hydrogen is applied to the organic insulating film without exposing the deposited organic insulating film to an oxidizing atmosphere. The method for forming an insulating film according to claim 5, further comprising a step of performing a plasma treatment. 7. An insulating film depositing step of depositing an organic insulating film containing an organic component as a main component on a substrate by a CVD method, and ion implantation for implanting hydrogen ions into the organic insulating film and then performing a heat treatment. And a method of forming an insulating film. 8. The CVD method in the insulating film depositing step is a plasma CVD method, and the ion implanting step includes applying hydrogen to the organic insulating film without exposing the deposited organic insulating film to an oxidizing atmosphere. The method for forming an insulating film according to claim 7, comprising a step of implanting ions. 9. A step of depositing an organic insulating film mainly containing an organic component on a substrate, and a step of patterning the organic insulating film by etching the organic insulating film in an oxygen atmosphere. Performing a heat treatment in a hydrogen atmosphere on the patterned organic insulating film. 10. A step of depositing an organic insulating film mainly containing an organic component on a substrate, and a step of patterning the organic insulating film by etching the organic insulating film in an oxygen atmosphere. Performing a hydrogen plasma treatment on the patterned organic insulating film. 11. A step of depositing an organic insulating film mainly containing an organic component on a substrate, and a step of patterning the organic insulating film by etching the organic insulating film in an oxygen atmosphere. Performing a heat treatment after implanting hydrogen ions into the patterned organic insulating film. 12. A step of performing a heat treatment in a hydrogen atmosphere on a base film formed on a substrate, and forming an organic material containing an organic component as a main component on the base film subjected to the heat treatment in a hydrogen atmosphere. A step of depositing an insulating film. 13. A step of performing a hydrogen plasma treatment on a base film formed on a substrate, and depositing an organic insulating film containing an organic component as a main component on the base film subjected to the hydrogen plasma heat treatment. A method of forming an insulating film. 14. An underlayer formed on a substrate,
A method of forming an insulating film, comprising: a step of implanting carbon ions; and a step of depositing an organic insulating film containing an organic component as a main component on the base film into which carbon ions have been implanted. . 15. The method according to claim 15, wherein a base film formed on the substrate is
A step of performing a heat treatment after hydrogen ion implantation, and a step of depositing an organic insulating film containing an organic component as a main component on the base film subjected to the heat treatment after hydrogen ion implantation. A method for forming an insulating film. 16. A step of depositing an organic film containing an organic component as a main component on a substrate; and an organic component formed on the organic film by a plasma CVD method using alkoxysilane as a raw material and in the absence of an oxidizing agent. Depositing a silicon oxide film containing silicon and forming an insulating film composed of the organic film and the silicon oxide film containing organic components. 17. A step of depositing an organic film containing an organic component as a main component on a substrate, and a plasma CVD method using alkoxysilane and silane as raw materials in the absence of an oxidizing agent on the organic film. Depositing an organic component-containing silicon oxide film to form an insulating film composed of the organic film and the organic component-containing silicon oxide film. 18. A step of applying a material containing an organic component as a main component on a substrate to form a coating film, and performing baking and baking on the coating film in a reducing atmosphere to form the coating film. Forming an organic insulating film made of a film.