KR20170060394A - Method for manufacturing silica layer, silica layer, and electronic device - Google Patents

Abstract

Applying a liquid material for pre-wetting comprising one or more carbon compounds represented by formula (1) on a substrate, applying a composition for forming a silica film on a substrate coated with liquid material for prewetting , And curing the substrate coated with the composition for forming a silica film. Formula 1 is as described in the specification.

Description

TECHNICAL FIELD The present invention relates to a method for producing a silica film, a silica film and an electronic device,

The present disclosure relates to a method for producing a silica film, a silica film produced thereby, and an electronic device including the silica film.

In a flat panel display device, a thin film transistor (TFT) including a gate electrode, a source electrode, a drain electrode, and a semiconductor is used as a switching element, and a gate line for transmitting a scanning signal for controlling the thin film transistor And a data line for transmitting a signal to be applied to the pixel electrode are provided in the flat panel display. In addition, an insulating film for separating the semiconductor and the various electrodes is formed. The insulating film may be a silica film containing a silicon component.

The silica film can be produced by applying a composition for forming a silica film on a substrate. If the wetting between the composition for forming a silica film, which is a liquid phase, and the substrate, which is a solid phase, is not performed well, This worsens and requires a large amount of the composition to be coated, which may reduce the efficiency of the process.

One embodiment provides a method for producing a silica film capable of forming a film having excellent process efficiency and excellent thickness uniformity.

Another embodiment provides a silica film produced according to the method.

Another embodiment provides an electronic device comprising the silica film.

According to one embodiment, there is provided a method for manufacturing a liquid crystal display device, comprising: applying a pre-wetting liquid material containing at least one carbon compound represented by the following formula (1) Applying a composition for forming a silica film, and curing the substrate to which the composition for forming a silica film is applied.

[Chemical Formula 1]

In Formula 1,

X ¹ and X ² are each independently a monovalent organic group,

L ⁰ is a C 1 to C 5 alkylene group,

m is an integer of 0 to 2,

The total number of carbon atoms contained in the structure of Formula 1 is 14 or less.

In Formula 1, X ¹ and X ² are each independently a C1 to C10 alkyl group or a C1 to C10 alkyl group in which at least one hydrogen is substituted with methyl, ethyl, propyl, butyl or pentyl.

The total number of carbon atoms contained in the structure of Formula 1 may be 6 to 14.

The carbon compound may be selected from the group consisting of isoamyl ether, heptyl ether, dipentyl ether, isopropyl pentyl ether, ethylene glycol diethyl ether, Triethyl orthoformate, or a combination thereof.

The composition for forming a silica film may include a silicon-containing polymer and a solvent.

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

The solvent is selected from the group consisting of benzene, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, triethylbenzene, cyclohexane, cyclohexene, decahydronaphthalene, dipentene, pentane, hexane, heptane, At least one selected from the group consisting of ethyl cyclohexane, methyl cyclohexane, cyclohexane, cyclohexene, p-menthane, dipropyl ether, dibutyl ether, anisole, butyl acetate, amyl acetate, methyl isobutyl ketone, . ≪ / RTI >

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

The curing may include a first heat treatment step performed at 100 ° C to 200 ° C and a second heat treatment step performed at 250 ° C to 400 ° C.

According to another embodiment, there is provided a silica film formed by the method for producing a silica film.

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

Since wetting between the composition for forming a silica film and the substrate is well performed by pre-treating the substrate with a predetermined liquid substance before the step of applying the composition for forming a silica film, a small amount of the coating liquid may cause the entire substrate So that a uniform film can be formed by coating efficiently.

Fig. 1 is a reference diagram for explaining a method of evaluating the uniformity of the thickness of a silica film.

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, a method for producing a silica film according to an embodiment of the present invention will be described.

The method for producing a silica film according to an embodiment of the present invention includes the steps of applying a liquid material for pre-wetting comprising one or more carbon compounds represented by the following formula (1) on a substrate, Applying a composition for forming a silica film on the substrate to which the liquid material is applied, and curing the substrate to which the composition for forming a silica film is applied.

[Chemical Formula 1]

In Formula 1,

X ¹ and X ² are each independently a monovalent organic group,

L ⁰ is a C 1 to C 5 alkylene group,

m is an integer of 0 to 2,

The total number of carbon atoms contained in the structure of Formula 1 is 14 or less.

The pre-wetting refers to a pre-treatment step performed before the wetting step, and is also referred to as a reduced resist consumption (RRC) process.

The method for preparing a silica film according to an embodiment of the present invention is a method for preparing a pre-wetting liquid material containing one or more carbon compounds represented by the above formula (1) before coating a composition for forming a silica film on a substrate And a step of applying.

The carbon compound contained in the liquid material for prewetting used in one embodiment contains at least one oxygen in its structure and has 14 or fewer carbon atoms in total. The method of manufacturing a silica film according to an embodiment of the present invention uses a carbon compound having such a structure in a pre-wetting process to improve the uniformity of a film thickness by improving affinity with a lower film, It is possible to minimize the amount of the pre-wetting material remaining in the hole and to reduce the hole defect. In addition, it is possible to form a uniform film while using a relatively small amount of the composition for forming a silica film, thereby improving the efficiency of the process.

For example, the carbon compound may include one or two oxygen atoms in its structure (i.e., m in the formula (1) is 0 or 1), and the total number of carbon atoms may be, for example, 6 to 14, but is not limited thereto . For example, the carbon compound may be a compound consisting solely of carbon and hydrogen.

For example, in Formula 1, X ¹ and X ² are each independently a C1 to C10 alkyl group, or a C1 to C10 alkyl group in which at least one hydrogen is substituted with methyl, ethyl, propyl, butyl or pentyl.

For example, in Formula 1, X ¹ and X ² are each independently selected from the group consisting of isoamyl ether, heptyl ether, dipentyl ether, isopropyl pentyl ether, But are not limited to, ethylene glycol diethyl ether, triethyl orthoformate, or combinations thereof.

For example, the boiling point of the carbon compound may be from 50 ° C to 260 ° C, for example, from 90 ° C to 190 ° C, but is not limited thereto.

The liquid material for prewetting may be the carbon compound itself, or a mixture of two or more carbon compounds, or a solution in which other components than the carbon compound are mixed.

The liquid material for prewetting can be applied by a method such as spin-on coating, slit coating, inkjet printing or the like, and there is no particular limitation on the coating method.

After the application of the liquid material for prewetting is completed, a step of applying a composition for forming a silica film on the substrate is performed.

The composition for forming a silica film may include a silicon-containing polymer and a solvent.

The silicon-containing polymer contained in the composition for forming a silica film may include 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.

For example, the silicon-containing polymer may be a polysilazane produced by the reaction of halosilane and ammonia.

For example, the silicon-containing polymer contained in the composition for forming a silica film may further include 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.

In this case, the silicon-containing polymer includes a silicon-oxygen-silicon (Si-O-Si) bonding moiety in addition to a silicon-nitrogen (Si- -Si) bond portion relaxes stress during curing by heat treatment and can reduce shrinkage.

For example, the silicon-containing polymer may further include a moiety represented by Formula 1, a moiety represented by Formula 2, and a moiety represented by Formula 3 below.

(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.

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 solvent contained in the composition for forming a silica film is not particularly limited as long as it is a solvent capable of dissolving the silicon-containing polymer. Specific examples thereof include benzene, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, But are not limited to, cyclohexane, cyclohexane, decahydronaphthalene, dipentene, pentane, hexane, heptane, octane, nonane, decane, ethylcyclohexane, methylcyclohexane, cyclohexane, cyclohexene, And may include at least one member selected from the group consisting of ether, anisole, butyl acetate, amyl acetate, methyl isobutyl ketone, and combinations thereof.

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 polymer 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. When the thermal acid generator is included in the range, the polymer can be developed at a relatively low temperature and the coating property can be improved .

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 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.

When the application of the composition for forming a silica film is completed, the substrate is then dried and cured. The curing may be performed in an atmosphere containing an inert gas at about 100 DEG C or higher, for example, and may be performed by applying energy such as heat, ultraviolet rays, microwaves, sonic waves, or ultrasonic waves.

The curing may include a first heat treatment step carried out at about 100 ° C to 200 ° C and a second heat treatment step carried out at about 250 ° C to 400 ° C. The solvent in the composition for forming a silica film can be removed by the first heat treatment step, and then the thin film can be converted into an oxide film by a second heat treatment step at a higher temperature than the first heat treatment step.

The silica film may be prepared by coating a liquid material for prewetting, which is composed of the above-described carbon compound, on the substrate before applying the composition for forming a silica film on the substrate, and then applying the composition for forming a silica film according to the subsequent spin- So that it can be uniformly coated with a smaller amount of the composition.

By performing the step of applying the substance of the pre-wetting solution solution made of the above-described carbon compound, it is possible to prevent generation of gas generated by the component contained in the composition for forming a silica film, for example, the polysilazane component, And it is possible to facilitate the physical behavior of the composition for forming a silica film upon application of the composition for forming a silica film on the substrate, thereby forming a dense silica film with minimum penetration into the atmosphere.

Accordingly, the silica film formed according to the above-described manufacturing method can be etched to a uniform thickness, for example, when the subsequent etching process is performed. Accordingly, when the conductor is laminated on the etched film, the current difference due to the thickness variation of the oxide film is minimized, and consequently the reliability of the semiconductor device can be improved.

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 protective film such as a hard coating, but is not limited thereto.

According to another embodiment of the present invention, there is provided an electronic device comprising 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.

Silica film  Preparation of composition for forming

A reactor having a capacity of 2 L and equipped with a temperature control device was replaced with dry nitrogen. Then, 1,500 g of dry pyridine was poured into the reactor, and the mixture was kept at 20 ° C. Subsequently, 100 g of dichlorosilane was slowly added over 1 hour. Then, 70 g of ammonia was gradually added thereto over 3 hours while stirring. Next, dry nitrogen was injected for 30 minutes to remove ammonia remaining in the reactor. The resulting white slurry product was filtered through a 1 mu m 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 content concentration to 20%. Finally, the pore size was adjusted to 0.03 탆 Of a Teflon filter. The obtained polysilazane had an oxygen content of 3.8%, SiH ₃ / SiH (total) of 0.22, and a weight average molecular weight of 4,000.

The polysilazane obtained above was mixed with dibutyl ether (DBE) to prepare a composition for forming a silica film having a solid content of 15 ± 0.1 wt%.

Manufacture of thin films

Example  One

3.0 ml of isoamyl ether was used as a liquid material for prewetting and spin-coated at 1,500 rpm on a central portion of a silicon wafer patterned with a diameter of 8 inches by a spin coater (K-SPIN8 equipment) , 3.0 ml of the composition for forming a silica film was spin-coated again under the same conditions as above. Thereafter, the pre-baking process was performed at 150 ° C to form a primary thin film, and then the uniformity of the film thickness was evaluated. Subsequently, curing was carried out at 300 캜 using a furnace for supplying water vapor to convert the film quality to an oxide film quality. Thereafter, the oxide film was removed by 1,000 angstroms or more through the etching process, and then the uniformity of the film thickness was evaluated again.

The film thickness evaluation method will be described later.

Example  2

A thin film was formed in the same manner as in Example 1 except that heptyl ether was used as a liquid material for prewetting.

Comparative Example  One

A thin film was formed in the same manner as in Example 1, except that decane was used as the liquid material for prewetting.

Comparative Example 2

A thin film was formed in the same manner as in Example 1, except that methyl isobutyl ketone was used as the liquid material for prewetting.

Comparative Example 3

A thin film was formed in the same manner as in Example 1, except that propylene glycol monomethyl ether was used as the liquid material for prewetting.

Evaluation 1: Confirmation of film thickness uniformity

As shown in Fig. 1, a reflection spectroscopic film thickness meter (ST-5000) manufactured by K-MAC Co., Ltd. was used to form a thin film on the wafer on which the thin film was formed from Examples 1 to 2 and Comparative Examples 1 to 3 The thickness was measured by specifying the points. Then, the average thickness, the maximum thickness, the minimum thickness and the uniformity of the film thickness at these points were confirmed.

The film thickness uniformity is evaluated based on the following formula (1).

[Formula 1]

Film Thickness Uniformity = [(Maximum Thickness - Minimum Thickness) / 2 / Average Thickness] * 100

The results are shown in Table 1 below.

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 After pre-baking
Film thickness uniformity (%) 2.64 2.92 3.54 6.78 6.28 After etching
Film thickness uniformity (%) 2.91 4.08 4.81 8.14 7.94

The results are shown in Table 1. Referring to Table 1, the thin films according to Examples 1 and 2 subjected to the pre-wetting process using a predetermined liquid material for pre-wetting had a uniform film thickness , And film thickness uniformity measured after etching.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. And falls within the scope of the present invention.

Claims (11)

Applying a liquid material for pre-wetting comprising one or more carbon compounds represented by the following formula (1) on a substrate;
Applying a composition for forming a silica film on a substrate to which a liquid material for prewetting is applied, and
And curing the substrate coated with the composition for forming a silica film
Containing
Method of producing silica film:
[Chemical Formula 1]

In Formula 1,
X ¹ and X ² are each independently a monovalent organic group,
L ⁰ is a C 1 to C 5 alkylene group,
m is an integer of 0 to 2,
The total number of carbon atoms contained in the structure of Formula 1 is 14 or less. The method of claim 1,
X ¹ and X ² in Formula 1 are each independently a C1 to C10 alkyl group or a C1 to C10 alkyl group in which at least one hydrogen is substituted with methyl, ethyl, propyl, butyl or pentyl. The method of claim 1,
Wherein the total number of carbon atoms contained in the structure of Formula (1) is 6 to 14. The method of claim 1,
The carbon compound may be selected from the group consisting of isoamyl ether, heptyl ether, dipentyl ether, isopropyl pentyl ether, ethylene glycol diethyl ether, Triethyl orthoformate, or a combination thereof. The method of claim 1,
Wherein the composition for forming a silica film comprises a silicon-containing polymer and a solvent. The method of claim 5,
Wherein the silicon-containing polymer comprises a polysilazane, a polysiloxazane, or a combination thereof. The method of claim 5,
The solvent is selected from the group consisting of benzene, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, triethylbenzene, cyclohexane, cyclohexene, decahydronaphthalene, dipentene, pentane, hexane, heptane, At least one selected from the group consisting of ethyl cyclohexane, methyl cyclohexane, cyclohexane, cyclohexene, p-menthane, dipropyl ether, dibutyl ether, anisole, butyl acetate, amyl acetate, methyl isobutyl ketone, ≪ / RTI > The method of claim 1,
Wherein the step of applying the composition for forming a silica film is carried out by a spin-on coating method. The method of claim 1,
Wherein the curing comprises a first heat treatment step carried out at 100 ° C to 200 ° C and a second heat treatment step carried out at 250 ° C to 400 ° C. 10. A silica film formed by the method according to any one of claims 1 to 9. An electronic device comprising a silica film according to claim 10.

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