JP2003289099A - Semiconductor device and method of manufacturing semiconductor device - Google Patents

Abstract

(57) [Problem] To provide a highly reliable semiconductor device having an interlayer insulating film having a sufficiently low dielectric constant and excellent adhesion. SOLUTION: A semiconductor substrate (10), a first insulating film (15) formed on the semiconductor substrate, and a second insulating film (18) formed directly on the first insulating film. A plug buried in a hole provided in the first insulating film, and a wiring layer reaching the first insulating film and buried in a groove provided in the second insulating film. (20) A semiconductor device comprising: The first and second insulating films are each composed of the same type of low dielectric constant film having a relative dielectric constant of 3.5 or less, and the relative dielectric constant of the first insulating film is equal to that of the second insulating film. It is characterized by being larger than the relative permittivity.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semiconductor device and a manufacturing method thereof, and more particularly to a semiconductor device having a multi-layer wiring structure using a low dielectric constant film as an interlayer insulating film and a manufacturing method thereof.

[0002]

2. Description of the Related Art As the size of wirings has become smaller due to the miniaturization of semiconductor elements, the capacitance between wirings has increased and the operating speed of devices has come to be greatly affected.
In order to achieve high-speed miniaturization of devices, it is necessary to reduce the product of wiring resistance and interline capacitance. To this end, low-resistance copper wiring and low dielectric constant are required to reduce wiring capacitance. Adoption of an interlayer insulating film becomes essential. In recent years, porous low dielectric constant films (relative dielectric constants) made of materials such as organic silicon oxide films and organic resin films containing no silicon.
2.5 or less) is required to be applied to the interlayer insulating film.

An example of a semiconductor device using a porous low dielectric constant film as an interlayer insulating film is shown in FIG. In the illustrated semiconductor device, an insulating film 11 and an insulating film 12 in which a lower wiring layer 14 is buried via a barrier metal layer 13 are sequentially formed on a semiconductor substrate 10 on which elements (not shown) are formed. Has been formed. An interlayer insulating film 21 made of a porous low dielectric constant film is provided on the insulating film 12, and a via plug 17 having a barrier metal layer 16 on its side surface and an upper wiring layer 20 via a barrier metal layer 19 are embedded. Be done.

In forming such a semiconductor device, when the groove for forming the upper wiring layer is processed into the insulating film 21, there is a problem that the wiring groove bottom is rough and the processing is difficult to control because it is porous. There is. The roughness of the bottom of the wiring groove may reduce the reliability of the semiconductor device.
In order to avoid this problem, as shown in FIG. 3, a structure in which an etching stopper layer is interposed between the insulating film of the wiring layer and the insulating film of the via layer is adopted. In the structure shown in the figure, on the insulating film 12 in which the lower wiring layer 14 similar to that described above is embedded, the insulating film 22 in which the via plug 17 is embedded and the insulating film 2 in which the upper wiring layer 20 is embedded
4 are stacked with the etching stopper layer 23 interposed therebetween. Generally, the relative dielectric constant of the film forming the etching stopper layer 23 is as large as about 5, so that when the porous low dielectric constant film is used as the insulating films 22 and 24, the effective dielectric constant increases. Further, in general, when the number of laminated films increases and the number of interfaces increases, there is a fear of peeling.

[0005]

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a highly reliable semiconductor device having an interlayer insulating film having a sufficiently low dielectric constant and excellent adhesion.

Further, the present invention provides a method of manufacturing a semiconductor device which can easily control the processing of an interlayer insulating film having a sufficiently low dielectric constant and excellent adhesion without causing roughness on the bottom of the wiring groove. The purpose is to

[0007]

In order to solve the above problems, according to one embodiment of the present invention, a semiconductor substrate, a first insulating film formed on the semiconductor substrate, and a first insulating film are provided. The second insulating film formed immediately above, the plug embedded in the hole provided in the first insulating film, and the second insulating film reaching the first insulating film and provided in the second insulating film A wiring layer embedded in the groove, wherein the first and second insulating films are made of the same type of low dielectric constant film having a relative dielectric constant of 3.5 or less. A relative dielectric constant of the film is larger than that of the second insulating film.

Another aspect of the present invention is a semiconductor substrate,
A first insulating film formed on the semiconductor substrate, a second insulating film formed directly on the first insulating film, and a hole formed in the first insulating film. A plug layer and a wiring layer that reaches the first insulating film and is embedded in a groove provided in the second insulating film;
And the second insulating film is made of a low dielectric constant film having a relative dielectric constant of 3.5 or less in which constituent elements match each other, and the density of the first insulating film is higher than that of the second insulating film. A characteristic semiconductor device is provided.

Yet another aspect of the present invention is to coat a semiconductor substrate with a solution material containing first and second polymers containing methylpolysiloxane as a main component and having a weight average molecular weight different by 10 times or more, A step of forming a coating film of 1;
Immediately above the first coating film, a solution material containing a third polymer containing methylpolysiloxane as a main component is applied to form a second coating film, and the first and second coating films are formed.
By applying heat treatment to the coating film of
Forming a first organic silicon oxide film having the following relative dielectric constant and a second organic silicon oxide film having a relative dielectric constant of 2.5 or less; and forming holes in the first organic silicon oxide film. And forming a groove in the second organic silicon oxide film so that the first organic silicon oxide film is exposed, and a plug and a wiring layer are formed by filling a conductive material in the hole and the groove. The present invention provides a method for manufacturing a semiconductor device, which comprises:

[0010]

DETAILED DESCRIPTION OF THE INVENTION An embodiment of the present invention will be described in detail below with reference to the drawings.

FIG. 1 is a sectional view of a semiconductor device according to an embodiment of the present invention.

In the illustrated semiconductor device, the insulating film 1 is formed on the semiconductor substrate 10 on which elements (not shown) are formed.
1 and 12 are sequentially formed, and the insulating film 12 has
A lower wiring layer 14 made of Cu or the like is buried via a barrier metal layer 13 made of TaN or the like. Insulating film 11
And 12 can be formed by, for example, a CVD method or a coating method.

On the insulating film 12, a via-layer insulating film 15 is formed.
And the insulating film 18 of the wiring layer is sequentially formed. Insulation film 1
The via plug 17 and the upper wiring layer 20 are respectively filled in the recesses formed by the holes and the grooves formed in succession with 5 and 18 by inserting Cu or the like through the barrier metal layers 16 and 19 made of TaN or the like. It is formed.

An insulating film such as a SiN film or a SiC film may be formed between the insulating film 12 and the via-layer insulating film 15 by the CVD method.

The insulating film 15 of the via layer and the insulating film 18 of the wiring layer are formed of a low dielectric constant film whose relative dielectric constant is 3.5 or less and whose constituent elements are completely the same. However, the density of the insulating film 15 is higher than that of the insulating film 18. Specifically, the density of the insulating film 15 is 1.2 g / cm ³ or more.2.
0 g / cm ³ or less, and the density of the insulating film 18 is 0.5
is less than g / cm ³ or more 1.2g / cm ^3.

The insulating film 15 of the via layer is required to have a high density while maintaining a low dielectric constant. However, when the density is excessively high, the relative dielectric constant is the low dielectric constant film of this embodiment. There is a possibility that the required 3.5 will be exceeded. In order to maintain the relative dielectric constant of 3.5 or less, it is desired that the density of the insulating film 15 of the via layer be suppressed to 2.0 g / cm ³ or less.
In order to secure a higher density than the insulating film 18 of the wiring layer, the lower limit of the density of the insulating film 15 of the via layer is 1.2 g / c.
It is preferably m ³ . On the other hand, the insulating film 18 of the wiring layer
Is preferable as the relative dielectric constant is lower. Specifically, the relative dielectric constant is preferably 2.5 or less, and the density of the insulating film having such a relative dielectric constant is less than 1.2 g / cm ³ . However, if the density is excessively low, it becomes difficult to keep the film as a film, and therefore the density of the insulating film 18 of the wiring layer is desired to be at least 0.5 g / cm ³ .

The insulating film 15 and the insulating film 18 are films whose constituent elements are completely the same as described above, but the composition ratio of the constituent elements in the two insulating films may be different. Specifically, these two insulating films 15 and 18
Can be formed by a coating type organic polymer (organic SOD) film such as polyarylene or polyarylene polyether, a hydrogensilsesquioxane film, or a methylpolysiloxane film. Since the via layer insulating film 15 and the wiring layer insulating film 18 are composed of the same type of film, these two insulating films are laminated with sufficient adhesion.

The insulating film 15 and the insulating film 18 will be described below.
An example in which both are formed by a coating method will be described.

As the material for the insulating film 15 of the via layer, a mixture of a high molecular weight polymer (first polymer) and a low molecular weight polymer (second polymer) which are homologous polymers having a weight average molecular weight different by 10 times or more is used. be able to.
The homogenous polymer is a polymer in which the constituent elements are completely the same, and the composition ratio thereof may be different. By mixing and using two homopolymers having different weight average molecular weights of 10 times or more, the density can be increased for the following reasons. That is, in an insulating film formed by using a mixture of two similar polymers of high molecular weight and low molecular weight, the high molecular weight first polymer constitutes the skeleton, and the low molecular weight second polymer is formed so as to fill the gap. Of polymers are present. The density of the obtained insulating film can be increased due to the blending of two homopolymers having different weight average molecular weights.

In order to increase the density of the insulating film 15,
The difference in weight average molecular weight between the two polymers is more preferably 100 times or more. For example, weight average molecular weight 10
A polymer having a molecular weight of 0,000 or more and a polymer having a molecular weight of 10,000 or less can be used as the first polymer and the second polymer, respectively.

Basically, the desired effects can be obtained if the weight average molecular weights of the high molecular weight first polymer and the low molecular weight second polymer are in the ranges described above. However, when the molecular weight of the first polymer is too large, it is difficult to prepare a solution and it is difficult to apply the solution onto the substrate. Therefore, it is desired that the weight average molecular weight of the first polymer be the maximum value within the range where the solution can be easily prepared, specifically, about 3,000,000. More preferably, the weight average molecular weight of the first polymer is about 1,000,000 to 2,000,000.

On the other hand, the low molecular weight second polymer can be present as a polymer in order to fill the gaps in the skeleton formed by thermal polymerization of the above high molecular weight first polymer. It is desired that the molecular weight is as low as possible.
Specifically, the molecular weight of the second polymer is 1,000 to
It is more preferably 10,000.

The mixing ratio of the high molecular weight polymer and the low molecular weight polymer can be appropriately selected, but the weight ratio is 10 /
When it is set within the range of 90 to 90/10, the crack resistance of the obtained insulating film is also improved, which is preferable. Also,
From the viewpoint of the dielectric constant, the above compounding ratio is 20/80 to 80.
It is desirable to be in the range of / 20.

Further, between the high molecular weight polymer having a weight average molecular weight and the low molecular weight polymer described above, an intermediate molecular weight polymer of the same kind as these may be blended. Since the intermediate molecular weight polymer has a molecular weight lower than that of the high molecular weight polymer and higher than that of the low molecular weight polymer, the intermediate molecular weight polymer further densifies the obtained insulating film to increase the density. In an insulating film formed by using a mixture further containing an intermediate molecular weight polymer in addition to a high molecular weight polymer and a low molecular weight polymer, since the polymers having different molecular weights are packed in a denser array, the density is further increased. To be enhanced.

On the other hand, as the material of the insulating film 18 of the wiring layer, the same kind of polymer (similar polymer) as the polymer compounded as the material of the insulating film 15 can be used. As described above, the insulating film 18 of the wiring layer is required to have a lower dielectric constant, and the relative dielectric constant is 2.5.
The following is preferable. For example, an insulating film having a relative dielectric constant of 2.5 or less is obtained by using a high molecular weight polymer (first polymer) having a weight average molecular weight of about 1,000,000 to 2,000,000, which is blended as a material of the insulating film 15, alone. Can be formed. Since it is composed of a polymer having a relatively large weight average molecular weight, voids are present in the obtained insulating film, and such voids cause low density. In addition, as long as it is a high molecular weight polymer that satisfies the above-described weight average molecular weight condition, the same kind of polymer different from the material of the insulating film 15 can be used. Further, as long as a desired relative dielectric constant can be secured, polymers having different weight average molecular weights having the same constituent elements may be further contained.

The above-mentioned polymer is dissolved in an organic solvent such as an alcohol solvent, a ketone solvent, an amide solvent, and an ester solvent to prepare a varnish which is a solution material for the insulating film. Specifically, as the organic solvent, propylene glycol monopropyl ether, propylene glycol monoethyl ether, cyclohexane or the like can be used. In the varnish,
Ti or Zr as a catalyst component may be contained in an amount of about 1 wt% or less. A component such as a surfactant may be added to such a chemical solution. Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants.
Further, silicone-based surfactants, polyalkylene oxide-based surfactants, fluorine-containing surfactants and the like can be mentioned.

The varnish thus prepared is applied onto a predetermined lower surface by, for example, a spin coating method, a dipping method or a roller blade method to form a coating film. Then, using a hot plate, an oven, a furnace or the like, the solvent is volatilized by heating in an argon atmosphere, under vacuum, under reduced pressure in which oxygen is controlled, or the like. Heating
1 to 10 minutes at 50 to 150 ° C, then 150 to 25
It is preferable to perform stepwise at 0 ° C. for 1 to 10 minutes.
By gradually heating, the coating film is fixed to the base.

In this example, methyl polysiloxane having a weight average molecular weight of 1,000,000 or more was used as the high molecular weight polymer, and methyl polysiloxane having a weight average molecular weight of 10,000 or less was used as the low molecular weight polymer. The mixing ratio of the high molecular weight polymer and the low molecular weight polymer is 3 by weight.
It was set to about 0/70. The two polymers were dissolved in cyclohexanone as a solvent to prepare a solution material for the insulating film 15 (hereinafter referred to as a first solution material).

On the other hand, as the material of the insulating film 18, the above-mentioned methylpolysiloxane having a weight average molecular weight of 1,000,000 or more is used, and it is dissolved in cyclohexanone as a solvent to form a solution material of the insulating film 18 (hereinafter referred to as a second solution material). Referred to as).

First, the first solution material was spin-coated using a coater on the insulating film 12 in which the lower wiring layer 14 was embedded to form a first coating film. This coating film was heated at 80 ° C for 1 minute using a hot plate, and then at 200 ° C for 1 minute.
By gradually heating for a minute, it was fixed to the lower insulating film 12.

A second solution material was spin-coated on the fixed first coating film using a coater to form a second coating film. This coating film was fixed to the first coating film by heating it stepwise at 80 ° C. for 1 minute and then at 200 ° C. for 1 minute using a hot plate as described above.

The fixed first and second coatings are 2
Further heating was performed using a hot plate maintained at 00 to 500 ° C, for example, 420 ° C. This heating is preferably carried out in an atmosphere of N ₂ atmospheric pressure (O ₂ concentration of 500 ppm or less) for about 1 to 60 minutes. If the substrate temperature is lower than 200 ° C, it becomes difficult to sufficiently accelerate the crosslinking reaction in the coating film, while if it exceeds 500 ° C, the residual stress may not be sufficiently reduced.

Thus, the via layer insulating film 15 made of the methyl polysiloxane film and the wiring layer insulating film 18 made of the methyl polysiloxane film were formed. Insulating film 15
Had a density of 1.35 g / cm ³ and the insulating film 18 had a density of 1.00 g / cm ³ . The relative dielectric constant of the insulating film 15 was about 3.0, and the relative dielectric constant of the insulating film 18 was about 2.2. Since the density is high, the etching rate of the via layer insulating film 15 is about three times the etching rate of the wiring layer insulating film 18.

Several varnishes having a compounding ratio within the above range were prepared in the first solution material, and the relative permittivity and density were measured. As a result, the density of a film having a relative dielectric constant of about 2.5 is about 1.2 g / cm ³ , and the density of a film having a relative dielectric constant of about 3.5 is about 2.0 g / cm 3.
^{Was 3} .

The relationship that the relative permittivity decreases as the density of the insulating film decreases in this way is not limited to the organic silicon oxide film, but is a relationship that generally holds for the insulating film.

In the above-mentioned embodiment, since the via layer insulating film 15 and the wiring layer insulating film 18 are formed by the coating method, these two insulating films can be baked together.

When the etching stopper layer 23 in the semiconductor device shown in FIG. 3 is formed of, for example, a CVD film, the insulating films 22 and 24 above and below it cannot be fired at the same time, and the number of steps in film formation is increased. Will increase. Further, since the interface is increased, there is a fear of peeling, and due to the large relative permittivity of the etching stopper layer 23, even if the insulating films 22 and 24 have a low permittivity, the effect may be canceled. is there.

On the other hand, in the method of this embodiment, not only the number of steps and the film forming time can be shortened,
The via layer insulating film 15 and the wiring layer insulating film 18 are composed of the same type of film, and this is effective in improving the adhesion between layers in combination with the baking of these two insulating films collectively. There is. Moreover, since the etching stopper layer is not interposed between the two insulating films 15 and 18, the problem that the effective dielectric constant is increased unlike the conventional case is avoided.

Via holes and wiring grooves were formed in the obtained insulating films 15 and 18 by RIE (reactive ion etching) by a conventional method. When the surface of the bottom surface of the wiring groove was observed by SEM, no roughness was confirmed. Further, no variation in the wiring groove depth was observed between the center and the edge of the 8-inch wafer. As described above, since the insulating film 15 of the via layer formed in this example has a high etching rate, it is considered that variations in the etching rate between the wafer center and the edge are absorbed, and variations in the wiring groove depth are reduced.

A barrier metal layer 16 is provided in the via hole.
The via plug 17 is formed through the via, and the upper wiring layer 20 is formed in the wiring groove through the barrier metal layer 19. Thus, the semiconductor device having the dual damascene wiring structure shown in FIG. 1 is obtained.

In the illustrated example, the bottom of the groove for burying the upper wiring layer 20 is formed of the insulating film 1 of the via layer.
Although it is in contact with the surface of No. 5, the upper wiring layer 20 may be embedded by processing a groove so that the insulating film 15 is recessed.

For comparison, the above-mentioned second solution was applied on the insulating film 12 in which the lower wiring layer 14 was buried to form an insulating film. Holes and trenches were formed in this insulating film, and the plug and the upper wiring layer were filled in to obtain a semiconductor device having the structure shown in FIG. In such a semiconductor device, it can be said that the insulating film of the via layer and the insulating film of the wiring layer are both composed of a porous low dielectric constant insulating film having a density of 1.00 g / cm ³ . When the surface of the bottom surface of the wiring groove was observed by SEM when the wiring groove was formed, roughness was observed on the bottom of the wiring groove. This is because the density of the insulating film exposed at the bottom of the wiring groove is low. Furthermore, variations in the wiring groove depth were observed between the center and the edge of the 8-inch wafer.

Although the embodiments of the present invention have been described above, the present invention is not limited to these embodiments. For example, although the organic silicon oxide film is given as an example of the insulating film 15 and the insulating film 18 described above, if the insulating film 15 of the via layer and the insulating film 18 of the wiring layer are of the same type, the present invention provides other insulating films. It can also be applied to membranes. For example, organic SOD such as polyarylene and polyarylene ether
Membrane, and hydrogen silsesquioxane (Hydr
gen silsesquioxane (HSQ) film and the like.

The insulating film 15 of the via layer in the semiconductor device shown in FIG. 1 can also be formed by the CVD method. In this case, the semiconductor device shown in FIG. 1 can be manufactured by forming the insulating film 18 of the wiring layer by the same method as described above except that the insulating film 15 is formed by the CVD method. Alternatively, by appropriately changing the conditions, the insulating film 18 of the wiring layer is formed on the insulating film 15 of the via layer formed by the coating method or the CVD method by the CVD method.
Can also be formed.

Regardless of the method for forming the via layer insulating film 15, no roughness was confirmed on the bottom surface of the wiring groove after the wiring groove was formed, and the wiring groove depth was formed between the center and the edge of the 8-inch wafer. There is no variation in size observed. Further, since no etching stopper film is present, an effective increase in the dielectric constant is suppressed in any case.

[0046]

As described in detail above, according to the present invention,
A highly reliable semiconductor device having an interlayer insulating film having a sufficiently low dielectric constant and excellent adhesion is provided.
Further, according to the present invention, there is provided a method for manufacturing a semiconductor device in which an interlayer insulating film having a sufficiently low dielectric constant and excellent adhesiveness can be easily processed and controlled without causing roughness on the wiring groove bottom. .

The present invention is extremely effectively used for manufacturing a semiconductor device having a multilayer wiring structure, especially a damascene wiring structure, and its industrial value is enormous.

[Brief description of drawings]

FIG. 1 is a sectional view showing an example of a semiconductor device according to the present invention.

FIG. 2 is a sectional view showing a semiconductor device having a conventional structure.

FIG. 3 is a cross-sectional view showing a semiconductor device having a conventional structure.

[Explanation of symbols]

10 ... Semiconductor substrate 11 ... Insulating film 12 ... Insulating film 13 ... Barrier metal layer 14 ... Lower wiring layer 15 ... Insulating film of via layer 16 ... Barrier metal layer 17 ... Via plug 18 ... Insulating film of wiring layer 19 ... Barrier metal layer 20 ... Upper wiring layer 21 ... Porous low dielectric constant film 22 ... Insulating film 23 ... Etching stopper layer 24 ... Insulating film

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Claims (14)

[Claims] 1. A semiconductor substrate, a first insulating film formed on the semiconductor substrate, a second insulating film formed directly on the first insulating film, and a first insulating film formed on the first insulating film. A plug layer embedded in the provided hole; and a wiring layer reaching the first insulating film and embedded in a groove provided in the second insulating film. Of the same kind of low dielectric constant films each having a relative dielectric constant of 3.5 or less, and the relative dielectric constant of the first insulating film is larger than the relative dielectric constant of the second insulating film. A semiconductor device characterized by: 2. A semiconductor substrate, a first insulating film formed on the semiconductor substrate, a second insulating film formed directly on the first insulating film, and a first insulating film formed on the first insulating film. A plug layer embedded in the provided hole; and a wiring layer reaching the first insulating film and embedded in a groove provided in the second insulating film. Is formed of a low dielectric constant film having a relative dielectric constant of 3.5 or less in which constituent elements match each other, and the density of the first insulating film is higher than the density of the second insulating film. Semiconductor device. 3. The density of the first insulating film is 1.2 g /
cm ³ or more and 2.0 g / cm ³ or less, and the density of the second insulating film is 0.5 g / cm ³ or more and less than 1.2 g / cm ^3; The semiconductor device described. 4. The relative dielectric constant of the first insulating film is more than 2.5 and 3.5 or less, and the relative dielectric constant of the second insulating film is 2.5 or less. The semiconductor device according to claim 1. 5. The semiconductor device according to claim 1, wherein the second insulating film is a porous film. 6. The first and second insulating films are both coating type organic polymer films, hydrogensilsesquioxane films, or methylpolysiloxane films. 2. The semiconductor device according to item 1. 7. A first coating film is formed on a semiconductor substrate by applying a solution material containing methylpolysiloxane as a main component and having a weight average molecular weight different by 10 times or more and containing a second polymer. A step of applying a solution material containing a third polymer containing methylpolysiloxane as a main component to form a second coating film immediately above the first coating film; By subjecting the second coating film to heat treatment at the same time, a first organic silicon oxide film having a relative dielectric constant of 3.5 or less and a second organic silicon oxide film having a relative dielectric constant of 2.5 or less are obtained. Forming a film, forming a hole in the first organic silicon oxide film, and forming a groove in the second organic silicon oxide film so that the first organic silicon oxide film is exposed, Conductivity in the holes and grooves The method of manufacturing a semiconductor device characterized by comprising the step of forming the plugs and the wiring layer by burying a fee. 8. The method of manufacturing a semiconductor device according to claim 7, wherein the heat treatment is performed at a temperature of 200 ° C. or higher and 500 ° C. or lower. 9. The method for manufacturing a semiconductor device according to claim 7, wherein the weight average molecular weight of the first polymer is 100 times or more the weight average molecular weight of the second polymer. 10. The weight average molecular weight of the first polymer is 1,000,000 or more, and the weight average molecular weight of the second polymer is 10,000 or less. A method of manufacturing a semiconductor device according to item. 11. The blending ratio of the first polymer and the second polymer is 10/90 to 90/10 by weight, and the blending ratio is 10/90 to 90/10. Of manufacturing a semiconductor device of. 12. The compounding ratio of the first polymer and the second polymer is 20/80 to 80/20 by weight, and the compounding ratio is 20/80 to 80/20. Of manufacturing a semiconductor device of. 13. The semiconductor according to claim 7, wherein the weight average molecular weight of the third polymer is 100 times or more the weight average molecular weight of the second polymer. Device manufacturing method. 14. The method of manufacturing a semiconductor device according to claim 7, wherein the third polymer is the same polymer as the first polymer.