KR20180056606A - Composition for forming silica layer, method for manufacturing silica layer, and silica layer - Google Patents

Abstract

The present invention relates to a composition for forming a silica layer, a method for manufacturing a silica layer, and a silica layer. According to an embodiment of the present invention, the composition for forming the silica layer comprises a silicon-containing polymer and a mixed solvent. According to the present invention, the composition for forming a silica layer, the method for manufacturing a silica layer, and the silica layer can form the silica layer having a uniform thickness.

Description

TECHNICAL FIELD The present invention relates to a composition for forming a silica film, a method for producing a silica film, and a silica film,

The present disclosure relates to a composition for forming a silica film, a method for producing a silica film, and a silica film produced thereby.

As semiconductor technology advances, researches on highly integrated and high-speed semiconductor memory cells with improved integration and higher performance in smaller-sized semiconductor chips are being continued. However, as the spacing between the wirings narrows in accordance with the demand for high integration of semiconductors, RC delay, cross-talk, response speed degradation, etc. may occur, which may cause problems in terms of semiconductor interconnection. Proper separation between devices is needed to solve this problem.

Accordingly, a silica film formed of a silicon-containing material is widely used as an interlayer insulating film, a planarization film, a passivation film, an interdevice separating insulating film, and the like of semiconductor devices for proper separation between devices. The silica film is used not only for semiconductor devices but also as a protective film and an insulating film for display devices and the like.

Generally, a silica film is formed by coating a silicon-containing material on a predetermined region of a device and then curing. Defects occurring on the surface of the film may adversely affect the yield and reliability of the device.

One embodiment provides a composition for forming a silica film capable of forming a film having a small thickness and a small defect occurrence.

Another embodiment provides a method for producing a silica film using the composition for forming a silica film.

Another embodiment provides a silica film with low defect occurrence and uniform thickness.

Another embodiment provides an electronic device comprising the silica film.

According to one embodiment, there is provided a composition for forming a silica film having a surface tension of 5 mN / m to 35 mN / m at 25 ° C, comprising a silicon-containing polymer and a mixed solvent comprising at least two solvents to provide.

The mixed solvent may have a surface tension of 15 mN / m to 35 mN / m at 25 ° C.

The mixed solvent is selected from the group consisting of benzene, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, triethylbenzene, cyclohexane, cyclohexene, decahydronaphthalene, dipentene, pentane, hexane, heptane, , Ethyl cyclohexane, methylcyclohexane, p-menthane, dipropyl ether, dibutyl ether, anisole, butyl acetate, amyl acetate, methyl isobutyl ketone, paramethyl anisole, tetramethyl benzene and combinations thereof At least two species selected from the group consisting of

The silicon-containing polymer may include polysilazane, polysiloxazane, or combinations thereof.

The silicon-containing polymer may have a weight average molecular weight of 1,000 to 160,000 g / mol.

The silicon-containing polymer may be contained in an amount of 0.1 to 30% by weight based on the total amount of the composition for forming a silica film.

According to another embodiment, there is provided a method for forming a silica film, comprising the steps of applying a composition for forming a silica film described above on a substrate, drying the substrate coated with the composition for forming a silica film, and curing in an atmosphere containing an inert gas at 150 캜 or higher And a method for producing the silica film.

The step of applying the composition for forming a silica film may be carried out by a spin-on coating method.

According to another embodiment, there is provided a silica film formed according to the above-described manufacturing method.

According to another embodiment, there is provided an electronic device comprising the silica film.

There is provided a composition for forming a silica film capable of forming a silica film having a small occurrence of defects and having a uniform thickness.

The embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

In the drawings, the thickness is enlarged to clearly represent the layers and regions. Like parts are designated with like reference numerals throughout the specification. Whenever a portion of a layer, film, region, plate, or the like is referred to as being "on" another portion, it includes not only the case where it is "directly on" another portion, but also the case where there is another portion in between. Conversely, when a part is "directly over" another part, it means that there is no other part in the middle.

Unless otherwise defined herein, "substituted" means that the hydrogen atom in the compound is a halogen atom (F, Br, Cl, or I), a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino group, A carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, an alkyl group, an alkenyl group of C2 to C16, a C2 to C16 alkenyl group, An aryl group, C7 to C13 arylalkyl, C1 to C4 oxyalkyl, C1 to C20 heteroalkyl, C3 to C20 heteroarylalkyl, cycloalkyl, C3 to C15 cycloalkenyl, C6 to C15 Substituted by a substituent selected from a cycloalkynyl group, a heterocycloalkyl group, and combinations thereof.

In addition, unless otherwise defined herein, "hetero" means containing 1 to 3 heteroatoms selected from N, O, S and P.

In the present specification, " * " means the same or different atom or part connected to a chemical formula.

Hereinafter, the composition for forming a silica film according to one embodiment of the present invention will be described.

The composition for forming a silica film according to an embodiment of the present invention includes a silicon-containing polymer and a mixed solvent comprising at least two kinds of solvents.

First, the mixed solvent will be described.

The mixed solvent may have a surface tension of 5 mN / m to 35 mN / m at 25 ° C, specifically, a surface tension of 15 mN / m to 35 mN / m Lt; / RTI > The surface tension of the mixed solvent can be measured under the following conditions.

※ Surface tension measurement condition

□ Measuring instrument: Force Tensiometer-K11

□ Measuring temperature: 25 ℃

□ Measurement standard: ASTM D 1331

The composition for forming a silica film according to one embodiment may be prepared by using a mixed solvent containing two or more kinds of solvents as a solvent for dissolving a solid content so that the surface tension of the mixed solvent satisfies the above range, It is possible not only to reduce the occurrence of the effect but also to ensure the thickness uniformity of the film.

Non-limiting examples of the solvent include benzene, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, triethylbenzene, cyclohexane, cyclohexene, decahydronaphthalene, dipentene, pentane, But are not limited to, hexane, octane, nonane, decane, ethylcyclohexane, methylcyclohexane, p-menthane, dipropyl ether, dibutyl ether, anisole, butyl acetate, amyl acetate, methyl isobutyl ketone, But is not limited thereto.

On the other hand, the silicon-containing polymer may include, for example, polysilazane, polysiloxazane, or a combination thereof as a polymer containing Si in its structure.

Specifically, the silicon-containing polymer contained in the composition for forming a silica film may include a hydrogenated polysilazane containing a moiety represented by the following formula (1).

[Chemical Formula 1]

Wherein R ₁ to R ₃ are each independently selected from the group consisting of hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl A substituted or unsubstituted C7 to C30 arylalkyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 alkenyl group , A substituted or unsubstituted alkoxy group, a carboxyl group, an aldehyde group, a hydroxy group, or a combination thereof,

The " * " means a connection point.

The hydrogenated polysilazane can be prepared by various methods, for example, by reacting halosilane with ammonia.

The silicon-containing polymer contained in the composition for forming a silica film may be a hydrogenated polysilazane further comprising a moiety represented by the following formula (2) in addition to the moiety represented by the formula (1).

(2)

R ₄ to R ₇ in Formula 2 are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group , A substituted or unsubstituted C7 to C30 arylalkyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, A substituted or unsubstituted alkoxy group, a carboxyl group, an aldehyde group, a hydroxy group, or a combination thereof,

The " * " means a connection point.

Thus, when the composition further comprises the moiety of Formula 2, the hydrogenated polysiloxazane prepared according to this embodiment has Si-O bond in addition to the silicon-nitrogen (Si-N) O-Si) bond moiety in the silicon-oxygen-silicon-silicon bond (Si-O-Si) bond moiety to reduce stress during curing by heat treatment to reduce shrinkage.

Furthermore, the polysilazane or polysiloxazane contained in the composition for forming a silica film may include a moiety represented by the following formula (3) at the terminal.

(3)

The portion represented by Formula 3 is a structure in which the terminal portion is capped with hydrogen, which may be included in the polysilazane or polysiloxane structure in an amount of 15 to 35% by weight based on the total amount of Si-H bonds. When the portion of Formula 3 is included in the polysilazane or polysiloxane structure within the above range, the SiH ₃ portion is prevented from being scattered due to SiH ₄ during the heat treatment, thereby preventing the shrinkage, Cracks can be prevented from occurring.

For example, the weight average molecular weight of the silicon-containing polymer may be from 1,000 to 160,000 g / mol, and in particular from 3,000 to 120,000 g / mol.

The silicon-containing polymer may be contained in an amount of 0.1 to 50 wt%, for example, 0.1 to 30 wt% based on the total amount of the composition for forming a silica film. When it is included in the above-mentioned range, an appropriate viscosity can be maintained and it can be formed evenly and without voids at the time of film formation.

The composition for forming a silica film may further include a thermal acid generator (TAG).

The thermal acid generator is an additive for improving the developability of the composition for forming a silica film, so that the organosilane-based condensate contained in the composition can be developed at a relatively low temperature.

The thermal acid generator is not particularly limited as long as it is a compound capable of generating acid (H ⁺ ) by heat, but it can be activated at 90 DEG C or higher to generate sufficient acid and have low volatility.

The thermal acid generators may be selected from, for example, nitrobenzyl tosylate, nitrobenzyl benzene sulfonate, phenol sulfonate, and combinations thereof.

The thermal acid generator may be contained in an amount of 0.01 to 25% by weight based on the total amount of the composition for forming a silica film. If the thermal acid generator is included in the range, the polymer can be developed at a relatively low temperature, have.

The composition for forming a silica film may further comprise a surfactant.

The surfactant is not particularly limited, and examples thereof include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether and polyoxyethylene oleyl ether, polyoxyethylene nonylphenol ether And polyoxyethylene alkyl allyl ethers such as polyoxyethylene alkyl allyl ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, polyoxyethylene sorbitol Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; polyoxyethylene sorbitan fatty acid esters such as Flax EF301, EF303 and EF352 Manufactured by Dainippon Ink and Chemicals, Inc.), Megafac F171 and F173 (manufactured by Dainippon Ink and Chemicals, Inc.), Prorad FC430 and FC431 (manufactured by Sumitomo 3M Ltd.) Fluorine surfactants such as Asahi Guard AG710, SHAPRON S-382, SC101, SC102, SC103, SC104, SC105 and SC106 (manufactured by Asahi Kasei Corporation), organosiloxane polymer KP341 (Shinetsu Kagaku Kogyo Co., Ltd.) and other silicone surfactants.

The surfactant may be included in an amount of 0.001 to 10% by weight based on the total amount of the composition for forming a silica film. When the surfactant is included in the above range, the dispersibility of the solution can be improved and the uniformity of the film thickness can be increased.

The composition for forming a silica film may be in the form of a solution in which the silicon-containing polymer and the components are dissolved in a mixed solvent.

According to another embodiment of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: applying a composition for forming a silica film described above onto a substrate; Drying the substrate coated with the composition for forming a silica film; And curing under an inert gas atmosphere at about 150 ° C or higher.

The composition for forming a silica film can be applied by a solution process, and can be applied by a method such as spin-on coating, slit coating, inkjet printing or the like.

The substrate may be, for example, a device substrate such as semiconductor or liquid crystal, but is not limited thereto.

According to another embodiment of the present invention, there is provided a silica film produced according to the above-described method. The silica film may be, for example, an insulating film, a separation film, a hard coating film, or the like, but is not limited thereto.

According to another embodiment of the present invention, there is provided an electronic device including a silica film produced according to the above-described method. The electronic device may be a display device such as an LCD or an LED, or a semiconductor device.

Hereinafter, embodiments of the present invention will be described in detail with reference to embodiments. The following examples are for illustrative purposes only and are not intended to limit the scope of the invention.

Preparation of composition for silica film formation

Synthesis Example 1

The inside of the 2 L reactor equipped with the stirring device and the temperature control device was replaced with dry nitrogen. Then, 2.0 g of pure water was poured into 1,500 g of dry pyridine, and the mixture was thoroughly mixed. The mixture was kept in a reactor at 5 ° C. Subsequently, 100 g of dichlorosilane was slowly added thereto over a period of 1 hour, and then 70 g of ammonia was slowly injected over 3 hours while stirring. Next, dry nitrogen was injected for 30 minutes to remove ammonia remaining in the reactor.

The obtained white slurry-like product was filtered using a 1 m-thick Teflon filter in a dry nitrogen atmosphere to obtain 1,000 g of a filtrate. 1,000 g of dry xylene was added thereto, and the operation of replacing the solvent with xylene in pyridine using a rotary evaporator was repeated three times in total to adjust the solid concentration to 20%, and a pore size 0.03 탆 Teflon And filtered through a filter.

Finally, while the dry di-n-butyl ether having a water content of 5 ppm or less was added by using a rotary evaporator, the operation of replacing the solvent with di-n-butyl ether in xylene was repeated three times in total to adjust the solid content to 20% And finally filtered through a Teflon filter having a pore size of 0.03 mu m to obtain a polysilazane polymer having a weight average molecular weight (Mw) of 7,000. The weight average molecular weight was determined by GPC; HPLC Pump 1515, RI Detector 2414 (Waters), and Column: LF804 (Shodex) .

Example 1

20 g of xylene and 20 g of decalin were mixed to prepare a mixed solvent.

The surface tension of the mixed solvent was measured to be 30.3 mN / m at 25 ° C using Force Tensiometer-K11.

Thereafter, 8 g of the polysilazane polymer prepared in Synthesis Example 1 was dissolved in 40 g of the mixed solvent and filtered to prepare a composition for forming a silica film.

Example 2

The procedure of Example 1 was repeated except that a mixed solvent (surface tension: 31.57 mN / m at 25 캜) in which 20 g of diethylbenzene and 20 g of p-methyleneisole were mixed was used instead of the mixed solvent used in Example 1 To prepare a composition for forming a silica film.

Example 3

The same procedure as in Example 1 was carried out except that a mixed solvent (surface tension: 30.75 mN / m at 25 캜) in which 20 g of tetramethylbenzene and 20 g of p-methyleneisole were mixed was used instead of the mixed solvent used in Example 1 To prepare a composition for forming a silica film.

Comparative Example 1

Except that a mixed solvent (surface tension: 35.30 mN / m at 25 캜) in which 20 g of anisole and 20 g of ethylhexyl ether were used in place of the mixed solvent used in Example 1 was used, A film-forming composition was prepared.

Comparative Example 2

A composition for forming a silica film was prepared in the same manner as in Example 1 except that 40 g of dibutyl ether (surface tension: 22.21 mN / m at 25 캜) was used alone instead of the mixed solvent used in Example 1 .

Evaluation 1: Membrane surface characteristics

The composition for forming a silica film according to Examples 1 to 3 and Comparative Examples 1 and 2 was coated on a patterned silicon wafer having a diameter of 8 inches by a spin-on coating method, and then baked at 150 캜 for 130 seconds to form a thin film .

Then, using a pyrogenic furnace, wet oxidation was performed at 350 ° C. for 1 hour in oxygen and water vapor atmosphere. A surface was etched by 100 nm dry etching using CF ₄ gas to prepare a sample.

Then, the AIT-XP defect tester was used to recognize the defect coordinates of the sample surface, and then the defect was reviewed by CD-SEM to classify hole defects and particle defects. The number of hole defects and the number of hole defects with a diameter of 175 nm or more were measured.

The membrane surface characteristics (%) were derived from the following formula (1).

[Formula 1]

Membrane surface characteristics (%) = number of hole defects having a diameter of 175 nm or more / total number of defects

(Total defect number = total number of total effects + total number of particle defects)

Evaluation 2: Film thickness uniformity

The composition for forming a silica film according to Examples 1 to 3 and Comparative Examples 1 and 2 was coated on a patterned silicon wafer having a diameter of 8 inches by a spin-on coating method, and then baked at 150 캜 for 130 seconds to form a thin film .

Then, the thickness of 51 points was measured at intervals of 6 mm from left to right using an Atlas thickness measuring apparatus, and the average thickness, maximum thickness, and minimum thickness of these points were measured. The sex was evaluated.

[Formula 2]

Film thickness uniformity (%) = [(maximum thickness - minimum thickness) / (2 * average thickness)] * 100

The results of the evaluations 1 and 2 are shown in Table 1 below.

menstruum Surface tension (mN / m)
(in 25 [deg.] C) Film thickness uniformity (%) Membrane surface properties
(%) Example 1 Xylene + Decalin 29.51 0.6 3 Example 2 Diethyl benzene + p-Methyl anisole 31.57 0.9 9 Example 3 Tetramethyl benzene + Phenetole 30.75 1.05 11 Comparative Example 1 Anisole + Ethyl hexyl ether 35.30 1.6 45 Comparative Example 2 Xylene 29.02 1.05 21

Referring to Table 1, the compositions for forming a silica film according to Examples 1 to 3 had lower hole defects than the compositions for forming a silica film according to Comparative Examples 1 and 2, It is to be understood that the scope of the present invention is not limited thereto and that the scope of the present invention is not limited to the above embodiments, Various modifications and improvements of those skilled in the art are also within the scope of the present invention.

Claims (8)

Polysilazane, polysiloxazane, or a combination thereof, and
A mixed solvent comprising at least two solvents
Lt; / RTI >
The mixed solvent has a surface tension of from 5 mN / m to 35 mN / m at 25 ° C,
The mixed solvent may be selected from the group consisting of benzene, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, triethylbenzene, cyclohexane, cyclohexene, dipentene, pentane, hexane, heptane, At least two kinds selected from the group consisting of methylcyclohexane, p-menthane, dipropyl ether, dibutyl ether, anisole, butyl acetate, amyl acetate, methyl isobutyl ketone, paramethyl anisole, tetramethyl benzene, Containing
Composition for forming a silica film. The method of claim 1,
Wherein the mixed solvent has a surface tension of 15 mN / m to 35 mN / m at 25 ° C. The method of claim 1,
Wherein the silicon-containing polymer has a weight average molecular weight of 1,000 to 160,000 g / mol. The method of claim 1,
Wherein the silicon-containing polymer is contained in an amount of 0.1 to 30% by weight based on the total amount of the composition for forming a silica film. Applying a composition for forming a silica film according to any one of claims 1 to 4 on a substrate,
Drying the substrate coated with the composition for forming a silica film, and
Curing in an atmosphere containing an inert gas at 150 DEG C or higher
≪ / RTI > The method of claim 5,
Wherein the step of applying the composition for forming a silica film is carried out by a spin-on coating method. A silica film formed by the method according to claim 5. An electronic device comprising a silica film according to claim 7.