JP2007023163A - Composition for forming film, insulating film and their production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for forming films, capable of forming silicone films suitable for using as interlayer insulating films usable for semiconductor elements and having uniform thickness, and excellent in dielectric constant property and film strength, to provide insulating films, and to provide their production methods. <P>SOLUTION: The composition for forming films comprises a compound represented by formula (I) or a polymer thereof. The insulating films produced by using the composition is provided. Wherein, in formula (I), R<SP>1</SP>and R<SP>2</SP>are each independently H or a substituent; at least one of a plurality of R<SP>1</SP>'s and R<SP>2</SP>'s is a group represented by general formula (II): (R<SP>3</SP>)<SB>3</SB>-Si-O-; m is an integer of 4-30; in general formula (II), R<SP>3</SP>is H or a substituent; and at least one of a plurality of R<SP>1</SP>'s to R<SP>3</SP>'s is a polymerizable group, wherein, R<SP>1</SP>to R<SP>3</SP>are neither hydroxy nor a hydrolyzable group. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a film-forming composition, and more specifically, as an interlayer insulating film material in a semiconductor element or the like, a coating film having an appropriate uniform thickness can be formed, and insulation having excellent dielectric constant characteristics, etc. The present invention relates to a film forming composition, an insulating film manufacturing method, and an insulating film.

Conventionally, a silica (SiO ₂ ) film formed by a vacuum process such as a vapor deposition (CVD) method is frequently used as an interlayer insulating film in a semiconductor element or the like. In recent years, for the purpose of forming a more uniform interlayer insulating film, a coating type insulating film called a SOG (Spin on Glass) film containing a hydrolysis product of tetraalkoxylane as a main component has been used. It has become. In addition, with high integration of semiconductor elements and the like, an interlayer insulating film having a low dielectric constant, which is mainly composed of polyorganosiloxane called organic SOG, has been developed.

However, even a CVD-SiO ₂ film showing the lowest dielectric constant among the inorganic material films has a dielectric constant of about 4. Moreover, the dielectric constant of the SiOF film, which has been recently studied as a low dielectric constant CVD film, is about 3.3 to 3.5, but this film has high hygroscopicity, and the dielectric constant increases during use. There is a problem.

Under such circumstances, as an insulating film material excellent in insulation, heat resistance, and durability, a method is known in which a high boiling point solvent or a thermally decomposable compound is added to organopolysiloxane to form voids and lower the dielectric constant. ing. However, the porous film as described above has problems such as a decrease in mechanical strength and an increase in dielectric constant due to moisture absorption even if the dielectric constant characteristics decrease due to porosity. In addition, since vacancies connected to each other are formed, copper used for wiring diffuses into the insulating film.
On the other hand, attempts to lower the dielectric constant using a siloxane compound having a cyclic structure are known (see Patent Documents 1 and 2). However, the methods disclosed in these documents have a small effect of reducing the density of the insulating film. The dielectric constant did not decrease sufficiently.
JP 2000-281904 A JP 2000-309753 A

  Accordingly, the present invention relates to a composition for solving the above problems, an insulating film manufacturing method, and an insulating film formed using the composition, and more particularly, suitable for use as an interlayer insulating film in a semiconductor element or the like. Another object of the present invention is to provide a composition, an insulating film, and a method for producing the same, which can form a silicone-based film having an appropriate uniform thickness, and have excellent dielectric constant characteristics and film strength.

  It has been found that the above object of the present invention can be achieved by the following means.

一般式（I）中、
Ｒ¹およびＲ²はそれぞれ独立に水素原子または置換基を表し、複数個存在するＲ¹およびＲ²のうち少なくとも１つは一般式（II）で表される基を表す。
ｍは４〜３０の整数を表す。
（Ｒ³）₃−Ｓｉ−Ｏ− (II)
一般式（II）中、
Ｒ³は水素原子または置換基を表す。
複数個存在するＲ¹〜Ｒ³のうち、少なくとも１つは重合性基を表す。
ただし、Ｒ¹〜Ｒ³は水酸基および加水分解性基を表さない。
（２）
一般式（I）において、ｍが５〜２０の整数である（１）に記載の組成物。
（３）
一般式（I）および一般式（II）における、Ｒ¹〜Ｒ³に含まれる重合性基が、ビニル基またはエチニル基である（１）または（２）に記載の組成物。
（４）
一般式（I）および一般式（II）における、複数個存在するＲ¹〜Ｒ³のうち、少なくとも１つはビニル基またはエチニル基であり、かつ、少なくとも１つはＳｉＨ基である（1）〜（３）のいずれかに記載の組成物。
（５）
一般式（I）および一般式（II）における、
Ｒ¹およびＲ²が水素原子、アルキル基、アリール基、重合性基または一般式（II）で表される基を表し、ｍ個存在するＲ¹およびＲ²のうち少なくとも１つは一般式（II）で表される基を表し、
Ｒ³は水素原子、アルキル基、アリール基または重合性基を表し、
複数個存在するＲ¹〜Ｒ³のうち、少なくとも１つは重合性基を表し、
Ｒ¹〜Ｒ³は水酸基および加水分解性基を表さないことを特徴とする、（１）〜（４）のいずれかに記載の組成物。
（６）
一般式（I）で表される化合物またはその重合物に加えて、ＨＳｉ基を分子内に２個以上含む化合物を含んでいることを特徴とする（１）〜（５）のいずれかに記載の組成物。
（７）
一般式（III）で表される化合物と一般式（IV）で表される化合物を反応させることを特徴とする（１）〜（５）のいずれかに記載の組成物の製造方法。

一般式（III）および一般式（IV）中、
Ｒ¹、ｍおよびＲ³はそれぞれ一般式（I）および一般式（II）におけるものと同意である。
Ａは水素原子または金属原子を表す。
Ｘは水酸基または加水分解性基を表す。
（８）
（１）〜（５）のいずれかに記載の組成物を用いて製造された絶縁膜。
（９）
（１）〜（５）のいずれかに記載の組成物を基板上に塗布した後、焼成することを特徴とする絶縁膜の製造方法。
（１０）
（１）〜（５）のいずれかに記載の組成物を用いて製造されたポリマー。 (1)
The film formation composition containing the compound represented by the following general formula (I), or its polymer.

In general formula (I),
R ¹ and R ² each independently represents a hydrogen atom or a substituent, and at least one of a plurality of R ¹ and R ² represents a group represented by the general formula (II).
m represents an integer of 4 to 30.
(R ³ ) ₃ —Si—O— (II)
In general formula (II),
R ³ represents a hydrogen atom or a substituent.
Among the plurality of R ^{1 to} R ³ , at least one represents a polymerizable group.
However, R ^{1 to} R ³ do not represent a hydroxyl group or a hydrolyzable group.
(2)
In General formula (I), m is an integer of 5-20, The composition as described in (1).
(3)
The composition as described in (1) or (2) whose polymerizable group contained in R < ¹ > -R < ³ > in general formula (I) and general formula (II) is a vinyl group or an ethynyl group.
(4)
In the general formula (I) and the general formula (II), at least one of R ^{1 to} R ³ is a vinyl group or an ethynyl group, and at least one is a SiH group (1) -Composition in any one of (3).
(5)
In general formula (I) and general formula (II),
R ¹ and R ² represent a hydrogen atom, an alkyl group, an aryl group, a polymerizable group or a group represented by the general formula (II), and at least one of m R ¹ and R ² is represented by the general formula ( II) represents a group represented by
R ³ represents a hydrogen atom, an alkyl group, an aryl group or a polymerizable group,
Of the plurality of R ^{1 to} R ³ , at least one represents a polymerizable group,
R < ¹ > -R < ³ > does not represent a hydroxyl group and a hydrolyzable group, The composition in any one of (1)-(4) characterized by the above-mentioned.
(6)
In addition to the compound represented by the general formula (I) or a polymer thereof, the compound contains a compound containing two or more HSi groups in the molecule, according to any one of (1) to (5) Composition.
(7)
The method for producing a composition according to any one of (1) to (5), wherein the compound represented by the general formula (III) is reacted with the compound represented by the general formula (IV).

In general formula (III) and general formula (IV),
R ¹ , m and R ³ are the same as in general formula (I) and general formula (II), respectively.
A represents a hydrogen atom or a metal atom.
X represents a hydroxyl group or a hydrolyzable group.
(8)
(1) The insulating film manufactured using the composition in any one of (5).
(9)
(1)-(5) apply | coating the composition in any one on a board | substrate, Then, it bakes, The manufacturing method of the insulating film characterized by the above-mentioned.
(10)
The polymer manufactured using the composition in any one of (1)-(5).

  According to the present invention, it is possible to form an insulating film excellent in dielectric constant characteristics suitable for use as an interlayer insulating film in a semiconductor element or the like.

  Hereinafter, the film forming composition of the present invention will be described.

  First, the compound represented by the following general formula (I) will be described.

In general formula (I),
R ¹ and R ² each independently represents a hydrogen atom or a substituent, and at least one of a plurality of R ¹ and R ² represents a group represented by the general formula (II).
m represents an integer of 4 to 30.
(R ³ ) ₃ —Si—O— (II)
In general formula (II),
R ³ represents a hydrogen atom or a substituent.
Among the plurality of R ^{1 to} R ³ , at least one represents a polymerizable group.
However, R ^{1 to} R ³ do not represent a hydroxyl group or a hydrolyzable group.

Examples of the substituent represented by R ^{1 to} R ³ include a cyclic or chain alkyl group, an aryl group, an alkenyl group, an alkynyl group, and the like. These substituents may further have a substituent.
R ¹ is preferably a cyclic or chain alkyl group, an aryl group, an alkenyl group, or an ethynyl group. Among them, a cyclic alkyl group (cyclopropyl group, cyclohexyl group, etc.) is preferable in terms of providing a low dielectric constant film, a methyl group is preferable in terms of providing a film having high heat resistance, and a film having high plasma resistance is provided. An aryl group (such as a phenyl group) is preferred.
Among the plurality of R ^{1 to} R ³ , at least one represents a polymerizable group. The polymerizable group is a group that reacts to give a polymer by the presence of heat, radiation, radical generator, acid, base, -SiH group, etc. Examples include vinyl group, ethynyl group, oxetane group, Examples of the epoxy group include a vinyl group and an ethynyl group in that a film having high heat resistance can be formed by a hydrosilylation reaction or thermal polymerization of an unsaturated carbon-carbon bond.
m represents an integer of 4 to 30, but 5 to 20 is preferable, 5 to 15 is more preferable, and 6, 8 and 12 are particularly preferable from the viewpoint of a dielectric constant lowering effect.
R ^{1 to} R ³ of the present invention do not represent a hydroxyl group or a hydrolyzable group, but the term “hydrolyzable group” as used herein refers to a group that leaves from a silicon atom by reaction with water. , An aryloxy group, an acyloxy group, an arylcarbonyloxy group, and a halogen atom.
It is preferable for reducing the dielectric constant that the composition of the present invention does not contain a compound containing a silicon atom having a hydroxyl group or a hydrolyzing group as a substituent.

The compound represented by the general formula (I) may be composed of one type of unit, or may be composed of a plurality of different units. That is, a plurality of R ^{1 to} R ³ existing in the general formula (I) may be the same or different from each other.
There is no particular limitation on the steric positional relationship of the substituents for the general formula (I), and all R ¹ may be present in the same direction with respect to the ring formed by —Si—O—, The direction of R ¹ may change regularly or may not be regular, but in order to form a homogeneous structure in the film, it is preferable that the direction of R ¹ has a certain regularity. .
The composition of the present invention may contain a plurality of different compounds represented by the general formula (I) or a polymer thereof.

  Specific examples of the compound represented by the general formula (I) are shown below, but the present invention is not limited thereto.

  The compound represented by the general formula (I) can be synthesized, for example, by reacting the compound represented by the general formula (III) with the compound represented by the general formula (IV). The compound represented by the general formula (III) is, for example, a method described in Inorganic Chemistry 2002, 41, 6898-6904, Russian Chemical Bulletin, International Edition, Vol. 52, No. 12, 2272-2731 (2003), etc. Can be synthesized according to

In the above formula,
R ¹ , m, and R ³ are the same as in general formula (I) and general formula (II), respectively.
X represents a hydrolyzable group or a hydroxyl group. Examples of the hydrolyzable group for X include an alkoxy group, an aryloxy group, a halogen atom, and an acyloxy group. Of these, an alkoxy group, an acyloxy group and a chlorine atom are preferable, and a chlorine atom is most preferable.
A represents a hydrogen atom or a metal atom. Examples of the metal atom represented by A include Na, K, Cu, Ni, and Mn.

The reaction between the compound represented by the general formula (III) and the compound represented by the general formula (IV) is, for example, represented by the compound represented by the general formula (III) and the general formula (III). The compound represented by the general formula (IV) having 1 to 100 moles of the Si—OA group contained in the compound is added, and the reaction is usually performed at 0 to 180 ° C. for 10 minutes to 20 hours while stirring. It is preferable that the reaction atmosphere does not contain moisture, and preferable examples of the reaction atmosphere include dried nitrogen, argon, air, and the like. As the solvent, organic solvents such as toluene, hexane, and tetrahydrofuran (THF) are preferable.
When the compound represented by the general formula (III) and the compound represented by the general formula (IV) are reacted, it is preferable to add a base such as triethylamine or pyridine.

When the composition of the present invention is polymerized by a hydrosilylation reaction, in addition to the compound represented by the general formula (I) or a polymer thereof, a compound containing two or more HSi groups in the molecule is included. It is preferable. A compound having two or more HSi groups in the molecule can form a film having higher heat resistance by a hydrosilylation reaction with the compound represented by the general formula (I) or a polymer thereof. Examples of compounds containing two or more HSi groups in the molecule include the following compounds.
A preferred ratio of the total number of polymerizable groups possessed by the compound represented by the general formula (I) or a polymer thereof and the total number of HSi groups possessed by a compound containing two or more HSi groups in the molecule is 1: 0.05. To 1: 2, more preferably from 1: 0.15 to 1: 1.5, and most preferably from 1: 0.25 to 1: 1.2.

  The film-forming composition of the present invention is preferably used after being dissolved in a suitable solvent and coated on a support. Solvents that can be used include ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, methyl isobutyl ketone, γ-butyrolactone, methyl ethyl ketone, methanol, ethanol, dimethylimidazolidinone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Glycol dimethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), tetraethylene glycol dimethyl ether, triethylene glycol monobutyl ether, triethylene glycol monomethyl ether, Isopropanol, ethyl Carbonate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran, diisopropylbenzene, toluene, xylene, mesitylene and the like are preferable, and these solvents are used alone or in combination.

  Among these, preferable solvents include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 2-heptanone, cyclohexanone, γ-butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl. Ether, propylene glycol monoethyl ether, ethylene carbonate, butyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, N-methylpyrrolidone, N, N-dimethylformamide, tetrahydrofuran, methyl isobutyl ketone, xylene, Mention may be made of mesitylene and diisopropylbenzene.

In producing the composition of the present invention, the compound of the general formula (I) may be used as it is by dissolving it in a solvent, or the compound of the general formula (I) may be polymerized by a method such as heating. You may use after making molecular weight. 1000-500000 is preferable, as for the mass average molecular weight in high molecular weight formation, 2000-200000 is more preferable, 5000-100000 is the most preferable. A base catalyst, an acid catalyst, a radical generator, and a metal catalyst may be added to the composition of the present invention as a catalyst for polymerization.
The total solid concentration of the composition of the present invention thus obtained is preferably 2 to 30% by mass, and is appropriately adjusted according to the purpose of use. When the total solid content concentration of the composition is 2 to 30% by mass, the film thickness of the coating film is in an appropriate range, and the storage stability of the coating solution is also more excellent.

When the film-forming material of the present invention thus obtained is applied to a substrate such as a silicon wafer, SiO ₂ wafer, or SiN wafer, it is applied by spin coating, dipping method, roll coating method, spray method or the like. Means are used.

In this case, as a dry film thickness, it is possible to form a coating film having a thickness of about 0.05 to 1.5 μm by one coating and a thickness of about 0.1 to 3 μm by two coatings. After that, by drying at normal temperature or heating using a hot plate, an oven, a furnace, or the like, an insulating film of glassy or giant polymer, or a mixture thereof can be formed.
In this case, the heating atmosphere can be a nitrogen atmosphere, an argon atmosphere, a vacuum, or the like, but it is preferable that the baking is performed under conditions where the maximum baking temperature is 300 ° C. or higher and 430 ° C. or lower.

  More specifically, the film-forming material of the present invention is applied onto a substrate (usually a substrate having metal wiring) by, for example, spin coating, preliminarily heat-treated to dry the solvent, and then 300 ° C. An insulating film having a low dielectric constant can be formed by performing final heat treatment (annealing) at a temperature of 430 ° C. or lower.

  By this method, an insulating film having a low dielectric constant, that is, an insulating film having a dielectric constant of 2.7 or less, preferably 2.5 or less can be obtained. The dielectric constant may be further lowered by making the composition porous according to the present invention by making it porous by adding a thermally decomposable compound or the like.

  Hereinafter, the present invention will be described more specifically with reference to examples. In addition, unless otherwise indicated, the part and% in an Example have shown that they are the mass part and the mass%, respectively.

[Synthesis Example 1]
1.1 g (0.664 mmol) of a compound represented by the following general formula (I-11-a) synthesized according to the method described in Inorganic Chemistry, 41, 6898-6904 (2002) was added to 3.87 ml (47. 85 mmol) and 6.61 ml (47.85 mmol) of vinyldimethylchlorosilane were added dropwise and heated to reflux for 1 hour. Toluene (35 ml) was added, and the mixture was further heated under reflux for 1 hour, and then poured into 100 ml of ice water and separated. The organic layer was washed twice with 100 ml of water, dehydrated with anhydrous magnesium sulfate, concentrated, purified by silica gel column chromatography, and 1.3 g (0.55 mmol) of the compound represented by the following general formula (I-11) ) This was dissolved in 20 ml of 4-methyl-2-pentanone to obtain a composition (11-1).

[Synthesis Example 2]
According to the method described in Russian Chemical Bulletin, International Edition, Vol. 52, No. 12, 2722-2731 (2003), a compound represented by the general formula (I-2) was synthesized. 0.4 g of the compound represented by general formula (I-2) and 0.6 g of the compound represented by general formula (V-5) synthesized by the same method as the compound represented by general formula (I-11) Was dissolved in 13 ml of 4-methyl-2-pentanone to synthesize a composition (2-1).

[Synthesis Example 3]
Platinum (0) -1,3-divinyl-1 is prepared by dissolving 0.4 g of the compound represented by the general formula (I-2) and 0.042 g of the compound represented by the general formula (V-2) in 8 ml of xylene. , 1,3,3, tetramethylsiloxane complex-xylene solution (manufactured by Aldrich) was added, and the mixture was heated to reflux for 1 hour to obtain a composition (2-2).

[Synthesis Example of Comparative Compound]
39.2 g (186 mmol) of trichlorophenylsilane dissolved in 72 ml of acetone was added dropwise to 1.42 kg of ice water and stirred at 0 ° C. for 20 hours. The precipitate was collected by filtration, washed with water, dried, suspended in 200 ml of carbon disulfide, collected by filtration, and recrystallized from acetone / toluene. 8 g (14.5 mmol) of comparative compound A was obtained.
Comparative compound A1g was dissolved in 13 ml of 4-methyl-2-pentanone to obtain a comparative composition.

(Example)
The composition obtained by the method shown in the above synthesis example was filtered through a Teflon (registered trademark) filter having a pore size of 0.2 μm, applied onto a 4-inch silicon wafer by spin coating, and then heated at 130 ° C. on a hot plate. Then, the substrate was dried at 230 ° C. for 1 minute, and further heated at 400 ° C. for 30 minutes in a clean oven in a nitrogen atmosphere, and measured using a mercury probe manufactured by Four Dimensions. .

  The evaluation results of this coating film are shown in Table 1.

  From the results shown in Table 1, it can be seen that a film having a low dielectric constant can be formed by using the composition of the present invention.

Claims (10)

The film formation composition containing the compound represented by the following general formula (I), or its polymer.

In general formula (I),
R ¹ and R ² each independently represents a hydrogen atom or a substituent, and at least one of a plurality of R ¹ and R ² represents a group represented by the general formula (II).
m represents an integer of 4 to 30.
(R ³ ) ₃ —Si—O— (II)
In general formula (II),
R ³ represents a hydrogen atom or a substituent.
Among the plurality of R ^{1 to} R ³ , at least one represents a polymerizable group.
However, R ^{1 to} R ³ do not represent a hydroxyl group or a hydrolyzable group.   In the general formula (I), m is an integer of 5-20, The composition of Claim 1 characterized by the above-mentioned. The composition according to claim 1 or 2, wherein the polymerizable group contained in R ^{1 to} R ³ in the general formula (I) and the general formula (II) is a vinyl group or an ethynyl group. Of the general formulas (I) and (II), at least one of R ^{1 to} R ³ is a vinyl group or an ethynyl group, and at least one is a SiH group. The composition according to any one of claims 1 to 3. In general formula (I) and general formula (II),
R ¹ and R ² represent a hydrogen atom, an alkyl group, an aryl group, a polymerizable group or a group represented by the general formula (II), and at least one of m R ¹ and R ² is represented by the general formula ( II) represents a group represented by
R ³ represents a hydrogen atom, an alkyl group, an aryl group or a polymerizable group,
Of the plurality of R ^{1 to} R ³ , at least one represents a polymerizable group,
The composition according to any one of claims 1 to 4, wherein R ^{1 to} R ³ do not represent a hydroxyl group or a hydrolyzable group.   The composition according to any one of claims 1 to 5, further comprising a compound containing two or more HSi groups in the molecule in addition to the compound represented by the general formula (I) or a polymer thereof. object. The method for producing a composition according to any one of claims 1 to 5, wherein the compound represented by the general formula (III) is reacted with the compound represented by the general formula (IV).

In general formula (III) and general formula (IV),
R ¹ , m and R ³ are the same as in general formula (I) and general formula (II), respectively.
A represents a hydrogen atom or a metal atom.
X represents a hydroxyl group or a hydrolyzable group.   The insulating film manufactured using the composition in any one of Claims 1-5.   A method for producing an insulating film, wherein the composition according to claim 1 is applied onto a substrate and then baked.   The polymer manufactured using the composition in any one of Claims 1-5.