JPH04181254A - Polysilphenylenesiloxane, its production, resist material, and semiconductor device - Google Patents

Abstract

PURPOSE:To provide a novel organosilicon polymemr useful in the filed of manufactures of semiconductor devices by forming a 3-dimensional spherical structure comprising the strong nucleus of silphenylsiloxane, triorganosilyl functional groups surrounding this nucleus. CONSTITUTION:The organosilicon polymer is represented by the molecular structure of formula I and it has the 3-dimensional spherical structure comprising the silphenylsiloxane nucleus and the triorganosilyl groups surrounding this nucleus and a weight average molecular weight of 1X10<3> - 5X10<6>. In formula I, R is H or a monovalent hydrocarbon group, optionally same or different, and each of a m and n is a positive integer, thus permitting a novel useful organosilicon polymer to be obtained, and the obtained resist to be superior in sensitivity and plasma resistance, small in swelling, and high in contrast and resolution.

Description

[Detailed Description of the Invention] [Summary] Regarding organosilicon polymers, the following molecular structural formula (
I): (In the above formula, R may be the same or different, each represents hydrogen or a monovalent hydrocarbon group, and m and n each represent a positive integer), silphenylene It has a three-dimensional Katsura-like structure consisting of a siloxane core and triorganosilyl groups surrounding the silphenylene core, and has a molecular weight of 1,000 to 5,000.
It is composed of polysilphenylene siloxane having a weight average molecular weight of 0.000.

[Industrial application field]

The present invention relates to novel organosilicon polymers, in particular polysilphenylene siloxanes. The invention also relates to a method of making such organosilicon polymers. Furthermore, the present invention relates to a resist material, particularly a resist material useful as an upper layer resist in a two-layer resist method, and a pattern forming method and a semiconductor device manufacturing method using such a resist material. Furthermore, the present invention provides a semiconductor device using the novel organosilicon polymer of the present invention as a glabella insulating film, a heat-resistant protective film, and the like.

The organosilicon polymer of the present invention has high sensitivity to high-energy radiation such as electron beams and deep ultraviolet rays, high contrast (for example, r=2.8), and small swelling during development (for example, , 0.2μ when used as an EB resist
M1/s), therefore has high resolution and has a softening temperature of 4
Since it has high oxygen plasma resistance (e.g., selectivity of 100 with respect to novolac resist) at over 00°C, it can be advantageously used as a resist in fields such as semiconductor device manufacturing. . In addition, the organosilicon polymer of the present invention has excellent heat resistance and insulation properties, and has a good planarization function, so it is advantageous in the multilayer wiring formation process in the manufacture of semiconductor devices such as various integrated circuits. can be used. For example, the organosilicon polymer of the present invention can be used to flatten underlying steps and provide excellent insulation when forming multilayer wiring for semiconductor devices with high integration density such as ICs and LSIs. Therefore, the reliability of the device can be improved.

[Conventional technology]

Thin film formation technology and photolithography are often used to form electronic circuit elements with fine patterns, such as semiconductor elements, magnetic bubble memory elements, and surface wave filter elements. In other words, when it comes to wiring patterns, thin films such as conductive layers and insulating layers are formed on the substrate by physical methods such as vacuum evaporation and sputtering, or chemical methods such as chemical vapor deposition, and then spin. A resist composition is coated using a method such as a coding method, and then exposed to light such as ultraviolet rays, and a resist pattern is formed by taking advantage of the difference in solubility of exposed areas in a developer. ing. Using this resist pattern as a mask, wet etching or dry etching is performed to form fine conductor patterns, insulating layer patterns, etc. on the substrate to be processed. In addition, as another method for forming a resist pattern, the diameter of an electron beam is narrowed down to a very small diameter, and the resist composition film is directly drawn by scanning, developed to create a resist pattern, and etched to form a fine pattern. A method of forming a .

However, in the manufacturing process of semiconductor devices such as VLSI, wiring is multilayered in order to increase the degree of integration, and a step of 1 to 2 meters is created on the surface of the substrate. Therefore, it is difficult to form fine patterns with high precision using the single-layer resist method as described above.

A two-layer resist method has been proposed as a method for forming fine patterns with high precision on substrates with high steps. As shown in the attached FIG. 1A, this method involves applying an organic resin to a thickness of, for example, 2 mm on a substrate 1 having, for example, a step (metal wiring in this case) 2, and forming a lower resist (flattening layer). Start by forming 3. After the substrate surface is planarized, a resist material sensitive to exposure radiation is thinly applied to a thickness of, for example, about 0.2 to 0.3 nm to form an upper resist 4. Next, as shown in FIG. 1B, the upper resist layer 4 is subjected to pattern exposure. Depending on the type of resist material used, the exposed areas of the upper resist 4 are rendered soluble or insoluble in the developer. The exposed upper resist 4 is then developed with a selected developer and patterned as shown in FIG. 1C. After this patterning is completed, the base (lower resist) 3 is etched using oxygen plasma using the pattern of the upper resist 4 obtained as a mask. As shown in FIG. 1D, the pattern of the upper resist 4 is transferred to the lower resist 3. In this two-layer resist method, the lower layer resist prevents the effects of substrate steps and light reflection from the substrate surface, and the upper layer resist can be made thinner, resulting in significantly improved resolution compared to the single-layer resist method. . The upper layer resist of this two-layer resist method is required to have oxygen plasma resistance in addition to the sensitivity and resolution required for conventional single-layer resists. Here, since organosilicon polymers have excellent oxygen plasma resistance, negative resist materials based on organosilicon polymers and useful as pattern forming materials are already known. Typical examples include siloxane and polysiloxane having a phenyl group, and these are well known as negative resists that constitute the upper layer resist of the two-layer resist method.

As an example of using polysiloxane with a ladder structure as a resist, for example, US Pat.
．． 863.833 may be mentioned. This pattern-forming material is made of polysilsesquioxane that does not contain a hydroxyl group in its molecule, and the polysilsesquioxane is represented by the following formula: (In the above formula, R1 and R2 may be the same or different and each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted vinyl group, and m is about 25 to 4,000
is a positive integer). Although this pattern-forming material has the advantages of high sensitivity to high-energy radiation, good dry etching resistance, good resolution, and good thermal stability, it needs improvement in terms of contrast and swelling. leaving room.

Further, as an example of using a polysiloxane having a phenyl group as a resist, there can be mentioned, for example, a pattern forming material described in European Patent Application Publication No. 0122398. This pattern-forming material is a siloxane polymer represented by the following formula: (In the above formula, R, R' and RII may be the same or different, and each represents hydrogen, an alkyl group, or a phenyl group, and or represents -CH, Y, Y is halogen etc., and f
, m and n are each 0 or a positive integer). This type of pattern-forming material, like the ladder-structured polysiloxane described above, has high sensitivity to high-energy radiation and good dry etching resistance, and therefore, for example, Tosoh Corporation.
It is commercially available as an SNR resist from . However, such patterning materials have low sensitivity to ultraviolet light;
Because the swelling during development is large and the contrast (T value) is low (for example, in SNR resist, γ = 1.2 to 1,
6) So-called space (cutout) patterns, such as spaces between thick line patterns, cannot be clearly resolved. This is a very serious problem especially when it comes to fine patterns of 0.5 nm or less. Therefore, VLS
In order to miniaturize I and improve throughput, it is desired to develop a high-resolution resist material that has excellent sensitivity and oxygen plasma resistance, exhibits little swelling during development, and has high contrast.

Organosilicon polymers are used in addition to resists. For example, as is well known, inorganic SOG (Spin-on -glass
) is an organic silicon polymer useful in the production of semiconductor devices 1 and the like, and its production method is also known. Furthermore, one of the uses of the above-mentioned organosilicon polymer is as an insulating film between the eyebrows of a semiconductor device having a multilayer wiring structure.

The interlayer insulating film is formed by forming the first layer wiring, forming an insulating film, forming through holes in the insulating film to establish continuity between the upper and lower wiring layers, and then applying the second layer wiring through the insulating film. ,
Since this process is repeated sequentially to form multilayer wiring,
It was mandatory. Conventionally, materials used as interlayer insulating films include inorganic materials such as silicon dioxide, silicon nitride, and phosphorous glass (PSG), which are formed by vapor phase growth using silane gas, oxygen gas, etc., or polyimide and silicone resin. Polymer insulating materials such as, or laminates of these materials are used, but as wiring patterns become finer, materials with better characteristics in terms of reliability are required.

When considering multilayer wiring, the surface of the semiconductor substrate with the first layer wiring has irregularities due to the wiring, so if this is used as a base and an inorganic film is formed on top of it, the surface of the glabella insulating film will reproduce the irregularities of the base as is. I end up. Therefore, unevenness on the surface of the substrate causes disconnection, poor insulation, etc. of the upper layer wiring formed on the substrate. Therefore, it has been desired to develop an insulating material that can flatten an uneven base substrate.

Therefore, a method of obtaining a flat surface through an insulating film manufacturing process such as an etch-back method or a bias sputtering method, and a method of obtaining a flat insulating film by forming a resin film by a spin code method are being considered. Among these methods, the resin coating method, which is simpler in terms of process, requires the resin to be spin-coated and then heated and cured. By curing, the process can be further simplified. However, since the semiconductor manufacturing process includes a heat treatment step of 400°C or higher, conventionally used polymeric materials such as polyimide and silicone resin may oxidize or thermally decompose the film during heat treatment, or harden. It has the disadvantage that cranks occur due to film distortion caused by reactions, film oxidation, decomposition, etc. Therefore, it has been desired to develop a heat-resistant resin material that does not change during the heat treatment process.

Further, a characteristic required of the interlayer insulating film is a low dielectric constant. That is, if the dielectric constant of the interlayer insulating film is low, wiring delay time is shortened, and high-speed devices can be realized.

However, the dielectric constant of conventionally used inorganic materials such as silicon dioxide, silicon nitride, and phosphorous glass (PSG) is 4.
．． The dielectric constant of the inorganic SOG is 0 or more, and it is desirable to lower the dielectric constant.On the other hand, since the composition of the inorganic SOG after heat curing is similar to that of silicon dioxide, it is difficult to lower the dielectric constant.

[Problem to be solved by the invention]

A first object of the present invention is to provide a novel organosilicon polymer useful in fields such as the manufacture of semiconductor devices, in view of eliminating the drawbacks of the conventional techniques as described above.

A second object of the present invention is to provide a method for producing such a novel organosilicon polymer.

A third object of the present invention is to provide a high-resolution resist material that is excellent in sensitivity and oxygen plasma resistance, exhibits little swelling during development, and has high contrast, and is particularly useful as an upper layer resist in a two-layer resist method. It is in.

A fourth object of the present invention is to provide a resist pattern forming method capable of forming a sharp and fine pattern even on an uneven base material.

A fifth object of the present invention is to provide a semiconductor device having a layered film that does not reproduce the unevenness even when applied on an uneven base and has excellent heat resistance, insulation properties, etc. .

A sixth object of the present invention is to provide a semiconductor device having an excellent glabella insulating film and/or a heat-resistant protective film.

Other objects of the present invention will be easily understood from the detailed description below.

[Means to solve the problem]

As a result of intensive research in order to solve the above-mentioned problems, the present inventors have discovered that, instead of forming an organosilicon polymer into a conventional ladder-type structure or a structure similar thereto, it has a three-dimensional spike-like structure, that is, silphenylene siloxane. It was discovered that the problem could be solved by creating a three-dimensional spike-like structure consisting of a strong core and a functional nitriorganosilyl group surrounding this core. The organosilicon polymer discovered by the present inventors is polysilphenylene siloxane, and its main characteristics are: (1) high sensitivity to high-energy radiation such as electron beams (EB) and deep UV radiation; (2) High contrast (for example, γ=2.8)
(3) Small swelling during development (for example, 0.2 μd/S when used as an EB resist); (4) Therefore, high resolution; (5) High softening temperature (400°C) (6) High oxygen plasma resistance (for example, selectivity to novolak resist of 100). In addition, in this specification, such novel polysilphenylene siloxane is referred to as TSPS (Three-dimensional
nal Polysilphenylenesilox
(abbreviation of ane).

In one aspect, the present invention has the following molecular structural formula (I
): (In the above formula, R may be the same or different, each represents hydrogen or a monovalent hydrocarbon group, and m and n each represent a positive integer), silphenylene siloxane It has a three-dimensional spike-like structure consisting of a nucleus of silphenylene and triorganosilyl groups surrounding the silphenylene nucleus,
The polysilphenylene siloxane is characterized by having a weight average molecular weight of 0,000.

In another aspect, the present invention provides the structural formula (i
) In producing polysilphenylene siloxane represented by the following formula (II): (In the above formula, R1 to R, may be the same or different, and hydrogen, Represents a monovalent hydrocarbon group, trichlorosilyl group or trialkoxysilyl group, provided that
At least two of these substituents are trichlorosilyl groups and/or trialkoxysilyl groups) are hydrolyzed, and the product of the hydrolysis is subsequently subjected to dehydration condensation polymerization. In the manufacturing method of siloxane.

In yet another aspect of the present invention, in producing the polysilphenylene siloxane represented by the structural formula (1), the production method is repeated, and the product obtained by the dehydration condensation polymerization is is a triorganosilane represented by the following formula: (R)zsiX (in the above formula, R is the same as defined above, and
represents a halogen, a cyano group, an isocyanato group, or an isothiocyanato group), hexaorganodisilazane represented by the following formula: (R) z
siNHsi (R) 3 (in the above formula, R is the same as defined above), hexaorganodisiloxane represented by the following formula: (R) zsi
O5i(R) 3 (in the above formula, R is the same as defined above), or a mixture thereof to remove the hydrogen atoms of the silanol groups remaining in the product that did not contribute to the dehydration condensation polymerization. A method for producing a polysilphenylene siloxane, characterized in that it is substituted with a triorganosilyl group represented by the following formula: (R) 1Si- (in the above formula, R is the same as defined above).

In yet another aspect of the present invention, in producing the polysilphenylene siloxane represented by the structural formula (1), the production method is repeated, and the product obtained by the dehydration condensation polymerization is A triorganosilane represented by the following formula: (RhSiX (in the above formula, R is the same as defined above, and
represents a halogen, a cyano group, an isocyanato group, or an isothiocyanato group), hexaorganodisilazane represented by the following formula: (R) z
siNHsi (R)! (In the above formula, R is the same as defined above), hexaorganodisiloxane represented by the following formula: (R) 3si
Osi (R) z (in the above formula, R is the same as the above definition), or a mixture thereof (provided that R, -R,
and at least 5% or more of the total number of R's are halogenated lower alkyl groups or halogenated aryl groups), hydrogen atoms of silanol groups remaining in the product that did not contribute to the dehydration condensation polymerization are A method for producing a polysilphenylene siloxane characterized by substitution with a triorganosilyl group represented by the formula: (R)zSi- (in the above formula, R is the same as defined above).

In another aspect of the present invention, in producing the polysilphenylene siloxane represented by the structural formula (I), a triorganosilane represented by the following formula: (R) 1siX (the above formula , R is as defined above, and X
represents a halogen, a cyano group, an isocyanato group, or an isothiocyanato group), hexaorganodisilazane represented by the following formula: (R) z
siNHsi (R)! (In the above formula, R is the same as defined above), hexaorganodisiloxane represented by the following formula: (R) 3si
O5i (R) z (in the above formula, R is the same as defined above), or a mixture thereof, is dissolved in an organic solvent, and the solution thus obtained is added to the following formula (II) in the presence of water. An organosilicon compound represented by
At least two of these substituents are trichlorosilyl groups and/or trialkoxysilyl groups) are gradually added thereto.

Another aspect of the present invention is a resist material comprising polysilphenylene siloxane represented by the structural formula (1). This resist material is preferably negative-working and is used as the top resist in a two-layer resist process.

Furthermore, in another aspect of the present invention, a resist material made of polysilphenylene siloxane represented by the structural formula (f) is applied to the surface of a base material, and the obtained resist film is exposed to deep ultraviolet rays. It comprises selectively exposing to ionizing radiation such as electron beams and X-rays to obtain a desired pattern, and developing the resist film after pattern exposure to dissolve and remove the resist material in unexposed areas. A method of forming a resist pattern is provided. Here, if there is a step on the surface of the base material, the resist film has a two-layer structure, and in this case, the lower resist is made of a resist material having a flattening function and the structural formula (
An upper resist is formed from a resist material consisting of polysilphenylene siloxane represented by I), and thus:
Preferably, the resist pattern formed in the upper resist layer is transferred to the lower resist layer by oxygen plasma etching or the like.

Furthermore, in another aspect of the present invention, a resist pattern formed from a resist material made of polysilphenylene siloxane represented by the structural formula (, 1) is used as a mask to dry-etch the underlying layer. A method of manufacturing a semiconductor device includes a step of selectively removing the semiconductor device.

Another aspect of the present invention is a semiconductor device characterized by having a layer film made of polysilphenylene siloxane represented by the structural formula (I). Although the layered film of the present invention can be advantageously used for various purposes, it is preferably used as an insulating film between the eyebrows of multilayer wiring and/or as a heat-resistant protective film.

[For production]

The organosilicon polymer TSPS according to the present invention has a molecular structure similar to that of a gel obtained by perundum crosslinking compared to a conventional linear polymer having a linear structure or ladder structure. is high. In addition, since a benzene ring is introduced into the molecular skeleton, the movement of each atom is restricted, so swelling during development is extremely small compared to polymers with conventional linear and ladder structures. Therefore, it is possible to clearly resolve punched patterns of one or less lines, which have been difficult to resolve in conventional negative resists based on organic silicon polymers.

In addition, by selecting the type of triorganosilyl group, which is a functional group, visible light, ultraviolet rays, far ultraviolet rays, excimer laser,
Highly sensitive to X-rays, electron beams, etc.

Furthermore, since the silicon content in the skeleton is high, the oxygen plasma resistance is sufficient.

Furthermore, the organosilicon polymer TSPS according to the present invention is
It is soluble in many available organic solvents and can be deposited using conventional spin-coating methods. Therefore, a semiconductor substrate surface having an uneven surface can be easily planarized.

In addition, these organosilicon polymers not only have excellent heat resistance, but also have the advantage of having a low dielectric constant because, unlike conventional inorganic SoC materials, many organic groups exist even after film formation. . Therefore, it is useful as a glabellar insulating film that does not cause damage in the manufacturing process of semiconductor devices and contributes to speeding up devices.

Furthermore, an organosilicon polymer according to the present invention, wherein at least 5 of the total number of substituents R, -Rh and R in the above formula
A polymer in which % is a halogenated lower alkyl group and/or a halogenated aryl group is highly sensitive to ionizing radiation, especially electron beams and X-rays, so it is possible to form a negative pattern, Through holes can be formed without resist. Therefore, it is useful as a glabellar insulating film that does not cause damage in the manufacturing process of semiconductor devices and contributes to speeding up the device and simplifying the process.

These effects of the present invention will become clearer by referring to the molecular structure model of the organosilicon polymer TSPS of the present invention shown in the accompanying drawings and others. That is: FIG. 2 shows a molecular structure model of TSPS of the present invention. As shown in the figure, TSPS is composed of a strong silphenylene core and a triorganosilyl group, which is a functional group surrounding this core. Due to its special three-dimensional superstructure, this TSPS is stronger and tougher than conventional linear or ladder structured polymers, and due to these properties, it has high contrast and low swelling. , and is thermostable.

As described above, the TSPS of the present invention is synthesized by hydrolyzing the organosilicon compound represented by the formula (n) and subsequently subjecting the hydrolyzed product to dehydration condensation polymerization. The residual silanol groups around the silphenylene nucleus are
It is terminated by substitution with a triorganosilyl group (eg triorganochlorosilane). Second T
The reaction formula for synthesizing SPS using a hexafunctional monomer as a starting material is as follows:
ORO）I Ol
1
1RO-5i-ORHO-5i-OH・・・・
-0-5i-0-・・---・RO-5i-ORHO-
Si-OH---0-5i-0------0R
OH0 By the way, conventional ladder structure polymer (Ladder 5PS)
was synthesized from a tetrafunctional monomer as a starting material according to the following reaction formula: In order to confirm the synthesis of TSPS described above, the present inventors synthesized TSPS in an intermediate state.
The structure of TSPS in the final state was determined by the ``5i-NAR spectrum (using model GX500 manufactured by JEOL) and G
Evaluation was performed using a PC-LALLS chromatogram (using models HLC-8020 and LS-8000 manufactured by Tosoh Corporation). The results obtained are shown in FIG. 3, as well as FIGS. 4 and 5. Note that GPC-LALLS refers to a chromatogram obtained using a gel permeation chromatography device equipped with a low-angle laser light scattering photometer (GPC-LALLS).
-LALLS=gel-permeatton chr
omato-graphy equipped wit
h a low-angle 1aser light
scattering photometer).

In the NMR spectrum of TSPS shown in FIG. 3, the intermediate state 1! (after hydrolysis) that of -60 pp- and -
shows two broad peaks centered at 10 pp-;
It was shown that residual 5tOH and 5i(OHh groups exist in the molecule. However, as the synthesis proceeded further, dehydration of the silanol group occurred, and in the final state of the synthesis, as shown in the figure, the silanol group The peak indicating the presence of was almost completely removed.

Figures 4 and 5 show the TSPS and rudder s, respectively.
This shows a GPC-LALLS chromatogram of ps. The elution curves shown were determined by using a LALLS photometer (LS) and a refractometer (R1), respectively. As shown, the top of the TSPS LS curve is shifted to the shorter time side than that of the R1 curve, but at the peak of the rudder 3PS shown in Figure 5, the LS and RI curves almost match. .

We also measured the weight average molecular weight (Mw) of TSPS and ladder SPS by conventional GPC (calibrated with polystyrene) and GPC-LALLS. The results are shown in Table 1 below.

As is clear from the above, Hw of TSPS measured by GPC-LALLS is larger than that of ladder SPS, while TSPS measured by conventional GPC
The IJw of is smaller than that of ladder SPS.

The second fact is that TSPS has a molecular size of ladder S.
Despite being smaller than PS, the weight average molecular weight (M
w ) is larger than that of ladder SPS. This shows that the TSPS molecules have a structure like a densely packed three-dimensional network.

The present inventors furthermore, TSPS and rudder SPS
The EB anger level and oxygen plasma resistance of the sample were measured according to the following methods, and the two were compared. TSPS was dissolved in methyl isobutyl ketone ([BK) and the resulting resist solution was applied onto a 1.0 mm thick lower resist (phenolic novolak resin; available from Silaplay under the trade name MP-1300). The film was spin-coded with a film thickness of 0.2-. The obtained upper layer resist was prebaked at 80°C for 20 minutes. Then, TSPS
In order to evaluate the EB sensitivity of
00) was used for EB exposure at an acceleration voltage of 20 kV. The exposure amount was controlled by changing the exposure time. In order to evaluate the oxygen plasma resistance of TSPS, the TSPS resist pattern obtained by EB exposure was transferred to the lower resist (MP-1300) by reactive ion etching (0□-RIE) using oxygen. The enching device used was model OEM~451 manufactured by Anelha.
Oxygen pressure is 2.6 Pa, oxygen flow rate is 10 sec++
+, and the applied power density was 0.16 W/cd.

Furthermore, the same operation as above was repeated for the rudder SPS. The results obtained are shown in FIGS. 6 and 7.

Figure 6 shows T with dispersion degree (Mw /Hn) = 1.6.
Ladder SP with the same dispersion as the EB sensitivity curve of SPS
This is a comparison plot of the EB sensitivity curve of S. The introduced functional group was a methyl group in both TSPS and ladder SPS. Changes in resist film thickness due to changes in exposure amount are controlled by α-step (Tenco, USA).
r Instruments). 6th
The T value of the TSPS determined from the EB sensitivity curve in the figure is about 2.8, and that of the rudder SPS is about 1.6. In the case of TSPS, higher contrast can be obtained compared to conventional siloxane negative resists, such as linear or ladder structures. Further, in the case of rsps, the EB exposure amount that gives a residual resist film thickness of 50% is 28 μC/ctll. As can be understood, a resist with higher sensitivity can be obtained by changing the type of functional group introduced to a more sensitive one (for example, a chloromethyl group).

FIG. 7 is a graph plotting the etching rates when the upper layer resist (TSPS) and the lower layer resist (MP-1300 after hard baking) were etched in oxygen plasma. The TSPS resist was etched at about 10 λ/min, whereas the MP-1300 was etched at about 1000 λ/min. This indicates that the oxygen plasma resistance of TSPS is 100 in selectivity (relative to novolac resist).

Figures 8A and 8B are electron micrographs (SEM) showing the results of EB exposure and development of a 0.2 m line and space pattern of a TSPS upper resist on an MP-1300 lower resist, respectively. As is clear from these photographs, the fine rectangular profiles are well resolved, supporting the fact that the three-dimensional molecular structure of the present invention suppresses swelling during development.

Moreover, FIG. 9A and FIG. 9B respectively show TSPS/
It is an electron micrograph of a two-layer resist pattern obtained using MP-1300 two-layer structure resist.

In the case of FIG. 9A, a 0.2-width isolated TSPS resist pattern was accurately transferred to the MP-1300 underlying resist by 0□-RIE without thermal distortion.

Similarly, a 0.3 dust space TSPS resist pattern was also accurately transferred to the MP-1300 underlying resist without thermal deformation (see Figure 9B).

Further, the present inventors evaluated the usefulness of TSPS as a far-ultraviolet resist according to the following method.

First, when the ultraviolet absorption of TSPS was measured according to a conventional method, an ultraviolet absorption spectrum as shown in FIG. 10 was obtained. As is clear from the spectrum shown, TSP
Since the silphenylene nucleus contained in the molecule of S absorbs deep ultraviolet rays, S can be used as a deep ultraviolet resist by introducing an appropriate functional group into the molecule.

FIG. 11 is a graph plotting the TSPSO deep ultraviolet sensitivity. The TSPS used here contained vinyl/phenyl groups as its functional groups. 20 For far-UV sensitivity measurement, after forming a TSPS/MP-1300 two-layer resist as explained in the previous section of measuring EB sensitivity and oxygen plasma resistance, Deep UV exposure was performed using a -Hg light source. The resolution was also evaluated by 1:1 contact exposure and by spin developing the exposed resist in an alcohol mixture for 30 seconds. As is clear from the graph of FIG. 11, the amount of deep ultraviolet exposure that gives a residual resist film thickness of 50% is 100n+J/all.

Figures 12A and 12B respectively show MP-130
2 is an electron micrograph showing the results of deep UV exposure and development of a 0.5 source spacing pattern of a TSPS top layer resist on a 0.0 bottom layer resist. As is clear from these photographs, a 0.5 tnn space pattern with almost vertical sidewalls could be clearly formed.

〔Example〕

As described above, the polysilphenylene siloxane which is the organosilicon polymer of the present invention is represented by the molecular structural formula (I), where R represents hydrogen or a monovalent hydrocarbon group,
Here, the monovalent hydrocarbon group is preferably a lower alkyl group, a halogenated lower alkyl group, a lower alkenyl group,
These include aryl groups and halogenated aryl groups. As mentioned above, this organosilicon polymer differs from conventional linear or ladder structured organosilicon polymers in that it has the following spike-like skeleton structure: ・・−1・−〇−5i−0 〜・−−−−・１−−−・
-0-3i-0-----.

As understood from the above description, the organosilicon polymer of the present invention includes first, second, and third organosilicon polymers. Here, the "first organosilicon polymer" is the former (I
It is obtained by hydrolyzing the organosilicon compound of I) and subsequently subjecting the hydrolyzed product to dehydration condensation polymerization.

In addition, the "second organosilicon polymer" is the above-mentioned first organosilicon polymer, in which the hydrogen atoms of the silanol groups contained in the polymer are triorganosilyl groups represented by the following formula. : (R)35i- (In the above formula, R is the same as defined above). Furthermore, the "third organosilicon polymer" is the second organosilicon polymer described above, and at least 5 of the total number of substituents R5 to R and R in the above formula
% is a halogenated lower alkyl group and/or a halogenated aryl group. Note that this third polymer has similar properties to the second polymer, can be produced by a similar manufacturing method, and has similar usefulness; however,
By containing a halogenated lower alkyl group or a halogenated aryl group as described above, it is characterized by having photosensitivity to ionizing radiation such as electron beams and X-rays. Here, the halogenated lower alkyl group may be any group in which a lower alkyl group is substituted with a halogen, but 01 to C3
It is preferable that it is a group in which the alkyl group of
zHaCl, -CJzCfz.

-C2H2C123 etc. are effective. The halogenated aryl group may be any halogen-substituted aromatic compound, but -C6H,l, -C6H3112, etc. are convenient.

The first, second and third organosilicon polymers according to the present invention are
Each can be manufactured according to various manufacturing methods, as already mentioned above. For example: The first organosilicon polymer described above can be produced as follows. That is, the organosilicon compound of the previous generation (If) is dissolved in one or more solvents, and hydrolyzed and polycondensed at an appropriate temperature in the presence of water and, if necessary, a catalyst. Here, as described above, at least two of the substituents R1 to R6 of the organosilicon compound (n) are
Although at least one of the substituents must be a trichlorosilyl group and/or a trialkoxysilyl group, it is particularly preferable that two or three of them are such groups, and the remaining substituents are preferably hydrogen. Moreover, in the case of two, from the viewpoint of ease of synthesis, it is preferable to use the b-position rather than the ortho- and meta-positions. Further, R3-R4 may have at least two trichlorosilyl groups or trialkoxysilyl groups, but from the viewpoint of polymerization control, trialkoxysilyl groups are preferred, particularly trimethoxysilyl groups and triethoxysilyl groups. Silyl groups are convenient.

Furthermore, in order to obtain a second organosilicon polymer, the above-mentioned first
A triorganosilane represented by the following formula: (R) 35iX (in the above formula, R and X are the same as defined above), a hexaorganodisilazane represented by the following formula: (R) 3
siNH3i (R): 1 (in the above formula, R is the same as the above definition), hexaorganodisiloxane represented by the following formula: (R)35iO5i(R)3 (in the above formula, R is the same as the above definition) ), or a mixture thereof, to convert the hydrogen atoms of the silanol groups remaining in the polymer that did not contribute to the dehydration condensation polymerization into a triorganosilyl group represented by the following formula: (R)35i- ( In the above formula, R is the same as defined above.

Further, the second organosilicon polymer can also be obtained by the method described below. That is, triorganosilane represented by the following formula: (R)zSiX (in the above formula, R and X are the same as defined above), hexaorganodisilazane represented by the following formula: (R) 3
siN)ISi (R) y (in the above formula, R is the same as the above definition), hexaorganodisiloxane represented by the following formula: (R) 1siO3i (R) 3 (in the above formula, R is the same as the above definition) ), or a mixture thereof in an organic solvent, and in the presence of water, the former (n)
Gradually mix the compounds.

The resulting polymer is ideally a cone-shaped resin having a three-dimensional random structure. Further, particularly in the case of the second organosilicon polymer, a structure in which the outside of the spike-like skeleton structure is surrounded by triorganosilyl groups is ideal.

Furthermore, the third organosilicon polymer described above can be produced as follows. That is, the organosilicon compound of the cutting allowance (II) is dissolved in one or more solvents, and hydrolyzed and polycondensed at an appropriate temperature in the presence of water and, if necessary, a catalyst. Furthermore, the obtained organosilicon polymer was converted into a triorganosilane represented by the following formula: (R) zsiX (R and X in the formula are the same as defined above, but R1-R4 of the cutting allowance (II) and of the total number of R, at least 5
% or more is a halogenated lower alkyl group or a halogenated aryl group), hexaorganodisilazane represented by the following formula: (R) z
siNFlsi (R) z (in the above formula, R is the same as the above definition), hexaorganodisiloxane represented by the following formula: (R) 3siO5i (R): 1 (in the above formula, R is the same as the above definition) (RhSi- , R is the same as defined above).

Moreover, this third organosilicon polymer can also be obtained by the method described below. That is, triorganosilane represented by the following formula: (R) asiX (in the above formula, R and X are the same as defined above), hexaorganodisilazane represented by the following formula: (R) 3
siNH5r (R) y (in the above formula, R is the same as defined above), hexaorganodisiloxane represented by the following formula: (R) :lS
its i (R) 3 (in the above formula, R is the same as defined above) or a mixture thereof is dissolved in an organic solvent, and the compound for cutting allowance (II) is gradually mixed in in the presence of water.

The obtained polymer, like the first and second organosilicon polymers described above, is ideally a cassava resin having a three-dimensional random structure. A structure surrounded by triorganosilyl groups is ideal.

Some examples of particularly preferred organosilicon polymers in the practice of the present invention are as follows: It is represented by the cutting allowance (If), and R5-R7 in the formula is -H,
-CH3, -C2H5, -5iCf! ] + −si
(OCHz) 3. -5i (OCJs) 3, etc., with a weight average molecular weight of 1,000, obtained by hydrolyzing an organosilicon compound such as
~5,000,000 organosilicon polymer (first organosilicon polymer). At least two of the substituents R1-Rh are -5iC13+ -5i (OCH!, -Si (
OCzHs) 3 and other trichlorosilyl groups and trialkoxysilyl groups, and the others are preferably hydrogen from the viewpoint of heat resistance.

The hydrogen atom of the silanol group contained in the first organosilicon polymer is substituted with a triorganosilyl group represented by the following formula: (R)zSi- (R in the formula is the same as defined above). (second organosilicon polymer). In this second organosilicon polymer, some or all of the silanol groups are substituted with triorganosilyl groups, so when used as a resist solution, resist properties are less likely to change due to crosslinking, and it has excellent stability. . Furthermore, when it is used as an interlayer insulating film, it is superior to the first organosilicon polymer in that the formed film is less prone to cracking. This is because the first organosilicon polymer tends to contain many silanol groups and is easily distorted by crosslinking during heating (on the other hand, in the second organosilicon compound, only one silanol group This is because distortion due to crosslinking is less likely to occur because part or all of it is substituted with a triorganosilyl group.

Further, the second organosilicon polymer contains more organic groups than the first organosilicon polymer, and has a lower dielectric constant. Here, R in the formula may be the same or different as described above, and may be any hydrogen or monovalent hydrocarbon group. Specifically speaking, the monovalent hydrocarbon groups include alkyl groups such as methyl group, ethyl group, and hexyl group; 1-chloromethyl group;
Haloalkyl groups such as 2-chloroethyl group and 3-chloropropyl group; Aralkyl groups such as 2-phenylethyl group and 2-phenylpropyl group; Alkoxy groups such as methoxy group and ethoxy group; Alkenyl groups such as vinyl group and allyl group ; Aryl groups such as phenyl group and tolyl group; Heroaryl group such as parachlorophenyl group; and epoxy group. Here, if the film is intended to be used as an insulating film between the eyebrows, R in the above formula preferably contains an aryl group because an aryl group has the best heat resistance. Specifically, they include triphenylsilyl group, methyldiphenylsilyl group, dimethylphenylsilyl group, and the like.

The organosilicon polymer of the present invention is useful as a resist material, and therefore, this resist material can be advantageously used to form resist patterns and manufacture semiconductor devices.

The resist material of the present invention can be prepared by dissolving the organosilicon polymer as detailed above in an organic solvent such as alcohol, ketone, or ether. The resulting resist solution is preferably filtered using a filter with a pore size of about 0.1 ta and, when spin-coded, has a pore size of about 0.1 ta.
The concentration is adjusted to obtain a desired film thickness in the range of 1 to 0.5. The coating liquid whose concentration has been adjusted in this way can be applied onto a suitable object using any coating technique including a spin code method, preferably as an upper layer resist of a two-layer resist method. I can do it.

13A to 13D show that the resist material of the present invention is used as an upper layer resist in a two-layer resist method to
The process of manufacturing gate 2MO8 is shown in cross section in order. In the illustrated example, it should be noted that there are steps in the polysilicon underlying the resist.

First, as shown in FIG. 13A, an n-type polysilicon film 13 to be used as a gate electrode (polysilicon) is formed on a silicon substrate 11 by, for example, CVD. In addition,
Examples of pre-processes leading to this are as follows.

(1) Formation of silicon oxide film 12 by thermal oxidation of silicon substrate 11.

(2) Channel stop diffusion.

(3) Formation of field oxide film.

(4) Formation of gate oxide film.

After forming the polysilicon film, a resist pattern consisting of a lower resist (flattening layer) 3 and an upper resist (TSPS of the present invention) 4 is formed on the polysilicon film 3, as shown in FIG. 13B. Formation of this resist pattern can preferably be carried out according to a conventional two-layer resist method, for example, according to the method described above with reference to FIGS. 1A to 1D.

When the underlying polysilicon film is etched using the resist pattern shown in FIG. 13B as a mask, a polysilicon pattern 13 is obtained as shown in FIG. 13C.

After forming the polysilicon pattern in this way, removal of the oxide film from the source/drain region, diffusion of the source/drain, formation of a silicon oxide film by CVD, formation of contact holes, vapor deposition of aluminum for wiring, etc. Processes such as patterning are performed according to conventional methods. As shown in FIG. 13D, the target St gate P? 'lO3 is obtained. Note that 14 in the figure is a glabellar insulating film made of a silicon oxide film, and 15 is an aluminum wiring.

In addition to being used as a resist material, the organosilicon polymer of the present invention can be advantageously used as various layers in semiconductor devices and the like. The organosilicon polymer of the present invention is particularly useful as an interlayer insulating film. ) may be used in combination with an inorganic film such as to form a layered insulating film. The advantages of using the organosilicon polymer of the present invention as a glabellar insulating film include: (1) excellent heat resistance, (2) ease of spin coding, (2) good planarization function, (2) good compatibility with ordinary resists, ■Good adhesion to SiO□, PSG, and wiring, ■Low hygroscopicity, ■Low dielectric constant, and others.

In particular, when the third organosilicon polymer is used to form the glabellar insulating film, the following points are important. The organosilicon polymer that can be used for forming the interlayer insulating film is preferably represented by a cutting allowance (II), in which R, ~R, is -H
, -CHl, -CHzCl, -CzHs.

-C2HaCjl! , -5iC13, -5i(OC
Weight average molecular weight 1,000-5, obtained by hydrolyzing an organosilicon compound such as Flx)z, -5i(OCzHs)3, followed by dehydration condensation polymerization.
000,000 organosilicon polymer, wherein the hydrogen atom of the silanol group contained in the organosilicon polymer is a triorganosilyl group represented by the following formula: (R)35i- (R in the formula is An organosilicon polymer which is the same as the definition, but as described above, at least 5% of the total number of R5-R6 and R is a halogenated lower alkyl group or a halogenated aryl group). be. At least two of the substituents R and -R are -5iC-3. -5l (OCH3) 3l-5l (OCJS)
From the viewpoint of heat resistance, it is preferable that the group is a trichlorosilyl group such as No. 3 or a trialkoxysilyl group, and the others are hydrogen. This organosilicon polymer is excellent in that when it is used as an interlayer insulating film, the formed film is less prone to cracking.

This is because organosilicon polymers containing many silanol groups tend to become distorted due to crosslinking during heating.
This is because in this organosilicon compound, some or all of the silanol groups are substituted with triorganosilyl groups, so that distortion due to crosslinking is less likely to occur. Moreover, this organosilicon polymer contains many organic groups and has a lower dielectric constant. Here, R in the formula may be the same or different as described above, and as long as it is hydrogen, a lower alkyl group, a halogenated lower alkyl group, a lower alkenyl group, an aryl group, or a halogenated aryl group. Any of these may be used, but in order to form through holes in the resin for conducting conduction between the upper and lower wiring layers by (7) irradiation with ionizing radiation such as X-rays and electron beams, the above-mentioned R1 to R6 are included. , halogenated lower alkyl groups and halogenated aryl groups must be contained in an amount of 5% or more of the total. That is, a negative pattern can be formed using ionizing radiation. Furthermore, R
Since an aryl group or a halogenated aryl group has the best heat resistance, it is preferable that the group contains an aryl group. Specifically, they include parachlorophenyldiphenylsilyl group, methyldiparaphenylsilyl group, dichloromethylphenylsilyl group, and the like.

FIGS. 14A to 14G are cross-sectional views showing steps for manufacturing a Si gate NMO3 using the organic silicon polymer of the present invention as an interlayer insulating film.

First, a field oxide film is formed. As shown in FIG. 14A, an LOC is formed on a p-type silicon (Si) substrate 21.
For O5, a silicon oxide film (SiOz) 22 and a silicon nitride film (SiJ4) 26 are sequentially deposited. Next, as shown in FIG. 14B, a photoresist pattern 2 is formed.
By photo-etching using 7 as a mask, 5i31a is etched only in the area where the transistor will be formed later.
The membrane 26 is left behind. When wet oxidation using water vapor is performed after removing the photoresist pattern 27, as shown in FIG. 14C, areas of the Si substrate 21 that do not have the 5iJ4 film 26 on the surface are selectively oxidized to form a field SiO□.
A membrane 22 is formed.

Next, a Si gate is formed. After removing the SiJ film and SiO□ film used in the previous LOGO 5, the underlying Si substrate is oxidized again to form the gate 5iOz film.

Next, polysilicon used for the gate electrode is deposited by CVD. As shown in FIG. 14D, the gate Si
A polysilicon thin film 28 is formed on the O□ film/field SiO□ film 22. Selective etching of this polysilicon thin film 28 results in a silicon (Si) gate (see Si gate 28 in Figure 14E).

After forming the Si gate, the source and drain are formed. First, as shown in FIG. 14E, As ions are implanted (II) using the Si gate 28 as a mask. Next, the organosilicon polymer (TSPS) of the present invention is deposited to form an insulating film between the eyebrows.

Since TSPS can be flattened, the resulting glabellar insulating film 29 has a flat surface despite the presence of the field oxide film 22 and the Si gate 28 underlying it, as shown in FIG. 14F. ing. Furthermore, through holes are formed in the formed glabellar insulating film by dry etching to serve as connecting holes to the source and drain (not shown).

Finally, two electrodes are formed to form wiring. This is Si
After sputtering the incoming AI, the formed A/2
This can be done by selectively etching three films. As shown in FIG. 14G, the target Si
A gate NMO3 is obtained.

Note that 25 in the figure is 142 wiring.

The organosilicon polymer of the present invention is also useful as a heat-resistant protective film. More specifically, the polymer of the present invention is useful as passivation for protecting the interface of semiconductor devices, passivation for protecting wiring, and others. The polymer of the present invention not only does not soften even at high temperatures, but also has good processability compared to, for example, conventionally used polyimide.
It has advantages such as low hygroscopicity and no need to change etching gas when drilling through holes.

Subsequently, the present invention will be explained in detail with reference to Examples including synthesis examples of organosilicon polymers.

tl (synthesis example) 1.4 to a mixed solvent of 50 cc of methyl isobutyl ketone (MIBK), 25 cc of acetone, and 25 cc of methanol.
16 g of -bis(trimethoxysilyl)benzene was dissolved, 5.4 cc of water was added, and the mixture was stirred at room temperature for 30 minutes.

The system was concentrated under reduced pressure to obtain an approximately 20% by weight resin solution.

Gel permeation chromatography (GP) of this resin
The weight average molecular weight measured by C) was 5.2 XIO3 in terms of standard polystyrene, and the dispersion was 2.8.

■Complex (synthesis example) Methyl isobutyl ketone (MIBK) 50cc,
16 g of 1,4-bis(trimethoxysilyl)benzene was dissolved in a mixed solvent of 25 cc of acetone and 25 cc of methanol, 5.4 cc of water was added, and the mixture was stirred at room temperature for 30 minutes. The system was concentrated under reduced pressure to obtain an approximately 20% by weight resin solution.

Thereafter, 90 g of phenyldimethylchlorosilane and 90 g of pyridine were added, and the mixture was stirred at 80°C for 2 hours.

After cooling, add 100 cc each of MIBK and water, use a separatory funnel to obtain the upper MIBK layer, and wash it several times with water.
Residual water was removed by azeotropy. Thereafter, the reaction solution was poured into a large amount of water to precipitate and collect the resin. Freeze-drying was performed to obtain a white powder of approximately Log.

Gel permeation chromatography (GP) of this resin
The weight average molecular weight measured by C) was 5.3×10 3 in terms of standard polystyrene, and the dispersion was 2.8.

Spot 1 (Synthesis example) In a 500 cc four-bottle flask, 40 cc of methyl isobutyl ketone, 25 cc of methanol, 25 cc of acetone, 50 cc of water, 5 cc of concentrated hydrochloric acid, and 4 cc of trimethylchlorosilane.
．． 05 g was charged, and heated and stirred to bring it to a reflux state. 15.9 g of 1°4-bis(trimethoxysilyl)benzene was dissolved in 35 cc of MIBK and added dropwise into the above flask over 20 minutes. After that, stirring was continued for 60 minutes, and then cooled.
50 cc each of MIBK and water were added, an upper MIBK layer was obtained using a separatory funnel, and after washing with water several times, the remaining water was removed by azeotropy. Thereafter, the reaction solution was poured into a large amount of water to precipitate and collect the resin. freeze-dried,
12 g of white powder was obtained. The weight average molecular weight of this resin measured by gel permeation chromatography (GPC) was 3.6×10' in terms of standard polystyrene, and the dispersion was 4.0.

Base (Synthesis Example) 10 cc each of trimethylchlorosilane and pyridine were added to 100 g of a 4% MIBK solution of the white powder obtained in Example 3, and the mixture was stirred at 80°C for 2 hours. After cooling, 50 cc each of old BK and water were added, and an upper MIBK layer was obtained using a separatory funnel. After washing with water several times, the remaining water was removed by azeotropy. Thereafter, the reaction solution was poured into a large amount of water to precipitate and collect the resin. Freeze-drying was performed to obtain 4.17 g of white powder. Thereafter, low molecular weight oligomers and impurities were washed and removed using ethanol and acetonitrile, and 2.16 g of white powder was finally obtained. This powder was dissolved in a mixed solution of isopropyl alcohol and ethanol at 70°C, and the temperature was controlled and lowered in a constant temperature bath to precipitate the resin, followed by molecular weight fractionation. Gel permeation chromatography (GPC) of the obtained resin
The weight average molecular weight measured by the method was 4.5 XIO' in terms of standard polystyrene, and the dispersion was 1.6.

Step (Synthesis Example) 10 cc each of vinyldimethylchlorosilane and pyridine were added to 100 g of a 4% old BK solution of the white powder obtained in Example 3, and the mixture was stirred at 80°C for 2 hours. After cooling, add 50cc each of old BK and water, and use a separating funnel to separate the upper layer of MIBK.
The layers were obtained and washed several times with water, after which the remaining water was removed by azeotropy. Thereafter, the reaction solution was poured into a large amount of water to precipitate and collect the resin. Freeze-drying was performed to obtain 4.0 g of white powder. Thereafter, low molecular weight oligomers and impurities were washed and removed using ethanol and acetonitrile, and 1.24 g of white powder was finally obtained. This powder is dissolved in isopropyl alcohol at 70°C, and the resin is precipitated by lowering the temperature while controlling it in a constant temperature bath.
Molecular weight fractionation was performed. The weight average molecular weight of the obtained resin measured by gel permeation chromatography (GPC) was 4.2 XIO' in terms of standard polystyrene, and the dispersion was 1.5.

Okudan (synthesis example) Add 10 cc each of phenyldimethylchlorosilane and pyridine to 100 g of the 4% MIBK solution of the white powder obtained in Example 3 above.
was added and stirred at 80°C for 2 hours. After cooling, add 50cc each of old BK and water, and use a separatory funnel to separate the upper layer of MIB.
The K layer was obtained, washed several times with water, and then the remaining water was removed by azeotropy. The solution was concentrated and a large amount of acetonitrile was added to precipitate the resin, which was collected by filtration. freeze-dried,
3.1 g of white powder was obtained.

After that, low molecular weight oligomers and impurities are washed and removed using ethanol and acetonitrile, and the final product is 2.20%
g of white powder was obtained. This powder was dissolved in a mixed solvent of isopropyl alcohol and methyl isobutyl ketone at 70"C, and the temperature was lowered in a constant temperature bath to precipitate the resin, followed by molecular weight fractionation. The resulting resin gel The weight average molecular weight measured by permeation chromatography (GPC) was 5.4×10' in terms of standard polystyrene, and the dispersion was 2.9.

Counterfeit (synthesis example) In a 300 cc four-bottle flask, 50 cc of methyl isobutyl ketone, 25 cc of methanol, 25 cc of acetone, 50 cc of water, 5 cc of concentrated hydrochloric acid, and 7 cc of trivinylchlorosilane.
．． 15 g was charged and stirred with heating to bring it to a reflux state. 20.1 g of 1°4-bis(triethoxysilyl)henzene was added dropwise into the flask over 20 minutes. After that, stirring was continued for 20 minutes, then cooled, 50 cc each of FIIBK and water were added, and an upper MIBK layer was obtained using a separatory funnel. After washing with water several times, remaining water was removed by azeotropy. . Thereafter, the reaction solution was poured into a large amount of water to precipitate and collect the resin. Freeze-drying was performed to obtain about 15 g of white powder. Gel permeation chromatography (GPC) of this resin
) The weight average molecular weight was 4.1 x 104 in terms of standard polystyrene, and the dispersion was 5.6.

Godan (Synthesis Example) Add 10 cc each of phenyldivinylchlorosilane and pyridine to 85 g of the 14% MIBK solution of the white powder obtained in Example 7 above.
was added and stirred at 80°C for 2 hours. After cooling, MIBK
Add 50 cc of water and 50 cc of each, and use a separatory funnel to separate the upper layer of MI.
A BK layer was obtained, washed several times with water, and then residual water was removed by azeotropy. The solution was concentrated and a large amount of acetonitrile was added to precipitate the resin, which was collected by filtration. Freeze-drying was performed to obtain 10.4 g of white powder.

This powder is dissolved in a mixed solvent of isopropyl alcohol and methyl isobutyl ketone at 70°C, and the resin is precipitated by lowering the temperature while controlling it in a constant temperature bath.
Molecular weight fractionation was performed. When the weight molecular weight of the obtained resin was measured by gel permeation chromatography (GPC), it was found that Mw = 3.5XIO', Mw/M
n=1.5.

How many times (synthesis example) The procedure described in Example 2 above was repeated, but in this example, 90 g of chloromethylphenyldimethylchlorosilane was used instead of phenyldimethylchlorosilane. The weight average molecular weight of the obtained approximately Log white powder measured by gel permeation chromatography (GPC) was 6.3 x 103 in terms of standard polystyrene, and the dispersion was 2.8.

U (Synthesis Example) 40 cc of methyl isobutyl ketone, 25 cc of methanol, 25 cc of acetone, 50 cc of water, 5 cc of conc. 1.4-bis(trimethoxysilyl)henzen 1
5.9 g was poured into 7 volumes of old BK35cc and dripped into the flask over 20 minutes. After continuing stirring for 30 minutes,
After cooling, 50 cc each of MILK and water were added, and an upper MIBK layer was obtained using a separatory funnel. After washing with water several times, the remaining water was removed by azeotropy. Thereafter, the reaction solution was poured into a large amount of water to precipitate and collect the resin. Freeze-drying was performed to obtain 12 g of white powder. The weight-average molecular weight of this resin measured by gel permeation chromatography (GPC) was 3.3% in terms of standard polystyrene. OXI
O', variance was 4.0.

Chuidan (synthesis example) 100g of 4% MIBK solution of white powder obtained in Example 10 above
10 cc each of vinyldimethylchlorosilane and pyridine
was added and stirred at 80″C for 2 hours. After cooling, MIBK
Add 50 cc of water and 50 cc of each, and use a separatory funnel to separate the upper layer of MI.
A BK layer was obtained, washed several times with water, and then residual water was removed by azeotropy. Thereafter, the reaction solution was poured into a large amount of water to precipitate and collect the resin. Freeze-dry, 4.17
g of white powder was obtained. Thereafter, low molecular weight oligomers and impurities were washed and removed using ethanol and acetonitrile, and 2.16 g of white powder was finally obtained. This powder was dissolved in isopropyl alcohol at 70"C, and the resin was precipitated by lowering the temperature while controlling it in a constant temperature bath, and molecular weight fractionation was performed. Gel permeation chromatography of the obtained resin ( The weight average molecular weight measured by GPC) is 5.2X1 in terms of standard polystyrene.
0', the variance was 1.7.

Punishment (Synthesis Example) 100 g of 4% MIBK solution of the white powder obtained in Example 10 above
1 each of chloromethyldimethylchlorosilane and pyridine
0 cc was added and stirred at 80°C for 2 hours. After cooling, M
50 cc each of IBK and water were added, an upper MIBK layer was obtained using a separatory funnel, and after washing with water several times, the remaining water was removed by azeotropy. Thereafter, the reaction solution was poured into a large amount of water to precipitate and collect the resin. Freeze-dry, 4
．． 0 g of white powder was obtained. Thereafter, low molecular weight oligomers and impurities were washed and removed using ethanol and acetonitrile, and 1.24 g of white powder was finally obtained. This powder was dissolved in a mixed solution of isopropyl alcohol and ethanol at 70°C, and the temperature was lowered in a constant temperature bath to precipitate the resin, followed by molecular weight fractionation. The weight average molecular weight of the obtained resin measured by gel permeation chromatography (GPC) was 4.8 XIO' in terms of standard polystyrene, and the dispersion was 1.5.

(Synthesis example) 100 g of 4% MIBK solution of the white powder obtained in Example 10 above
10 cc each of P-chlorophenyldimethylchlorosilane and hibiridine were added to the mixture, and the mixture was stirred at 80°C for 2 hours.

After cooling, 50 cc each of MrBK and water were added, and an upper MIBK layer was obtained using a separatory funnel. After washing with water several times, the remaining water was removed by azeotropy. The solution was concentrated and a large amount of acetonitrile was added to precipitate the resin, which was collected by filtration. Freeze-drying was performed to obtain 3.1 g of white powder. Thereafter, low molecular weight oligomers and impurities were washed and removed using ethanol and acetonitrile, and 2.20 g of white powder was finally obtained. This powder was dissolved in a mixed solvent of isopropyl alcohol and methyl isobutyl ketone at 70°C, and the temperature was controlled and lowered in a constant temperature bath to precipitate the resin, followed by molecular weight fractionation. The weight average molecular weight of the obtained resin measured by gel permeation chromatography (GPC) was 5 in terms of standard polystyrene.
2 XIO', the variance was 1.5.

(Synthesis example) 100 g of 4% MIBK solution of the white powder obtained in Example 10 above
10 cc each of allyldimethylchlorosilane and pyridine
was added and stirred at 80°C for 2 hours. After cooling, MIBK
Add 50 cc of water and 50 cc of each, and use a separatory funnel to separate the upper layer of MI.
A BK layer was obtained, washed several times with water, and then residual water was removed by azeotropy. Thereafter, the reaction solution was poured into a large amount of water to precipitate and collect the resin. Freeze-dried, 4.0g
A white powder was obtained. Thereafter, low molecular weight oligomers and impurities were washed and removed using ethanol and acetonitrile, and 1.24 g of white powder was finally obtained. This powder was dissolved in isopropyl alcohol at 70°C, and the temperature was lowered in a constant temperature bath to precipitate the resin, followed by molecular weight fractionation. The weight average molecular weight of the obtained resin measured by gel permeation chromatography (GPC) was 5.5 x 10' in terms of standard polystyrene.
The variance was 1.7.

Group leader In this example, use as an electron beam resist will be explained.

13% by weight MIB of the organosilicon polymer obtained in Example 4 above
A K solution was prepared and filtered through a membrane filter with a pore size of 0.1 tna to obtain a resist solution. Next, 2. Phenol novolac resin (product name MP-1300, Silapray Co., Ltd.) was applied with a spin code to a thickness of Otna, hard baked to form a lower resist, and the above resist solution was applied on top of this to a film thickness of 0.2 mm. It was coated with a spin cord so that the coating was coated, and baked at 80° C. for 20 minutes. The two-layer resist film thus obtained was scanned with an electron beam at an accelerating voltage of 20 kV, developed with isopropyl alcohol for 60 seconds, and then rinsed with ethanol for 30 seconds. After baking at 8°C for 20 minutes, the sample was placed in a parallel plate type dry etching device and etched using oxygen plasma (2 Pa, 0.22 W/cm) for 15 minutes to transfer the upper layer pattern to the lower layer. .

As a result, this resist had a high contrast of T-2.3, and also had small swelling, so it was possible to resolve a punched pattern of 0.3n. Further, the electron beam exposure amount DJJ', which leaves an initial film thickness of 50%, which is a measure of sensitivity, was determined to be 50 uC/c+ll.

Punishment The method described in 15 above was repeated. However, in this example,
In place of the organosilicon polymer obtained in Example 4, Examples 1-
The polymers obtained in Examples 3 and 5 to 14 were used. Minimum space pattern and DZ that could be resolved! The results of determining (μC/ad) are shown in the following table.

Measured items 1235678 Measured items 9 10 11 12 13
14 In this example, use as a photoresist will be explained.

13% by weight MIB of the organosilicon polymer obtained in Example 8 above
A K solution was prepared and filtered through a membrane filter with a pore size of 0.1 μm to obtain a resist solution. Next, a phenol novolac resin (product name MP-1300, Silapray Co., Ltd.) is coated on the silicon substrate with a spin code to a thickness of 2.0 mm, hard baked to form a lower resist, and the above resist is applied on top of this. The solution was applied with a spin cord to a film thickness of 0.2 μm, and baked at 80° C. for 20 minutes. The two-layer resist film thus obtained has a wavelength of 248 nm.
After irradiating with mO far ultraviolet light, it was developed with old BK for 60 seconds,
Next, rinsing treatment was performed with isopropyl alcohol for 30 seconds. After baking at 80"C for 20 minutes, the sample was placed in a parallel plate type dry etching device and dry etched with oxygen plasma (2 Pa, 0.22 W/C111) for 15 minutes to transfer the upper layer pattern to the lower layer.

As a result, this resist had a high contrast of T=2.5, and because the swelling was small, a space pattern of 0.5 tnn could be resolved. In addition, the amount of deep ultraviolet exposure D l1lt that leaves an initial film thickness of 50%, which is a guideline for sensitivity.
When v was determined, it was 240 mJ/cnT.

The procedure described in Example 17 above was repeated. However, in this example, the organosilicon polymer obtained in Example 8 was replaced with Example 5.
The polymer obtained in Example 7, Example 11 or Example 4 was used. The following table shows the results of determining the minimum space pattern that could be resolved and D l1lfV.

Immediately In this example, the use as a chi-ray resistor will be explained.

13% MI by weight of the organosilicon polymer obtained in Example 13 above
A BKf4 solution was prepared and filtered through a membrane filter with a pore size of 0.1 mm to obtain a resist solution. Next, a phenol novolank resin (product name MP-1300, Silapray Co., Ltd.) is applied with a spin cord to a thickness of 2.0 mm on the silicon substrate, hard-baked to form a lower resist, and the above-mentioned A resist solution was applied with a spin cord to a film thickness of 0.2p, and baked at 80°C for 20 minutes. The two-layer resist film thus obtained was exposed to PdLα rays (4,37 people) through an X-ray mask, and MIBK
The film was developed for 60 seconds and rinsed with isopropyl alcohol for 30 seconds.

After baking at 80°C for 20 minutes, the sample was placed in a parallel plate dry etching device and exposed to oxygen plasma (2P
A, 0.22 W/d) for 15 minutes to transfer the upper layer pattern to the lower layer.

As a result, this resist had a high contrast of γ-2, 3 and also had little swelling, so it was possible to resolve a 0.4p space pattern. In addition, the X-ray exposure amount D5x leaves an initial film thickness of 50%, which is a guideline for sensitivity. It was found to be 350+++J/d.

Cage The procedure described in Example 19 above was repeated. However, in this example, the organic silicon polymer obtained in Example 13 was replaced with the polymer obtained in Examples 5 to 6, Example 8, Example 11, Example 12, or Example 14. Take the minimum space pattern that could be resolved. The results of determining (raJ/CIJ) are shown in the following table.

Heavy ANcL (synthesis example) 50 cc of methyl isobutyl ketone, 25 cc of methanol, 25 cc of acetone, 50 cc of water, 5 cc of conc. And so.

1.4-bis(triethoxysilyl)benzene 20.1
g was added dropwise into the flask over 20 minutes. After that, stirring was continued for 20 minutes, then cooled and 50cc each of MIBK and water was added.
In addition, the upper old BK layer was obtained using a separatory funnel, washed several times with water, and then the remaining water was removed by azeotropy. Thereafter, the reaction solution was poured into a large amount of water to precipitate and collect the resin. Freeze-drying was performed to obtain about 15 g of white powder. Gel permeation chromatography (GPC) of this resin
) The weight average molecular weight was 4.1 x 104 in terms of standard polystyrene, and the dispersion was 5.6.

Punishment (Synthesis Example) Add 10 cc each of phenyldimethylchlorosilane and pyridine to 85 g of the 14% old BK solution of the white powder obtained in Example 21 above.
was added and stirred at 80°C for 2 hours. After cooling, MIBK
Add 50 cc of water and 50 cc of each, and use a separatory funnel to separate the upper layer of MI.
A BK layer was obtained, washed several times with water, and then residual water was removed by azeotropy. The solution was concentrated and a large amount of acetonitrile was added to precipitate the resin, which was collected by filtration. Freeze-drying was performed to obtain 10.4 g of white powder.

Gel permeation chromatography (GP) of this resin
The weight average molecular weight measured by C) is 5.0 in terms of standard polystyrene. I XIO', variance was 5.3.

(Synthesis example) In a 500 cc four-bottle flask, 40 cc of methyl isobutyl ketone, 25 cc of methanol, 25 cc of acetone, 50 cc of water, 5 cc of concentrated hydrochloric acid, and 1,3-dichloromethyl-
1゜1.3,3. -Tetramethyldisiloxane 4.05
g was charged, and heated and stirred to bring it to a reflux state. 1.15.9 g of 4-bis(trimethoxysilyl)benzene
It was dissolved in 35 cc of BK and added dropwise into the flask over 20 minutes. After that, stirring was continued for 30 minutes, cooled, and MIBK
Add 50 cc of water and 50 cc of each, and use a separatory funnel to separate the upper layer of MI.
A BK layer was obtained, washed several times with water, and then residual water was removed by azeotropy. Thereafter, the reaction solution was poured into a large amount of water to precipitate and collect the resin. Freeze-drying was performed to obtain 12 g of white powder. The weight average molecular weight of this resin measured by gel permeation chromatography (GPC) is 1.2 XIO' in terms of standard polystyrene, and the dispersion is 4.
．． It was 0.

5C (Synthesis Example) 100 g of 4% MIBK solution of the white powder obtained in Example 23 above
1 each of chloromethyldimethylchlorosilane and pyridine
0 cc was added and stirred at 80″C for 2 hours. After cooling, M
50 cc each of IBK and water were added, an upper old BK layer was obtained using a separatory funnel, and after washing with water several times, the remaining water was removed by azeotropy. Thereafter, the reaction solution was poured into a large amount of water to precipitate and collect the resin. 4. Lyophilize;
17 g of white powder was obtained. Thereafter, low molecular weight oligomers and impurities were washed and removed using ethanol and acetonitrile, and 2.16 g of white powder was finally obtained. Gel permeation chromatography (GPC) of this resin
The weight average molecular weight as measured by standard polystyrene was 4.3XIO', and the dispersion was 3.5.

4% MIBK (synthesis example) The white powder obtained in Example 23 above? 8 liquid 100
g, vinyldimethylchlorosilane and pyridine each 10c
c was added, and the mixture was stirred at 80°C for 2 hours. After cooling, old BK
Add 50 cc of water and 50 cc of each, and use a separatory funnel to separate the upper layer of MI.
A BK layer was obtained, washed several times with water, and then residual water was removed by azeotropy. Thereafter, the reaction solution was poured into a large amount of water to precipitate and collect the resin. Freeze-dried, 4.0g
A white powder was obtained. Thereafter, low molecular weight oligomers and impurities were washed and removed using ethanol and acetonitrile, and 1.24 g of white powder was finally obtained. The weight average molecular weight of this resin measured by gel permeation chromatography (GPC) is 4.8 in terms of standard polystyrene.
X10', the dispersion was 4.2.

Material (Synthesis Example) 100 g of 4% old BK solution of the white powder obtained in Example 23 above
10 cc each of p-chlorophenyldimethylchlorosilane and pyridine were added to the mixture, and the mixture was stirred at 80°C for 2 hours.

After cooling, 50 cc each of MIBK and water were added, an upper MIBK layer was obtained using a separatory funnel, and after washing with water several times, the remaining water was removed by azeotropy. The solution was concentrated and a large amount of acetonitrile was added to precipitate the resin, which was collected by filtration. Freeze-drying was performed to obtain 3.1 g of white powder. Thereafter, low molecular weight oligomers and impurities were washed and removed using ethanol and acetonitrile, and 2.20 g of white powder was finally obtained. The weight average molecular weight of this resin measured by gel permeation chromatography (GPC) was 4.4 XIO' in terms of standard polystyrene, and the dispersion was 2.
It was 7.

The resin solution obtained in Example 1 above was diluted to 15% by weight with MIBK to form a silicon substrate on which a semiconductor element was formed and a first layer polysilicon wiring was applied (the thickness of polysilicon was 1n, the minimum line width was 1n). (In general, the minimum line spacing is 1.5 ts)
It was coated on top by a spin code method at 2000 rpm for 45 seconds. After coating, the coating was dried with the solvent at 80°C for 20 minutes, and then heat-treated at 450°C for 60 minutes in the air. The level difference on the substrate surface after the heat treatment was approximately 0.3 degrees, and the level difference caused by the wiring had been flattened. Next, through holes were formed, aluminum wiring between the two layers was formed, and a PSG film with a thickness of one layer was deposited as a protective layer by atmospheric pressure CVD, and then a window for taking out the electrodes was opened to obtain a semiconductor device. No defects were observed in this device even after a 1-hour heating test at 450°C in the atmosphere and 10 heat cycle tests from -65°C to 150°C.

The white powders obtained in Example 2 and Example 4 were each dissolved in methyl isobutyl ketone to obtain a 25% by weight resin solution. Each resin solution prepared as described above was applied to a silicon substrate on which a semiconductor element was formed and a second layer polysilicon wiring was applied (the thickness of polysilicon was 1-1, the minimum line width was 1-5, the minimum line spacing was 1. 5) by a spin cord method under the conditions of 200 rpm and 45 seconds. After application, 80°
After solvent drying at C for 20 minutes, heat treatment was performed at 400 C for 60 minutes. The level difference on the substrate surface after heat treatment is approximately 0.2
-, and the level difference caused by the wiring was flattened. Next, through-holes are formed, a second layer of aluminum wiring is formed, and a PSG film with a thickness of one tone is coated as a protective layer at normal pressure C.
After deposition by the VD method, a window for taking out the electrodes was opened to obtain a semiconductor device. No defects were observed in this device even after a heating test in nitrogen at 450°C for 1 hour and a heat cycle test from -65°C to 150°C 10 times.

The white powders obtained in Example 3 and Example 21 were each dissolved in methyl isobutyl ketone to obtain a 15% by weight resin solution. Each resin solution prepared as described above was applied to a silicon substrate on which a semiconductor element was formed and a -th layer polysilicon wiring was applied (the thickness of polysilicon was 1 pm, the minimum line width was 1 -
1 minimum line spacing is 1.5p) 200Orpm on top, 45
Coating was performed by the spin code method under conditions of 10 seconds. After application, 8
After solvent drying at 0°C for 20 minutes, heat treatment was performed at 400°C for 60 minutes. The level difference on the substrate surface after heat treatment is approximately 0.
．． 3 tnp, and the level difference caused by the wiring had been flattened. Next, through holes are formed, a second layer of aluminum wiring is formed, and a 1-thick PSG layer is used as a protective layer.
After the film was deposited by normal pressure CVD, a window for taking out the electrodes was opened to obtain a semiconductor device. This device uses 4
Heating test for 1 hour at 50°C, 1 at -65→150°C
No defects were observed even after 0 thermal cycle tests.

The white powder obtained in Example 6 above was dissolved in methyl isobutyl ketone to obtain a 25% by weight resin solution. The resin solution prepared as described above was applied to a silicon substrate on which a semiconductor element was formed and a second layer polysilicon wiring was applied (the thickness of the polysilicon was 1-1, the minimum line width was 1itIm, the minimum line interval was 1.5. m) by a spin code method under the conditions of 200 rpm and 45 seconds. After application, heat at 80°C for 20
After drying the solvent for 40” in the atmosphere,
Heat treatment was performed at C for 60 minutes.

The height difference on the substrate surface after the heat treatment was approximately 0.11M, and the height difference caused by the wiring had been flattened. Next, through holes are formed and the second layer of aluminum wiring is formed.
After depositing a PSG film with a thickness of one layer as a protective layer by atmospheric pressure CVD, a window for taking out the electrodes was opened to obtain a semiconductor device. No defects were observed in this device even after a heating test in nitrogen at 450°C for 1 hour and a heat cycle test from -65°C to 150°C 10 times.

Opening: The white powder obtained in Example 22 was dissolved in methyl isobutyl ketone to obtain a 25% by weight resin solution. The resin solution prepared as described above was applied to a silicon substrate on which a semiconductor element was formed and a first layer polysilicon wiring was applied (the thickness of polysilicon was IR1, the minimum line width was 1 line, and the minimum line spacing was 1 line).
．． 51!1a) by a spin cord method under the conditions of 200 rpm and 45 seconds. After application, heat at 80°C for 20
After drying the solvent for a minute, further dry it at 450° in the atmosphere.
Heat treatment was performed at C for 60 minutes.

The level difference on the substrate surface after heat treatment is approximately 0.1 pm, and the level difference caused by the wiring has been flattened. Next (at 1,
A through hole was formed, a second layer of aluminum wiring was formed, and a PSG film with a thickness of 1 μm was deposited as a protective layer by normal pressure CVD, and then a window for taking out an electrode was opened to obtain a semiconductor device. This device showed no defects at all even after a heating test at 450°C in nitrogen for 1 hour and a heat cycle test from -65°C to 150°C 10 times.

Punishment (Example of dielectric constant measurement) Lower layer aluminum was deposited on a 2-inch silicon substrate by CVD method, and the resin obtained in Example 4 was deposited to a thickness of 0.5 tnp or 1.5 tnp by spin cord method. 〇-Apply thick G, 8
After solvent drying at 0°C for 20 minutes, heat treatment was performed at 400°C for 60 minutes. Thereafter, the upper layer aluminum deposited by the CVD method was patterned into 1φ, 2φ, 3φ, 4φ and 5φ, electrodes were taken out from the upper and lower layers, and the canomassitance was measured at an AC voltage of 20 kV.

When the results were converted into dielectric constants, satisfactory values of 2.9 to 3.1 were obtained for each film thickness and measurement point.

The white powder obtained in Example 9 above was dissolved in methyl isobutyl ketone to obtain a 25% by weight resin solution. The resin solution prepared above was applied to a silicon substrate on which a semiconductor element was formed and a first polysilicon wiring was applied (the thickness of polysilicon was IJ!rn, the minimum line width was 1-1, the minimum line spacing was 1
．． 5 tea) by a spin code method under the conditions of 200 rpm and 45 seconds. 2 at 80°C after application
After drying the solvent for 0 minutes, X-ray exposure was performed through a mask to form through holes.

Next, heat treatment was performed at 400°C for 60 minutes. The level difference on the substrate surface after the heat treatment was about 0.2 irm, and the level difference caused by the wiring had been flattened. Next, a second layer of aluminum wiring is formed, and a 1μ thick PS layer is applied as a protective film.
After depositing the G film by atmospheric pressure CVD, a window for taking out the electrodes was opened to obtain a semiconductor device.

This device was tested in nitrogen at 450°C for 1 hour, -
No defects were observed even after 10 thermal cycle tests at 65 to 150'C.

The white powder obtained in Example 23 was dissolved in methyl isobutyl ketone to obtain a 15% by weight resin solution. The resin solution prepared as described above was applied to a silicon substrate on which a semiconductor element was formed and a first polysilicon wiring was applied (the thickness of polysilicon was 1 square foot, the minimum line width was 1-1, the minimum line spacing was 1.5
1) It was coated on top by a spin code method under the conditions of 200 rpm and 45 seconds. After coating, the solution was dried at 80° C. for 20 minutes, and then exposed to X-rays through a mask to form through holes.

Next, heat treatment was performed at 400°C for 60 minutes. The level difference on the substrate surface after the heat treatment was approximately 0.3 tag, and the level difference caused by the wiring had been flattened. Next, a second layer of aluminum wiring is formed, and a P layer with a thickness of 1 layer is used as a protective film.
After depositing the SG film by atmospheric pressure CVD, a window for taking out the electrodes was opened to obtain a semiconductor device. This device was tested for heating at 450°C in nitrogen for 1 hour, from -65 to 150°C.
No defects were observed even after 10 thermal cycle tests.

The white powders obtained in Examples 24, 25 and 26 above were each dissolved in methyl isobutyl ketone to give 25% by weight.
A resin solution was obtained. Each resin solution prepared as described above was applied to a silicon substrate on which a semiconductor element was formed and a first polysilicon wiring was applied (the thickness of the polysilicon was l, m, the minimum line width was 1-1, the minimum line spacing was 1, 5 ta) 200 Or on top
Coating was performed by a spin code method under the conditions of pm and 45 seconds. After coating, the film was dried with the solvent at 80° C. for 20 minutes, and then exposed to X-rays through a mask to form through holes. Next, heat treatment was performed at 400"C for 60 minutes. After the heat treatment, the steps on the substrate surface were approximately 0.2 steps each, and the steps caused by the wiring had been flattened. Next, the second layer of aluminum After wiring was performed and a 1-thick PSG film was deposited as a protective film by normal pressure CVD, a window was opened for taking out the electrodes to obtain a semiconductor device.
No defects were observed even after a 1-hour heating test at °C and 10 heat cycle tests from -65 to 150 °C.

Example of dielectric constant measurement: A lower layer of aluminum was deposited on a 2-inch silicon substrate by the CVD method, and the resin obtained in Example 24 was applied to a thickness of 0.5 m or 1.0 m by the spin cord method. ,80°
After solvent drying at C for 20 minutes, the entire surface was exposed to X-rays,
Heat treatment was performed at 400°C for 60 minutes.

After that, the upper layer aluminum deposited by CVD method is
The electrodes were patterned into φ, 2φ, 3φ, 4φ, and 5φ, and the electrodes were taken out from the upper and lower layers, respectively, and the capacitance was measured at an AC voltage of 20 kV.

When the results were converted into dielectric constants, satisfactory values of 2.9 to 3.1 were obtained for each film thickness and measurement point.

〔Effect of the invention〕

According to the present invention, not only can a new and useful organosilicon polymer be obtained, but it also has excellent sensitivity and oxygen plasma resistance, and has low swelling during development and low contrast (T value).
It is possible to obtain a high-resolution upper layer resist, particularly for use in a double-layer resist method, which has a high level of resolution, thereby making it possible to improve the accuracy of integrated circuits.

Further, according to the present invention, a semiconductor device having a highly reliable interlayer insulating film that can be patterned, has a flattening function, has a low dielectric constant, and does not cause cranking even when used at high temperatures. You can also get it.

[Brief explanation of drawings]

FIGS. 1A to 1D are cross-sectional views showing the processing steps of the two-layer resist method in order. FIG. 2 is a schematic diagram showing a molecular structure model of TSPS according to the present invention. FIG. , a graph showing the 29Si-NMR spectrum of TSPS, Fig. 4 is a graph showing the GPC-LALLS chromatogram of TSPS, Part 5 is a graph showing the GPC-LALLS chromatogram of ladder sps, Fig. 6 is a graph showing the EB sensitivity of TSPS and rudder sps, Figure 7 is a graph showing 0□-RIE of TSPS and MP-1300
Figures 8A and 8B are electron micrographs (photos in place of drawings) of the TSPS upper layer resist pattern, Figures 9A and 9B are TSPS/MP-1300 two-layer resist patterns. Electron micrograph of structured resist pattern (photo in place of drawing), Figure 10 is a graph showing the ultraviolet absorption spectrum of TSPS, Figure 11 is a graph showing TSPSO deep ultraviolet sensitivity, Figures 12A and 12B The figure is an electron micrograph (photograph in place of a drawing) of the TSPS upper layer resist pattern, Figures 13A to 13D are cross-sectional views showing the step-by-step manufacturing process of Si gate PMOS, and Figures 14A to 14G. The figure is a cross-sectional view showing the manufacturing process of SiGe NMO5 in order. In the figure, 1 is a substrate, 2 is a wiring, 3 is a lower resist (flattening layer), and 4 is an upper resist. e-e'e' Figure 1C Figure 1D Processing step 1 of two-layer resist method Substrate 4 Molecular structure model of upper resist functional group TSPS Figure 2 Figure 3 Elution time (minutes) TSPS GPC-LALLS chromatogram of Ladder SPS Fig. 4 Elution time (min) GPC-LALLS chromatogram of Ladder SPS Fig. 5
Figure Exposure amount (uC/cm2) EB sensitivity of TSPS and ladder SPS Figure 6 Etching time (minutes) 02-RI Etching time Figure 7 Figure 8A! ) 7 rods Figure 88 Figure 9A E, Jrl Rin 9B 1 Figure wavelength (nm) Ultraviolet absorption spectrum of TSPS Figure 10 Far ultraviolet sensitivity of TSPS Figure 11 Figure 1 Tomi 1. 12A Figure 1. Manufacturing of the stone/Si gate PMO5. Figure 14A. Figure 14D. Manufacturing of the S1 gate NMO5 (part 1). Figure 14E. Figure 14F. 2. Manufacturing of the S1 gate NMO5 (part 2).

Claims (1)

[Claims] 1. The following molecular structural formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the above formula, R may be the same or different, and each represents hydrogen or a monovalent represents a hydrocarbon group, and m and n each represent a positive integer), and is a three-dimensional cone-shaped structure consisting of a silphenylene siloxane nucleus and a triorganosilyl group surrounding the silphenylene nucleus. and a weight average molecular weight of 1,000 to 5,000,000. 2. In producing the polysilphenylene siloxane according to claim 1, an organosilicon compound represented by the following formula (II): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the above formula, R_1 to R_6 may be the same or different, and represent hydrogen, a monovalent hydrocarbon group, a trichlorosilyl group, or a trialkoxysilyl group, provided that at least two of these substituents are a trichlorosilyl group and 1. A method for producing polysilphenylene siloxane, which comprises hydrolyzing a compound (or trialkoxysilyl group) and subsequently subjecting the hydrolysis product to dehydration condensation polymerization. 3. The product obtained by the dehydration condensation polymerization is converted into a triorganosilane represented by the following formula: (R)_3SiX (In the above formula, R is the same as defined above, and
represents a halogen, a cyano group, an isocyanato group, or an isothiocyanato group), hexaorganodisilazane represented by the following formula: (R)_3
SiNHSi(R)_3 (in the above formula, R is the same as defined above), hexaorganodisiloxane represented by the following formula: (R)_3Si
OSi(R)_3 (in the above formula, R is the same as defined above), or a mixture thereof, to remove the hydrogen atoms of the silanol groups remaining in the product that did not contribute to the dehydration condensation polymerization. The method for producing polysilphenylene siloxane according to claim 2, characterized in that the substitution is carried out by a triorganosilyl group represented by the following formula: (R)_3Si- (in the above formula, R is the same as defined above). 4. The product obtained by the dehydration condensation polymerization is converted into a triorganosilane represented by the following formula: (R)_3SiX (in the above formula, R is the same as defined above, and
represents a halogen, a cyano group, an isocyanato group, or an isothiocyanato group), hexaorganodisilazane represented by the following formula: (R)_3
SiNHSi(R)_3 (in the above formula, R is the same as defined above), hexaorganodisiloxane represented by the following formula: (R)_3Si
OSi(R)_3 (in the above formula, R is the same as defined above), or a mixture thereof (However, R_1 to R in the above formula (II)
_6 and at least 5% or more of the total number of R are halogenated lower alkyl groups or halogenated aryl groups),
The hydrogen atoms of the silanol groups remaining in the product that did not contribute to the dehydration condensation polymerization are replaced by triorganosilyl groups represented by the following formula: (R)_3Si- (In the above formula, R is the same as the above definition. ) The method for producing polysilphenylene siloxane according to claim 2, characterized in that the substitution is carried out by: 5. In producing the polysilphenylene siloxane according to claim 1, a triorganosilane represented by the following formula: (R)_3SiX (in the above formula, R is the same as the above definition, and
represents a halogen, a cyano group, an isocyanato group, or an isothiocyanato group), hexaorganodisilazane represented by the following formula: (R)_3
SiNHSi(R)_3 (in the above formula, R is the same as defined above), hexaorganodisiloxane represented by the following formula: (R)_3Si
OSi(R)_3 (in the above formula, R is the same as defined above), or a mixture thereof, is dissolved in an organic solvent, and the solution obtained in this manner is added to the following formula (II) in the presence of water. Organosilicon compounds represented by: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) (In the above formula, R_1 to R_6 may be the same or different, and hydrogen, monovalent hydrocarbon group, trichlorosilyl or trialkoxysilyl group, provided that at least two of these substituents are trichlorosilyl group and/or trialkoxysilyl group) are added gradually. Manufacturing method. 6. A resist material comprising the polysilphenylene siloxane according to claim 1. 7. The resist material according to claim 6, which is a negative type and is used as an upper resist in a two-layer resist method. 8. The following steps: A resist material made of polysilphenylene siloxane according to claim 1 is coated on the surface of a base material, and the resulting resist film is exposed to desired ionizing radiation such as deep ultraviolet rays, electron beams, and X-rays. 1. A method for forming a resist pattern, comprising selectively exposing the resist film to obtain a pattern, and developing the resist film after pattern exposure to dissolve and remove resist material in unexposed areas. 9. When there is a step on the surface of the base material, the resist film has a two-layer structure, and in this case, the lower resist is made of a resist material having a flattening function, and the polysilphenylene siloxane according to claim 1 is used. 9. The method for forming a resist pattern according to claim 8, further comprising forming an upper resist from a resist material comprising: and transferring a resist pattern formed in the upper resist to a lower resist. 10. A semiconductor device comprising the step of selectively removing a base under the resist pattern by dry etching using a resist pattern formed from a resist material made of polysilphenylene siloxane according to claim 1 as a mask. How to manufacture. 11. A semiconductor device comprising a layer film made of the polysilphenylene siloxane according to claim 1. 12. The semiconductor device according to claim 11, wherein the layer film is an interlayer insulating film of multilayer wiring. 13. The semiconductor device according to claim 11, wherein the layer film is a heat-resistant protective film.