JP3195248B2 - Organic insulating film material and method of manufacturing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an insulating film material, and particularly to an organic insulating film material used in manufacturing a semiconductor device.

[0002]

2. Description of the Related Art As is well known, an increase in the speed of an LSI is basically achieved by miniaturization of transistors constituting the LSI. However, when elements are further integrated at a high density and wiring intervals are reduced in the future, delay of a signal propagating through the wiring and crosstalk between adjacent wirings become remarkable. It is expected that these will be important factors that hinder high performance of the LSI.

As one of the measures for solving such wiring delay and crosstalk, it has been studied to lower the dielectric constant of an insulating film filling between wirings. Since many organic polymers have a considerably lower dielectric constant than a silicon oxide film, when an organic polymer is used as an insulating film material (organic insulating film material) to form an insulating film (organic insulating film), a wiring delay and It is considered that the effect of reducing crosstalk is large.

[0004] For example, benzocyclobutene
butene (referred to as BCB)) from Dow Chemical Co., Ltd.
(Product name). This material has an isotropic relative permittivity of 2.7 (1 MHz), a glass transition temperature of 350 ° C. or higher, and shows good embedding characteristics (Reference 1: “1995 Dielectrics for VLSI / ULSI Multilevel”).
Inerconnection Conference (DUMIC 95), 1995, pp.269-27
5.)).

[0005]

However, there are some problems in applying the above materials to an LSI process. That is, since this material is made of an organosilicon polymer containing silicon atoms, when O ₂ -RIE (reactive ion etching), which is a method of processing an organic insulating film, is applied, silicon in the film becomes silicon oxide. Become. This becomes an etching residue. This material is 35
Due to thermal decomposition at 0 ° C., it is necessary to lower the process temperature below this. Therefore, this material cannot be used in a process requiring a temperature of about 400 ° C., such as a wiring step.

[0006] Accordingly, it has been desired to develop an organic insulating film material made of an organic polymer containing no different elements such as silicon and having higher heat resistance.

[0007] More desirably, an organic insulating film material having a small relative dielectric constant has been desired.

[0008]

Accordingly, the inventor of the present application has designed an organic polymer that can be used as an organic insulating film material based on the following known facts (1) to (4).

When an aromatic ring is introduced into a polymer, the heat resistance of the polymer can be improved.

Many polymers having a linear structure are inferior in heat resistance to polymers having a crosslinked structure.
Even with a polymer having a linear structure, heat resistance can be increased by adopting a structure that suppresses the movement of the main chain.

When fluorine is introduced into a polymer, the relative dielectric constant of the polymer can be reduced.

According to the first organic insulating film material of the present invention, which is designed based on the above-mentioned known facts (1) to (4), oxygen is directly contained in any two benzene rings one by one including a plurality of benzene rings. A linear structure comprising a bonded bisphenol-type structural unit and an aryl-type structural unit containing one or more benzene rings and directly linking the oxygen to the bisphenol-type structural unit. Characterized by comprising an organic polymer having: However, the benzene ring includes a case where all or a part of the benzene ring is a condensed benzene ring. The fused benzene ring is a fused ring composed of a plurality of six-membered rings such as a naphthalene ring, an anthracene ring, and a pyrene ring. The bisphenol-type structural unit may be a case where two or more kinds of bisphenol-type structural units are present in the organic insulating film material. Similarly, the aryl type structural unit may be a case where two or more types of the aryl type structural unit exist in the organic insulating film material.

According to the first organic insulating film material of the present invention, a benzene ring (in the case of a condensed benzene ring, both a benzene ring and a condensed benzene ring may be introduced) in each structural unit. I have. For this reason, the heat resistance of the organic insulating film material of the present invention is increased.

In a preferred embodiment of the first organic insulating film material according to the present invention, the bisphenol-type structural unit is formed of benzene rings having oxygen directly bonded thereto (in the case of condensed benzene rings, a benzene ring and a condensed benzene ring). Or a benzene ring to which oxygen is directly bonded (in the case of condensed benzene rings, a benzene ring and a condensed benzene ring are not bonded to each other). May be a structural unit bonded via a polycyclic alicyclic compound.

When the bisphenol-type structural unit is a structural unit in which benzene rings to which oxygen is directly bonded are connected by one single bond, focusing on the bisphenol-type structural unit, the polymer between two oxygens Is composed of two benzene rings (in the case of two condensed benzene rings, there may be a benzene ring and a condensed benzene ring), and carbon atoms having sp ³ hybridized orbitals are introduced into the main chain. Absent. For this reason, the main chain is prevented from moving laterally or eccentrically due to heat, and heat resistance is increased. As such a bisphenol-type structural unit, for example, 2,2′-bi-1-naphthol represented by the following formula (1) (the chemical name shown here means that hydrogen is bonded to oxygen, This is the name of an aromatic compound when a hydroxyl group is directly bonded to the ring. The same applies to the following formulas (2) to (8).)
2′-biphenol, represented by the following formula (3),
4'-biphenol can be mentioned. That is,
It has two monohydric phenols (two monohydric naphthols in the case of formula (1)), and the benzene rings (naphthalene rings in the case of formula (1)) are bonded by one single bond. Corresponding to the aromatic compound used.

[0016]

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When the bisphenol-type structural unit is a structural unit in which benzene rings to which oxygen is directly bonded are bonded via a polycyclic alicyclic compound, attention is paid to the bisphenol-type structural unit. The main chain of the polymer between two oxygens is composed of two benzene rings (in the case of two condensed benzene rings, a benzene ring and a condensed benzene ring may be used) and a polycyclic ring connecting the two benzene rings. And an alicyclic compound. The polycyclic alicyclic compound introduced into the main chain is rigid, so that the main chain is prevented from laterally swaying or deforming due to heat, and has high heat resistance. Examples of such a bisphenol-type structural unit include 1,3-adamantylidenebisphenol represented by the following formula (4) and 2,5-adamantylidene bisphenol represented by the following formula (5)
Norbornylidene bisphenol can be mentioned. That is, it corresponds to an aromatic compound having two monohydric phenols and benzene rings bonded to each other via a polycyclic alicyclic compound. Here, the alicyclic compound in 1,3-adamantylidenebisphenol is tetracyclic,
The alicyclic compound in 2,5-norbornylidenebisphenol is tricyclic.

[0018]

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According to the second organic insulating film material of the present invention, any one of a plurality of benzene rings containing one or more benzene rings can be used.
A bisphenol-type structural unit in which two oxygens are directly bonded to one benzene ring, and an aryl-type structure containing one or more benzene rings and which is directly bonded to the oxygen to connect the bisphenol-type structural units It is characterized by comprising an organic polymer having a linear structure composed of units. However, the benzene ring includes a case where all or a part of the benzene ring is a condensed benzene ring. The bisphenol-type structural unit may be a case where two or more kinds of bisphenol-type structural units are present in the organic insulating film material. Similarly, the aryl type structural unit may be a case where two or more types of the aryl type structural unit exist in the organic insulating film material.

According to the second organic insulating film material of the present invention, a benzene ring (in the case of a condensed benzene ring, both a benzene ring and a condensed benzene ring may be introduced) in each structural unit. I have. For this reason, the heat resistance of the organic insulating film material of the present invention is increased. Focusing on the bisphenol-type structural unit, the main chain of the polymer is composed of one benzene ring (may be a condensed benzene ring) between two oxygen atoms, and the main chain has carbon atoms having sp ³ hybridized orbitals. Has not been introduced. For this reason, the main chain is prevented from moving laterally or eccentrically due to heat, and heat resistance is increased. Focusing on the bisphenol-type structural unit,
Between two oxygens, the main chain of the polymer is composed of one benzene ring (sometimes a fused benzene ring), and no single bond is introduced into the main chain. For this reason, the rotation of the main chain does not occur between the two oxygens, the movement of the main chain due to heat is suppressed, and the heat resistance is increased. Examples of the bisphenol-type structural unit in the present invention include 1,5-dihydroxynaphthalene represented by the following formula (6) and 2,6-dihydroxynaphthalene represented by the following formula (7). That is, it corresponds to bivalent naphthol. The polyphenol-type structural units shown in the formulas (6) and (7) each have a naphthalene ring, but have a benzene ring (here, a condensed benzene is not included).
Even those having an anthracene ring can be used as the bisphenol-type structural unit in the present invention.

[0021]

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In a preferred embodiment of the second organic insulating film material according to the present invention, the bisphenol-type structural unit may contain one or more benzene rings (including a case where all or a part thereof is a condensed benzene ring). Is preferably a structural unit to which fluorine is directly bonded. When an organic insulating film material is constituted by such a bisphenol-type structural unit, the relative dielectric constant of the organic insulating film material is reduced because fluorine is introduced into the organic insulating film material. As such a bisphenol-type structural unit, for example, 2,2 represented by the following formula (8)
3,5,6-tetrafluoro-1,4-hydroquinone can be mentioned. That is, it corresponds to a fluorine-substituted dihydric phenol. The polyphenol-type structural unit represented by the formula (8) has a benzene ring,
Even those having a naphthalene ring or an anthracene ring can be used as the bisphenol-type structural unit in the present invention.

[0023]

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In a preferred embodiment of the first and second organic insulating film materials of the present invention, the aryl-type structural unit may be replaced with an arbitrary one or more benzene rings (when all or a part is a condensed benzene ring, ) Is preferably a structural unit in which fluorine is directly bonded. When an organic insulating film material is constituted by such an aryl-type structural unit, the relative dielectric constant of the organic insulating film material becomes small because fluorine is introduced into the organic insulating film material. As such an aryl-type structural unit, for example, 1,4-perfluorophenylene represented by the following formula (9) (the chemical name shown here is a name as a fluoroaryl-type structural unit in an organic polymer. The same applies to the following equations (10) to (14).)
4,4′-perfluorobiphenylene represented by the following formula (10), 1,5-perfluoronaphthalenylene represented by the following formula (11), 2,6 represented by the following formula (12)
-Perfluoronaphthalenylene, 1,6-perfluoronaphthalenylene represented by the following formula (13), and 1-trifluoromethyl-2,4-trifluorophenylene represented by the following formula (14) may be mentioned. it can.

[0025]

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The first and second organic insulating film materials of the present invention may have any suitable molecular weight depending on the purpose of use. However, when forming an organic insulating film made of the organic insulating film material of the present invention, since a coating method is used,
The upper limit of the molecular weight is preferably 2,000,000 in consideration of the ease of preparation of the coating solution and the thickness of the formed organic insulating film. Further, the lower limit of the molecular weight is preferably set to 10000 in consideration of the heat resistance of the organic insulating film. Molecular weight 100
In the case of the range of 00 to 2,000,000, the solubility of the organic insulating film material in the solvent for preparing the coating liquid is sufficiently large, and thus it is possible to form an organic insulating film having a thickness of about 1 μm. Further, when the molecular weight is in the above range, the glass transition point is as high as 200 ° C. to 350 ° C., so that the lower limit of the process temperature can be maintained at 400 ° C. or more.

Further, according to the first method for producing an organic insulating film material of the present invention, an aromatic compound containing a plurality of benzene rings and a hydroxyl group directly bonded to any two benzene rings one by one And an aromatic halogen compound containing one or more benzene rings, and two or more halogens are directly bonded to any one or more benzene rings as a whole of the aromatic halogen compound. And polymerizing the second monomer comprising an aromatic halogen compound in the presence of a basic catalyst. However, the benzene ring includes a case where all or a part of the benzene ring is a condensed benzene ring.

According to the second method for producing an organic insulating film material of the present invention, an aromatic compound containing one or more benzene rings and two hydroxyl groups directly bonded to any one benzene ring is provided. A first monomer comprising a compound and an aromatic halogen compound containing one or more benzene rings, wherein two or more halogens are directly bonded to any one or more benzene rings as a whole of the aromatic halogen compound; Of a halogenated aromatic compound
Is polymerized in the presence of a basic catalyst. However, the benzene ring includes a case where all or a part of the benzene ring is a condensed benzene ring.

Thus, the first and second embodiments of the present invention
When the organic insulating film material is manufactured, the first monomer present as a phenoxide ion in the reaction solution is replaced by the halogen in the second monomer by the action of the basic catalyst. Such a substitution reaction occurs at two positions in the first monomer, and bonds to the second monomer at each position, whereby a polymer having a linear structure is formed.

Here, examples of the basic catalyst in the present invention include potassium carbonate, sodium carbonate and an organic base.

[0031]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below. However, it should be understood that the used materials and their amounts, the processing temperature, the processing time, the numerical conditions such as the film thickness, and the processing methods mentioned in the following description are only examples within the scope of the present invention.

1. First Example The organic insulating film material of this example has a linear structure composed of a bisphenol-type structural unit represented by the following formula (1) and an aryl-type structural unit represented by the following formula (10). Is an organic polymer having This organic polymer is a poly (aryl ether) whose main chain is composed of a benzene ring, a naphthalene ring and oxygen.

[0033]

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The organic insulating film material of this example was manufactured by the following method. First, 2,2′-bi-1- as a first monomer was placed in a reactor equipped with a stirrer, a cooling pipe, and a thermometer.
Naphthol 28.6 g (0.10 mol) and perfluorobiphenyl 33.4 g (0.
10 mol) and potassium carbonate 3 as a basic catalyst
0.4 g (0.22 mol) was added thereto, and 200 ml of N, N-dimethylacetamide as a solvent was further added to dissolve the first and second monomers and the basic catalyst. After the inside of the reactor was sufficiently purged with nitrogen, the reaction solution was promptly heated to 80 ° C. and stirred under a nitrogen atmosphere for 24 hours to carry out a polymerization reaction. Then, after cooling the reaction solution to room temperature, the reaction solution was poured into dilute hydrochloric acid to form a precipitate. After the precipitate thus obtained was filtered off using a filter paper, the precipitate was washed with water until the washing liquid became neutral. The precipitate washed with water was finally washed with methanol, air-dried, and then dried in a vacuum dryer at 80 ° C. for 24 hours to obtain 55 g of a polymer as an organic insulating film material.

The weight average molecular weight of the polymer produced as described above was 65,000. However, the weight-average molecular weight was measured by gel permeation chromatography (the weight-average molecular weight was measured in the same manner as in each of the examples below).

The glass transition temperature of this polymer is 25
It was 0 ° C. However, the glass transition temperature was determined by differential scanning calorimetry (in each of the examples described below, the glass transition temperature was determined in the same manner as in this example).

The weight loss of this polymer in the temperature range of 400 ° C. to 500 ° C. was 0% (below the measurement limit). However, the weight loss was measured by thermogravimetric differential thermal analysis (in each of the examples described below, the weight loss was measured in the same manner as in this example).

The relative dielectric constant of this polymer was 2.70. However, the relative dielectric constant of this polymer was determined by the following method (in each of the examples described below, the relative dielectric constant was determined by the same method as in this example). That is, first, 5.0 g of this polymer was mixed with 50% of 2-methoxyethyl acetate.
The solution was dissolved in the solution and the solution was filtered through a 0.2 μm membrane filter to prepare a coating solution. Thereafter, this coating solution is spin-coated on a silicon substrate (resistivity of 10 μΩcm or less), baked on a hot plate at 200 ° C. for 30 minutes, and then at 360 ° C. in a nitrogen atmosphere for 1 hour, to a thickness of 0.5 μm.
A 0 μm film of this polymer was formed. Thereafter, holes of an appropriate size (for example, 0.14 m in diameter) are formed on the membrane.
Aluminum was deposited by a vacuum deposition method through a stencil mask having a plurality of sizes (m to 8.0 mm). Then, the capacitance was measured at a high frequency (1 MHz) using the metal / insulating film / semiconductor structure obtained on the silicon substrate to determine the relative dielectric constant.

As described above, the organic insulating film material of this embodiment does not thermally decompose in the temperature range of 400 ° C. to 500 ° C., and has improved heat resistance by 150 ° C. or more than the conventional material. Accordingly, it can sufficiently withstand a process that requires a temperature of about 400 ° C. in which connection holes between wirings are filled with metal, and can be used as an organic insulating film material for LSI. Further, the relative dielectric constant is as small as 2.7. When an insulating film (organic insulating film) is formed using this material, a further effect of reducing signal propagation delay can be expected. Therefore, development of a high-speed LSI using an organic insulating film having a low dielectric constant is facilitated.

A 0.5 μm-thick film made of this polymer prepared by spin-coating the above coating solution on a silicon substrate and baking at 360 ° C. for 1 hour was used as a measurement sample for IR measurement (for IR measurement). Used FTS-60 (model number) manufactured by Biolzd as a measuring device.)
(In each of the examples described below, IR measurement was performed in the same manner as in this example.) IR of this polymer
During chart, the 1610 cm ^-1 of the naphthalene ring C-
A broad peak due to stretching vibration of the C bond was observed. The peak due to the stretching vibration of the CC bond of the naphthalene ring is a peak derived from the first monomer. Also,
Peak 1500 cm ^-1 and 1488cm ^-1 due to stretching vibration of C-F bond was observed. The peak due to the stretching vibration of the CF bond is a peak derived from the second monomer. Also, a peak due to stretching vibration of the CO bond was observed at 1260 cm ^-1 . The peak due to the stretching vibration of the C—O bond is a peak derived from an ether bond formed by bonding the first monomer and the second monomer. In addition, other peaks could not be observed because they overlapped with other peaks or because the peaks themselves were small.

As described above, in the IR chart, a peak derived from the first monomer, a peak derived from the second monomer, and an ether bond formed by bonding the first monomer and the second monomer. Was observed. From the above, the polymer produced by the above-described method has a polyphenol-type structural unit represented by the above formula (1),
It is considered to be an organic polymer composed of the aryl-type structural unit represented by the above formula (10). Further, considering the reaction conditions, it is considered that this organic polymer has a linear structure.

2. Second Embodiment The organic insulating film material of this embodiment has a linear structure composed of a bisphenol-type structural unit represented by the following formula (2) and an aryl-type structural unit represented by the following formula (10). Is an organic polymer having This organic polymer is a poly (aryl ether) whose main chain is composed of a benzene ring and oxygen.

[0043]

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The organic insulating film material of this example was manufactured using the same method as that of the first example, except that 2,2′-biphenol was used as the first monomer.
That is, 2,2′-biphenol 1 as a first monomer was placed in a reactor equipped with a stirrer, a cooling pipe, and a thermometer.
8.6 g (0.10 mol) and 33.4 g (0.10 mol) of perfluorobiphenyl as the second monomer
And 30.4 g of potassium carbonate (0.
22 mol), and 400 ml of N, N-dimethylacetamide as a solvent was added thereto.
Was dissolved as well as the basic catalyst. After the inside of the reactor is sufficiently purged with nitrogen, the reaction solution is quickly replaced with 8
The mixture was heated to 0 ° C. and stirred under a nitrogen atmosphere for 3 hours to cause a polymerization reaction. Thereafter, by performing the same operation as in the first example, 41 g of a polymer was obtained as an organic insulating film material.

The weight average molecular weight of the polymer produced as described above was 74,000. The glass transition temperature of this polymer was 230 ° C. The weight loss of this polymer in the temperature range of 400 ° C. to 500 ° C. is 0%.
(Below the measurement limit). The relative dielectric constant of this polymer was 2.65.

As described above, the organic insulating film material of this embodiment does not thermally decompose in the temperature range of 400 ° C. to 500 ° C., and has improved heat resistance by 150 ° C. or more than the conventional material. Accordingly, it can sufficiently withstand a process that requires a temperature of about 400 ° C. in which connection holes between wirings are filled with metal, and can be used as an organic insulating film material for LSI. In addition, the relative dielectric constant is as small as 2.65. When an insulating film (organic insulating film) is formed using this material, a further effect of reducing signal propagation delay can be expected. Therefore, development of a high-speed LSI using an organic insulating film having a low dielectric constant is facilitated.

In the IR chart of this polymer, a peak due to stretching vibration of the CC bond of the benzene ring was observed at 1605 cm ^-1 . C-C of this benzene ring
The peak due to the stretching vibration of the bond is a peak derived from both the first and second monomers. Also, 1
Peak 500 cm ^-1 and 1488cm ^-1 due to stretching vibration of C-F bond was observed. The peak due to the stretching vibration of the CF bond is a peak derived from the second monomer. Also, a peak due to stretching vibration of the CO bond was observed at 1260 cm ^-1 . The peak due to the stretching vibration of the C—O bond is a peak derived from an ether bond formed by bonding the first monomer and the second monomer.
Further, a peak due to out-of-plane bending vibration of the CH bond of the benzene ring was observed at 850 cm ^-1 . C of this benzene ring
The peak due to out-of-plane bending vibration of the -H bond is a peak derived from the first monomer. In addition, other peaks could not be observed because they overlapped with other peaks or because the peaks themselves were small.

As described above, in the IR chart, a peak derived from the first monomer, a peak derived from the second monomer, and an ether bond formed by bonding the first monomer and the second monomer. Was observed. From the above, the polymer produced by the above-described method has a polyphenol-type structural unit represented by the above formula (2),
It is considered to be an organic polymer composed of the aryl-type structural unit represented by the above formula (10). Further, considering the reaction conditions, it is considered that this organic polymer has a linear structure.

3. Third Embodiment The organic insulating film material of this embodiment has a linear structure composed of a bisphenol-type structural unit represented by the following formula (4) and an aryl-type structural unit represented by the following formula (10). Is an organic polymer having This organic polymer is a poly (aryl ether) whose main chain is composed of a benzene ring, a polycyclic alicyclic compound and oxygen.

[0050]

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The organic insulating film material of this example was manufactured using the same method as that of the first example, except that 1,3-adamantylidenebisphenol was used as the first monomer. That is, a reactor equipped with a stirrer, a cooling pipe and a thermometer was charged with 32.0 g (0.10 m
ol), 33.4 g (0.10 mol) of perfluorobiphenyl as a second monomer, and 30.4 g (0.22 mol) of potassium carbonate as a basic catalyst, and further N, N- as a solvent. 400 ml of dimethylacetamide was added to dissolve the first and second monomers and the basic catalyst. After the inside of the reactor was sufficiently purged with nitrogen, the reaction solution was quickly heated to 80 ° C., and stirred under a nitrogen atmosphere for 4.5 hours to cause a polymerization reaction. Thereafter, by performing the same operation as in the first embodiment, 53 g of a polymer was obtained as an organic insulating film material.

The weight average molecular weight of the polymer produced as described above was 36,000. The glass transition temperature of this polymer was 280 ° C. The weight loss of this polymer in the temperature range of 400 ° C. to 500 ° C. is 0%.
(Below the measurement limit). The relative dielectric constant of this polymer was 2.50.

As described above, the organic insulating film material of this example does not thermally decompose in the temperature range of 400 ° C. to 500 ° C., and has improved heat resistance by 150 ° C. or more than the conventional material. Accordingly, it can sufficiently withstand a process that requires a temperature of about 400 ° C. in which connection holes between wirings are filled with metal, and can be used as an organic insulating film material for LSI. Further, the dielectric constant is as small as 2.50, and when an insulating film (organic insulating film) is formed using this material, a further effect of reducing signal propagation delay can be expected. Therefore, development of a high-speed LSI using an organic insulating film having a low dielectric constant is facilitated.

In the IR chart of this polymer, stretching vibration of CH bond of methylene was observed at 2920 cm ^-1 . The peak due to stretching vibration of the CH bond of methylene is a peak derived from the first monomer.
Further, a peak due to stretching vibration of the CC bond of the benzene ring was observed at 1600 cm ^-1 . C- of this benzene ring
The peak due to the stretching vibration of the C bond is a peak derived from both the first and second monomers. Also,
Peak 1500 cm ^-1 and 1488cm ^-1 due to stretching vibration of C-F bond was observed. The peak due to the stretching vibration of the CF bond is a peak derived from the second monomer. Also, a peak due to stretching vibration of the CO bond was observed at 1260 cm ^-1 . The peak due to the stretching vibration of the C—O bond is a peak derived from an ether bond formed by bonding the first monomer and the second monomer. Further, a peak due to out-of-plane bending vibration of the CH bond of the benzene ring was observed at 840 cm ^-1 . The peak due to out-of-plane bending vibration of the CH bond of the benzene ring is a peak derived from the first monomer. In addition, other peaks could not be observed because they overlapped with other peaks or because the peaks themselves were small.

As described above, in the IR chart, a peak derived from the first monomer, a peak derived from the second monomer, and an ether bond formed by bonding the first monomer and the second monomer. Was observed. From this, the polymer produced by the above-described method has a polyphenol-type structural unit represented by the above formula (4),
It is considered to be an organic polymer composed of the aryl-type structural unit represented by the above formula (10). Further, considering the reaction conditions, it is considered that this organic polymer has a linear structure.

4. Fourth Embodiment The organic insulating film material of this embodiment has a linear structure composed of a bisphenol-type structural unit represented by the following formula (6) and an aryl-type structural unit represented by the following formula (10). Is an organic polymer having This organic polymer is a poly (aryl ether) whose main chain is composed of a benzene ring, a naphthalene ring and oxygen.

[0057]

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The organic insulating film material of this example was manufactured by using the same method as that of the first example except that 1,5-dihydroxynaphthalene was used as the first monomer. That is, 16.0 g (0.10 mol) of 1,5-dihydroxynaphthalene as a first monomer and 33.4 g of perfluorobiphenyl as a second monomer were placed in a reactor equipped with a stirrer, a cooling pipe, and a thermometer.
(0.10 mol), 30.4 g (0.22 mol) of potassium carbonate as a basic catalyst, and 400 ml of N, N-dimethylacetamide as a solvent were added, and the first and second monomers and base were added. The acidic catalyst was dissolved. After sufficiently replacing the inside of the reactor with nitrogen, the reaction solution was quickly heated to 100 ° C.,
The polymerization reaction was carried out by stirring for hours. Thereafter, the same operation as in the first embodiment is performed to obtain 28% as an organic insulating film material.
g of polymer were obtained.

The weight average molecular weight of the polymer produced as described above was 11,000. The glass transition temperature of this polymer was 210 ° C. The weight loss of this polymer in the temperature range of 400 ° C. to 500 ° C. is 0%.
(Below the measurement limit). The relative dielectric constant of this polymer was 2.75.

As described above, the organic insulating film material of this embodiment does not thermally decompose in the temperature range of 400 ° C. to 500 ° C., and has improved heat resistance by 150 ° C. or more than the conventional material. Accordingly, it can sufficiently withstand a process that requires a temperature of about 400 ° C. in which connection holes between wirings are filled with metal, and can be used as an organic insulating film material for LSI. Further, the relative dielectric constant is as small as 2.75. When an insulating film (organic insulating film) is formed using this material, a further effect of reducing signal propagation delay can be expected. Therefore, development of a high-speed LSI using an organic insulating film having a low dielectric constant is facilitated.

In the IR chart of this polymer, a broad peak was observed at 1620 cm ⁻¹ due to stretching vibration of the CC bond of the naphthalene ring. The peak due to the stretching vibration of the CC bond of the benzene ring is a peak derived from the first monomer. The peak due to stretching vibration of C-F bond was observed at 1500 cm ^-1 and 1488cm ^-1. The peak due to the stretching vibration of the CF bond is a peak derived from the second monomer. Also, 1
A peak due to stretching vibration of the C—O bond was observed at 260 cm ⁻¹ . The peak due to the stretching vibration of the C—O bond is a peak derived from an ether bond formed by bonding the first monomer and the second monomer. In addition, other peaks could not be observed because they overlapped with other peaks or because the peaks themselves were small.

As described above, in the IR chart, a peak derived from the first monomer, a peak derived from the second monomer, and an ether bond formed by bonding the first monomer and the second monomer. Was observed. From this, the polymer produced by the above-described method has a polyphenol-type structural unit represented by the above formula (6),
It is considered to be an organic polymer composed of the aryl-type structural unit represented by the above formula (10). Further, considering the reaction conditions, it is considered that this organic polymer has a linear structure.

5. Fifth Embodiment The organic insulating film material of this embodiment has a linear structure composed of a bisphenol-type structural unit represented by the following formula (7) and an aryl-type structural unit represented by the following formula (10). Is an organic polymer having This organic polymer is a poly (aryl ether) whose main chain is composed of a benzene ring, a naphthalene ring and oxygen.

[0064]

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The organic insulating film material of this example was manufactured using the same method as that of the first example except that 2,6-dihydroxynaphthalene was used as the first monomer. That is, 16.0 g (0.10 mol) of 2,6-dihydroxynaphthalene as a first monomer and 33.4 g of perfluorobiphenyl as a second monomer were placed in a reactor equipped with a stirrer, a cooling pipe, and a thermometer.
(0.10 mol), 30.4 g (0.22 mol) of potassium carbonate as a basic catalyst, and 400 ml of N, N-dimethylacetamide as a solvent were added, and the first and second monomers and base were added. The acidic catalyst was dissolved. After sufficiently replacing the inside of the reactor with nitrogen, the reaction solution was quickly heated to 100 ° C.,
The polymerization reaction was carried out by stirring for hours. After that, the same operation as in the first embodiment is performed to obtain 32 as an organic insulating film material.
g of polymer were obtained.

The weight average molecular weight of the polymer produced as described above was 43,000. The glass transition temperature of this polymer was 230 ° C. The weight loss of this polymer in the temperature range of 400 ° C. to 500 ° C. is 0%.
(Below the measurement limit). The relative dielectric constant of this polymer was 2.95.

As described above, the organic insulating film material of this embodiment does not thermally decompose in the temperature range of 400 ° C. to 500 ° C., and has improved heat resistance by 150 ° C. or more than the conventional material. Accordingly, it can sufficiently withstand a process that requires a temperature of about 400 ° C. in which connection holes between wirings are filled with metal, and can be used as an organic insulating film material for LSI.

In the IR chart of this polymer, a broad peak was observed at 1615 cm ^-1 due to stretching vibration of the CC bond of the naphthalene ring. The peak due to the stretching vibration of the CC bond of the benzene ring is a peak derived from the first monomer. The peak due to stretching vibration of C-F bond was observed at 1500 cm ^-1 and 1488cm ^-1. The peak due to the stretching vibration of the CF bond is a peak derived from the second monomer. Also, 1
A peak due to stretching vibration of the C—O bond was observed at 260 cm ⁻¹ . The peak due to the stretching vibration of the C—O bond is a peak derived from an ether bond formed by bonding the first monomer and the second monomer. In addition, other peaks could not be observed because they overlapped with other peaks or because the peaks themselves were small.

As described above, in the IR chart, a peak derived from the first monomer, a peak derived from the second monomer, and an ether bond formed by bonding the first monomer and the second monomer. Was observed. From this, the polymer produced by the above-described method has a polyphenol-type structural unit represented by the above formula (7),
It is considered to be an organic polymer composed of the aryl-type structural unit represented by the above formula (10). Further, considering the reaction conditions, it is considered that this organic polymer has a linear structure.

6. Sixth Embodiment The organic insulating film material of this embodiment has a linear structure composed of a bisphenol-type structural unit represented by the following formula (8) and an aryl-type structural unit represented by the following formula (10). Is an organic polymer having This organic polymer is a poly (aryl ether) whose main chain is composed of a benzene ring and oxygen.

[0071]

Embedded image

The material for the organic insulating film of this embodiment is composed of 2,3,5,6-tetrafluoro-1,4-
Except for using hydroquinone, it was manufactured using the same method as in the first example. That is, 18.2 g (0.10 mol) of 2,3,5,6-tetrafluoro-1,4-hydroquinone as a first monomer was added to a reactor equipped with a stirrer, a cooling pipe, and a thermometer. 33.4 g of perfluorobiphenyl as a monomer (0.10 mol
1) and 30.4 g of potassium carbonate as a basic catalyst
(0.22 mol), and N,
400 ml of N-dimethylacetamide was added to dissolve the first and second monomers and the basic catalyst. Then, after sufficiently replacing the inside of the reactor with nitrogen, the reaction solution was quickly heated to 80 ° C., and stirred under a nitrogen atmosphere for 3 hours to cause a polymerization reaction. Thereafter, the same operation as in the first example was performed to obtain 38 g of a polymer as an organic insulating film material.

The weight average molecular weight of the polymer produced as described above was 43,000. The glass transition temperature of this polymer was 230 ° C. The weight loss of this polymer in the temperature range of 400 ° C. to 500 ° C. is 0%.
(Below the measurement limit). The relative dielectric constant of this polymer was 2.45.

As described above, the organic insulating film material of this embodiment does not thermally decompose in the temperature range of 400 ° C. to 500 ° C., and has improved heat resistance by 150 ° C. or more than the conventional material. Accordingly, it can sufficiently withstand a process that requires a temperature of about 400 ° C. in which connection holes between wirings are filled with metal, and can be used as an organic insulating film material for LSI. Further, the relative dielectric constant is as small as 2.45. When an insulating film (organic insulating film) is formed using this material, a further effect of reducing signal propagation delay can be expected. Therefore, development of a high-speed LSI using an organic insulating film having a low dielectric constant is facilitated.

[0075] Also, in an IR chart of this polymer, the peaks due to the stretching vibration of C-F bonds to 1500 cm ^-1 and 1487cm ^-1 were observed. The peak due to the stretching vibration of the CF bond is a peak derived from both the first and second monomers. Also, 125
A peak due to stretching vibration of the C—O bond was observed at 5 cm ⁻¹ . The peak due to the stretching vibration of the C—O bond is a peak derived from an ether bond formed by bonding the first monomer and the second monomer. In addition, other peaks could not be observed because they overlapped with other peaks or because the peaks themselves were small.

As described above, in the IR chart, a peak derived from the first monomer, a peak derived from the second monomer, and an ether bond formed by bonding the first monomer and the second monomer. Was observed. From this, the polymer produced by the above-described method is composed of a polyphenol-type structural unit represented by the above formula (8),
It is considered to be an organic polymer composed of the aryl-type structural unit represented by the above formula (10). Further, considering the reaction conditions, it is considered that this organic polymer has a linear structure.

In order to form an organic insulating film using a coating solution, a spin coating method, a dipping method,
A spraying method, a press method, or the like can be used.

Further, as a substrate on which the organic insulating film is provided, a wiring metal such as Cu, Al, W, or a substrate provided with an oxide film or the like can be used.

[0079]

As is apparent from the above description, the first organic insulating film material of the present invention has two benzene rings (2
In the case of one fused benzene ring, there may be a benzene ring and a fused benzene ring. ) Is an organic polymer composed of a bisphenol-type structural unit and an aryl-type structural unit in which oxygen is directly bonded one by one. That is, a benzene ring (in the case of a condensed benzene ring, both a benzene ring and a condensed benzene ring may be introduced) into each structural unit of the first organic insulating film material of the present invention. Therefore, the organic insulating film material of the present invention has high heat resistance.

Further, in the first organic insulating film material of the present invention, the bisphenol-type structural unit is formed by combining benzene rings directly bonded with oxygen (in the case of a condensed benzene ring, in the case of a benzene ring and a condensed benzene ring). Is a structural unit bonded by one single bond, or between benzene rings to which oxygen is directly bonded (in the case of condensed benzene rings, or in the case of a benzene ring and a condensed benzene ring). Is a structural unit bonded via a polycyclic alicyclic compound, the movement of the main chain is suppressed, and the heat resistance is further increased.

The second organic insulating film material of the present invention comprises a bisphenol-type structural unit and an aryl-type structural unit in which two oxygens are directly bonded to one benzene ring (sometimes a fused benzene ring). And an organic polymer composed of That is, a benzene ring (in the case of a condensed benzene ring, both a benzene ring and a condensed benzene ring may be introduced) in each structural unit of the second organic insulating film material of the present invention. Therefore, the organic insulating film material of the present invention has high heat resistance. Focusing on the bisphenol-type structural unit, the main chain of the polymer is composed of one benzene ring (may be a condensed benzene ring) between two oxygen atoms, and the main chain has carbon atoms having sp ³ hybridized orbitals. Is not introduced, so that the motion of the main chain due to heat, such as side-to-side motion or bending motion, is suppressed. For this reason,
The organic insulating film material of the present invention has high heat resistance. Focusing on the bisphenol-type structural unit,
Between two oxygens, the main chain of the polymer is composed of one benzene ring (sometimes a condensed benzene ring), and no single bond is introduced into the main chain. It does not occur, and the movement of the main chain due to heat is suppressed. Therefore, the organic insulating film material of the present invention has high heat resistance.

Further, in the second organic insulating film material of the present invention, the bisphenol-type structural unit is formed by directly adding fluorine to one or a plurality of benzene rings (including a case where all or a part thereof is a condensed benzene ring). In the case of a bonded structural unit, the relative dielectric constant of the organic insulating film material is small because fluorine is introduced into the organic insulating film material.

Further, in the first and second organic insulating film materials of the present invention, the aryl-type structural unit is formed on any one or a plurality of benzene rings (including a case where all or a part thereof is a condensed benzene ring). When a structural unit in which fluorine is directly bonded is used, fluorine is introduced into the organic insulating film material, so that the relative dielectric constant of the organic insulating film material decreases.

Further, the first organic insulating film material of the present invention contains a plurality of benzene rings (including a case where all or a part thereof is a condensed benzene ring) and one for every two benzene rings. A first monomer comprising an aromatic compound to which a hydroxyl group is directly bonded, and an aromatic halogen compound containing one or more benzene rings (including a case where all or a part thereof is a condensed benzene ring), And a second monomer comprising an aromatic halogen compound in which two or more halogens are directly bonded to an arbitrary one or a plurality of benzene rings as a whole of the aromatic halogen compound in the presence of a basic catalyst. Thus, it can be easily manufactured.

Further, the second organic insulating film material of the present invention contains one or a plurality of benzene rings (including a case where all or a part thereof is a condensed benzene ring), and two or more benzene rings are contained in any one benzene ring. A first monomer composed of an aromatic compound to which two hydroxyl groups are directly bonded, and an aromatic halogen compound containing one or more benzene rings (including a case where all or a part thereof is a condensed benzene ring). And a second monomer comprising an aromatic halogen compound in which two or more halogens as a whole are directly bonded to any one or more benzene rings in the presence of a basic catalyst. By doing so, it can be easily manufactured.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) H01L 21/312 C08G 65/40 H01L 21/768

Claims (9)

(57) [Claims] 1. A bisphenol-type structural unit containing a plurality of benzene rings and oxygen being directly bonded to any two benzene rings one by one, and containing one or more benzene rings and being directly bonded to the oxygen And an organic insulating film material comprising an organic polymer having a linear structure composed of the above-mentioned bisphenol-type structural unit and an aryl-type structural unit connecting the bisphenol-type structural units (provided that the benzene ring is entirely or partially a condensed benzene ring) Wherein the bisphenol-type structural unit is a structural unit in which the benzene rings to which oxygen is directly bonded are bonded via a polycyclic alicyclic compound. Organic insulating film material. 2. The organic insulating film material according to claim 1, wherein said bisphenol-type structural unit is one of 1,3-adamantylidenebisphenol and 2,5-norbornylidenebisphenol. An organic insulating film material comprising: 3. Oxygen is directly bonded to one of two arbitrary benzene rings containing a plurality of benzene rings, and the benzene rings to which the oxygen is directly bonded are bonded by one single bond. Organic polymer having a linear structure composed of a bisphenol-type structural unit and an aryl-type structural unit containing one or more benzene rings and directly bonding to the oxygen to connect the bisphenol-type structural units. Wherein the aryl-type structural unit is 1,5-perfluoronaphthalenylene, 1,6-perfene, wherein the whole or part of the benzene ring is a condensed benzene ring. An organic insulating film material comprising one kind selected from loronaphthalenylene and 1-trifluoromethyl-2,4-trifluorophenylene. 4. Oxygen is directly bonded to any two benzene rings each containing a plurality of benzene rings, and the benzene rings to which the oxygen is directly bonded are bonded via a polycyclic alicyclic compound. A linear structure composed of a bisphenol-type structural unit that is bonded by bonding, and an aryl-type structural unit that includes one or more benzene rings and that is directly bonded to the oxygen to link the bisphenol-type structural units. In an organic insulating film material made of an organic polymer having a structure (including a case in which a benzene ring is entirely or partially a condensed benzene ring), the aryl-type structural unit is 1,5-perfluoronaphthalenylene; An organic insulating film comprising one kind selected from 1,6-perfluoronaphthalenylene and 1-trifluoromethyl-2,4-trifluorophenylene. Fee. 5. A bisphenol-type structural unit containing one or more benzene rings and two oxygens directly bonded to any one benzene ring, and one or more benzene rings containing a benzene ring and the oxygen being directly An organic insulating film material made of an organic polymer having a linear structure composed of an aryl-type structural unit bonded to the above-mentioned bisphenol-type structural unit (where the benzene ring is entirely or partially a condensed benzene ring) Wherein the aryl-type structural unit is selected from the group consisting of 1,5-perfluoronaphthalenylene, 1,6-perfluoronaphthalenylene, and 1-trifluoromethyl-2,4-trifluorophenylene. An organic insulating film material, which is selected from one kind. 6. Oxygen is directly bonded to two arbitrary benzene rings each containing a plurality of benzene rings, and the benzene rings to which the oxygen is directly bonded are bonded by one single bond. Organic polymer having a linear structure composed of a bisphenol-type structural unit, and an aryl-type structural unit containing one or more benzene rings and being directly bonded to the oxygen to connect the bisphenol-type structural units. Wherein the bisphenol-type structural unit is 2,2′-bi-1-
Naphthol, and the aryl-type structural unit is 1,
An organic insulating film material comprising one of 4-perfluorophenylene and 4,4'-perfluorobiphenylene. 7. Oxygen is directly bonded to each of two arbitrary benzene rings containing a plurality of benzene rings, and the benzene rings to which the oxygen is directly bonded are bonded by one single bond. Organic polymer having a linear structure composed of a bisphenol-type structural unit and an aryl-type structural unit containing one or more benzene rings and directly bonding to the oxygen to connect the bisphenol-type structural units. Wherein the bisphenol-type structural unit is 2,2′-biphenol, and the aryl-type structural unit is an organic insulating film material (including a case where the benzene ring is entirely or partially a condensed benzene ring). Wherein the material is any one of 1,4-perfluorophenylene and 4,4′-perfluorobiphenylene. 8. Oxygen is bonded directly to two arbitrary benzene rings each containing a plurality of benzene rings, and the benzene rings to which the oxygen is directly bonded are bonded by one single bond. Organic polymer having a linear structure composed of a bisphenol-type structural unit, and an aryl-type structural unit containing one or more benzene rings and being directly bonded to the oxygen to connect the bisphenol-type structural units. Wherein the bisphenol-type structural unit is 4,4′-biphenol, and the aryl-type structural unit is an organic insulating film material (including a case where the benzene ring is wholly or partially a condensed benzene ring). Wherein the material is any one of 1,4-perfluorophenylene and 4,4′-perfluorobiphenylene. 9. A bisphenol-type structural unit containing one or more benzene rings and two oxygens directly bonded to any one benzene ring, and one or more benzene rings containing the benzene ring and the oxygen being directly An organic insulating film material made of an organic polymer having a linear structure composed of an aryl-type structural unit bonded to the above-mentioned bisphenol-type structural unit (where the benzene ring is entirely or partially a condensed benzene ring) Wherein the bisphenol-type structural unit is 2,3,5,6,-
Tetrafluoro-1,4-hydroquinone, and the aryl-type structural unit is a structural unit in which fluorine is directly bonded to any one or more benzene rings (provided that 2,
2 ′ difluoro-6,6 ′ difluoro-biphenyl-4,
Excludes 4'-diol. An organic insulating film material characterized in that: