KR102471747B1 - Composition for forming silica layer, silica layer, and electronic device - Google Patents

Abstract

A composition for forming a silica film comprising a silicon-containing polymer and a solvent, wherein the silicon-containing polymer has a weight average molecular weight (Mw1) of 1,000 to 20,000, and the silicon-containing polymer is a polar polymer detected by a multi-angle light scattering detector (MALS). A molecular weight (Mw2) is 50,000 to 200,000, and the polar polymer has a peak area of 3% or less with respect to the silicon-containing polymer when measured by a multi-angle light scattering detector (MALS).

Description

Composition for forming silica film, silica film, and electronic device

The present disclosure relates to a composition for forming a silica film, a silica film, and an electronic device manufactured thereby.

A flat panel display device uses a thin film transistor (TFT) including a gate electrode, a source electrode, a drain electrode, and a semiconductor as a switching element, and a gate line for transmitting a scan signal to control 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 device. In addition, an insulating film is formed between the semiconductor and various electrodes to separate them.

As the insulating film, it is common to use a silica film formed by converting a silicon-containing polymer into silica. At this time, depending on the characteristics of the silicon-containing polymer, the storage stability or the number of particles of the composition for forming a silica film may be affected, which may interfere with gap-fill during coating of the composition, thereby affecting the quality of the silica film.

The composition for forming a silica film according to an embodiment of the present invention can improve the storage stability of the composition for forming a silica film and reduce the number of particles by controlling the molecular weight and content of the polar polymer included in the silicon-containing polymer to a predetermined range. .

The silica film according to another embodiment of the present invention has excellent planarity because void defects generated on the surface of the film are reduced.

Another embodiment of the present invention provides an electronic device including the silica film.

According to one embodiment, a composition for forming a silica film comprising a silicon-containing polymer and a solvent, wherein the silicon-containing polymer has a weight average molecular weight (Mw1) of 1,000 to 20,000, and the silicon-containing polymer is measured by a multi-angle light scattering detector (MALS) A composition for forming a silica film having a molecular weight (Mw2) of 50,000 to 200,000, and the polar polymer having a peak area of 3% or less with respect to the silicon-containing polymer when measured by a multi-angle light scattering detector (MALS). .

However, the ultra high molecular weight polymer refers to a polymer corresponding to a region showing peaks at one or both extremes on the time axis when the silicon-containing polymer is measured by a multi-angle light scattering detector (MALS).

The polar polymer may have a peak area greater than 0 and less than or equal to 3% with respect to the silicon-containing polymer when measured by a multi-angle light scattering detector (MALS).

The polar polymer may have a peak area of 0.1% to 3% with respect to the silicon-containing polymer when measured by a multi-angle light scattering detector (MALS).

The silicon-containing polymer may have a weight average molecular weight (Mw1) of 3,000 to 10,000.

The composition for forming a silica film may include 50 particles/ml or less of particles having a particle diameter of 0.1 μm or more.

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

The silicon-containing polymer may be included 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, a silica film containing a silica component obtained by curing the above-described composition for forming a silica film is provided.

According to another embodiment, an electronic device including the above-described silica film is provided.

The composition for forming a silica film according to an embodiment has excellent storage stability and thus has good gap-fill characteristics during coating, so that a thin film with high flatness can be realized.

1 is an example of MALS measurement results to explain the concept of polar polymers.

Embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention. However, the present invention may be embodied in many different forms and is not limited to the embodiments set forth herein.

Unless otherwise defined herein, 'substituted' means that a hydrogen atom in a 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, an azido group, An amidino group, a hydrazino group, a hydrazono group, a carbonyl group, a carbamyl group, a thiol group, an ester group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C1 to C30 alkoxy group, C1 to C20 heteroalkyl group, C2 to C20 heteroaryl group, C3 to C20 heteroarylalkyl group, C3 to C30 cycloalkyl group, It means that it is substituted with a substituent selected from a C3 to C15 cycloalkenyl group, a C6 to C15 cycloalkynyl group, a C2 to C30 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 addition, in this specification, "*" means a part connected to the same or different atom or chemical formula.

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

A composition for forming a silica film according to an embodiment includes a silicon-containing polymer and a solvent, the silicon-containing polymer has a weight average molecular weight (Mw1) of 1,000 to 20,000, and the silicon-containing polymer is measured by a multi-angle light scattering detector (MALS). The molecular weight (Mw2) of the detected polar polymer is 50,000 to 200,000, but the polar polymer has a peak area of 3% or less with respect to the silicon-containing polymer when measured by a multi-angle light scattering detector (MALS).

The weight average molecular weight (Mw1) of the silicon-containing polymer measured using gel permeation chromatography (GPC) has a value in the range of 1,000 to 20,000, for example, 2,000 to 20,000, 3,000 to 20,000, or 3,000 to 10,000 days It can, but is not limited thereto.

The silicon-containing polymer has a polar polymer region under multi-angle light scattering detector (MALS) measurement. In general, when measuring a multi-angle light scattering detector (MALS) for a polymer, the horizontal axis is the time value, and the vertical axis is the relative value of the peak. When the ultra high molecular weight polymer is measured with a multi-angle light scattering detector (MALS) for the silicon-containing polymer, the molecular weight is much larger than that of the polymer region showing the largest peak, and therefore the time to pass through the column is short. Therefore, it is possible to detect a region that appears in a shorter time on the time axis. In this way, when measuring MALS, a polymer present in an extreme region is referred to as an 'extreme polymer'.

1 is an example of MALS measurement results to explain the concept of polar polymers.

Referring to the graph on the right of FIG. 1 , in addition to the region showing the largest peak in the center, regions showing small peaks at both extremes can be observed. The polymer present in this region corresponds to a polar polymer. The graph on the left of FIG. 1 is an enlarged view of the extreme peak region occupied by the polar polymer.

The silicon-containing polymer included in the composition for forming a silica film according to an embodiment includes a polar polymer having a molecular weight (Mw2) of 50,000 to 200,000 as measured by a multi-angle light scattering detector (MALS). The molecular weight (Mw2) of the polar polymer is measured using MALS.

According to one embodiment, the content of the polar polymer has a peak area of greater than 0 and less than or equal to 3% with respect to the silicon-containing polymer when measured by a multi-angle light scattering detector (MALS), for example, may have a peak area of 0.1% to 3%. . Accordingly, storage stability of the composition for forming a silica film may be improved, and a thin film having high flatness may be realized due to good gap-fill characteristics during coating.

Here, the ultra-high molecular content (%) is calculated as (integral value of the polar polymer peak) / (integral value of the silicon-containing polymer peak) * 100, or (area of the polar polymer region on the peak) / (molecular weight distribution of the silicon-containing polymer It can be calculated as total area) * 100.

The composition for forming a silica film according to one embodiment may include particles in a liquid state, but the number may be controlled to 50 particles/ml or less. At this time, the particles having a particle diameter of 0.1 μm or more are counted as effective particles. Here, the number of particles of the composition is measured using a Liquid Particle Counter (LPC) (KS-42BF, manufactured by RION).

The silicon-containing polymer contained in the composition for forming a silica film may be, for example, polysilazane (organic-inorganic polysilazane), polysiloxazane (organic-inorganic polysiloxazane), or a combination thereof.

The silicon-containing polymer may include, for example, a moiety represented by Chemical Formula 1 below.

[Formula 1]

In Formula 1, R ₁ to R ₃ are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group , or a substituted or unsubstituted C6 to C30 aryl group. Group, substituted or unsubstituted C7 to C30 arylalkyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, 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 polysilazane produced by reacting halosilane with ammonia.

For example, the silicon-containing polymer included in the composition for forming a silica film may include a moiety represented by Chemical Formula 2 below.

[Formula 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, or 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, carboxyl group, aldehyde group, hydroxy group, or a combination thereof;

The "*" means a connection point.

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

[Formula 3]

The portion represented by Formula 3 has a structure in which terminal portions are capped with hydrogen, which may be included in an amount of 15 to 35% by weight based on the total content of Si-H bonds in the polysilazane or polysiloxazane structure. When the portion of Chemical Formula 3 is included in the above range in the polysilazane or polysiloxazane structure, oxidation reaction occurs sufficiently during heat treatment, while preventing the SiH ₃ portion from being scattered as SiH ₄ during heat treatment to prevent shrinkage, thereby preventing cracks can be prevented from occurring.

For example, the silicon-containing polymer may be included in an amount of 0.1% to 30% by weight based on the composition for forming a silica film.

The solvent included in the composition for forming a silica film is not particularly limited as long as it can dissolve the silicon-containing polymer, and specifically, benzene, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, triethylbenzene, Cyclohexane, cyclohexene, decahydronaphthalene, dipentene, pentane, hexane, heptane, octane, nonane, decane, ethylcyclohexane, methylcyclohexane, cyclohexane, cyclohexene, p-mentane, dipropylether, dibutyl It may include at least one selected from the group consisting of ether, anisole, butyl acetate, amyl acetate, methyl isobutyl ketone, and combinations thereof.

According to another embodiment, the steps of applying the above-described composition for forming a silica film, drying the substrate coated with the composition for forming a silica film, and curing the composition for forming a silica film may be included. .

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

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

When the application of the composition for forming the silica film is completed, the substrate is then dried and cured. The drying and curing may be performed at a temperature of, for example, about 100° C. or higher, and may be performed by applying energy such as heat, ultraviolet rays, microwaves, sound waves, or ultrasonic waves.

For example, the drying may be performed at about 100° C. to about 200° C., and the solvent in the composition for forming a silica layer may be removed through the drying step. In addition, the curing may be performed at about 250° C. to 1,000° C., and the composition for forming a silica film may be converted into an oxide film by passing through the corresponding curing step.

According to another embodiment of the present invention, a silica film containing a silica component obtained by curing the above-described composition for forming a silica film is provided.

An electronic device including the silica film of the present invention is provided. The electronic device may be, for example, a display device such as an LCD or LED, or a semiconductor device.

Hereinafter, embodiments of the present invention described above will be described in more detail through examples. However, the following examples are for illustrative purposes only and do not limit the scope of the present invention.

Preparation of a composition for forming a silica film

Example One

The inside of a reactor equipped with a stirring device and a temperature control device having a capacity of 2 L was replaced with dry nitrogen. Then, 1,500 g of dry pyridine was injected into the reactor and kept warm at 5°C. Subsequently, 100 g of dichlorosilane was gradually injected over 1 hour, and then 70 g of ammonia was gradually injected over 3 hours while stirring. Next, dry nitrogen was injected for 30 minutes, and ammonia remaining in the reactor was removed. The resulting white slurry product was filtered in a dry nitrogen atmosphere using a 1 μm Teflon filter to obtain 1,000 g of a filtrate. After adding 1,000 g of dry xylene to this, the operation of substituting the solvent from pyridine to xylene using a rotary evaporator was repeated three times in total to adjust the solid content concentration to 20%, and a pore size of 0.1 μm was obtained. It was filtered through a Teflon filter to obtain a semi-finished hydrogenated polysilazane having a weight average molecular weight (Mw1) of 3,000 and a polar polymer content of 0.3%.

Substituting the solvent with dibutyl ether for the semi-finished hydrogenated polysilazane using a rotary evaporator was repeated four times at 70° C. to adjust the solid content concentration to 20%, and then filtered through a 0.1 μm Teflon filter, Finally, a composition for forming a silica film containing inorganic polysilazane having a weight average molecular weight (Mw1) of 3,000 and an extremely high polymer content of 0.5% was prepared.

The weight average molecular weight was measured using GPC (HPLC Pump 1515, RI Detector 2414, manufactured by Waters), and the peak area ratio and molecular weight of polar polymers were determined by MALS (manufacturer WYATT, MALS Detector: DAWN HELEOS-2, VISCOSTAR- 2, OPTILAB T-Rex, Column: Shodex KF-805L).

Example 2

250 g of dry pyridine was added to the semi-finished hydrogenated polysilazane of Example 1, heated at 90 ° C, and the operation of replacing the solvent with dibutyl ether using a rotary evaporator was repeated four times at 70 ° C to increase the solid content concentration to 20 %, and then filtered through a 0.1 μm Teflon filter to finally prepare a composition for forming a silica film containing inorganic polysilazane having a weight average molecular weight (Mw1) of 8,000 and a polar polymer of 1.2%.

Example 3

250 g of dry pyridine was added to the semi-finished hydrogenated polysilazane of Example 1, heated at 100 ° C, and the operation of replacing the solvent with dibutyl ether using a rotary evaporator was repeated four times at 70 ° C to reduce the solid content concentration to 20%. After adjusting, the mixture was filtered through a 0.1 μm Teflon filter to finally prepare a composition for forming a silica film containing inorganic polysilazane having a weight average molecular weight (Mw1) of 10,000 and a polar polymer content of 1.5%.

Example 4

250 g of dry pyridine was added to the semi-finished hydrogenated polysilazane of Example 1 and polymerized at 120°C. The operation of replacing the solvent with dibutyl ether using a rotary evaporator was repeated 4 times at 70°C to adjust the solid content concentration to 20%, and then filtered through a 0.1 μm Teflon filter to obtain a weight average molecular weight (Mw1) of 9,000. , A composition for forming a silica film containing inorganic polysilazane having a polar polymer content of 1.8% was prepared.

comparative example One

250 g of dry pyridine was added to the semi-finished hydrogenated polysilazane of Example 1 and polymerized at 70°C. The operation of replacing the solvent with dibutyl ether using a rotary evaporator was repeated 4 times at 70°C to adjust the solid content concentration to 20%, and then filtered through a 0.1 μm Teflon filter to obtain a weight average molecular weight (Mw1) of 9,000. , A composition for forming a silica film containing inorganic polysilazane having a polar polymer content of 3.5% was prepared.

comparative example 2

250 g of 20 ppm moisture pyridine was added to the semi-finished hydrogenated polysilazane of Example 1 and polymerized at 100°C. The operation of replacing the solvent with dibutyl ether using a rotary evaporator was repeated 4 times at 70°C to adjust the solid content concentration to 20%, and then filtered through a 0.1 μm Teflon filter to obtain a weight average molecular weight (Mw1) of 10,000. , A composition for forming a silica film containing inorganic polysilazane having a polar polymer content of 4% was prepared.

The polar molecular weight (Mw2) of the inorganic polysilazane polymer contained in the composition for forming a silica film according to Examples 1 to 4 and Comparative Examples 1 to 2 is summarized in Table 1 below.

evaluation

1. Composition for Forming a Silica Film particle number measure

The number of particles in the composition for forming a silica film prepared according to Examples 1 to 4 and Comparative Examples 1 to 2 was measured using a Liquid Particle Counter (LPC) (KS-41B, manufactured by RION) according to the following methods 1) to 4). It was measured according to the evaluation criterion, when the number of particles having a particle diameter of 0.1 μm or more was less than 50 ea / ml, it was judged to be good, and when it was 50 ea / ml or more, it was judged to be bad.

1) Turn on the power of the KS-41B device and stabilize it for 30 minutes.

2) After purging three times with the same solvent as the solvent used in the composition for forming a silica film to be measured, LPC measurement is performed.

3) When the LPC measurement result is 10 ea/ml or more, the solvent is replaced with a new solvent and measured, and when the LPC measurement result is 10 ea/ml or less, it is included in the measured value.

4) After measuring three times, enter the average value.

2. Evaluation of storage stability

The composition for forming a silica film prepared according to Examples 1 to 4 and Comparative Examples 1 to 2 was stored in a vacuum oven at 40 ° C., and the molecular weight increase rate up to 30 days was measured using GPC, and the evaluation criterion was that the increase rate was less than 3% It was judged good if it was good, and it was judged bad if it was 3% or more.

Table 1 shows the evaluation results.

Weight average molecular weight (Mw1) polar polymer
Molecular Weight
(Mw2) polar polymer
content LPC keep
stability Example 1 3,000 51,450 0.5% 30ea/ml Good Example 2 8,000 58,950 1.2% 10ea/ml Good Example 3 10,000 104,230 1.5% 15ea/ml Good Example 4 9,000 89,845 1.8% 20ea/ml Good Comparative Example 1 9,000 100,534 3.5% 100ea/ml error Comparative Example 2 10,000 101,300 4.0% 500ea/ml error

※ In Table 1, the pole polymer content (%) means the percentage of the peak area of the pole polymer with respect to the peak area of the silicon-containing polymer.

Referring to Table 1, the composition for forming a silica film according to Examples 1 to 4 containing inorganic polysilazane having an ultra-polymer content of 3% or less contains inorganic polysilazane having an ultra-polymer content of more than 3%. Compared to the compositions for forming a silica film according to Comparative Examples 1 and 2, it can be seen that the number of particles (LPC) in the composition is relatively low and storage stability is also good.

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concepts of the present invention defined in the following claims are also made. It belongs to the scope of the present invention.

Claims (9)

A composition for forming a silica film comprising a silicon-containing polymer and a solvent,
The weight average molecular weight (Mw1) of the silicon-containing polymer is 1,000 to 20,000,
The silicon-containing polymer has a molecular weight (Mw2) of the polar polymer detected when measured by a multi-angle light scattering detector (MALS) of 50,000 to 200,000,
The polar polymer has a peak area of more than 0 and less than 3% with respect to the silicon-containing polymer when measured by a multi-angle light scattering detector (MALS)
A composition for forming a silica film:
However, the ultra high molecular weight refers to a polymer corresponding to a region showing peaks at one or both extremes on the time axis when the silicon-containing polymer is measured by a multi-angle light scattering detector (MALS). delete In paragraph 1,
The polar polymer has a peak area of 0.1% to 3% with respect to the silicon-containing polymer when measured by a multi-angle light scattering detector (MALS). In paragraph 1,
The silicon-containing polymer has a weight average molecular weight (Mw1) of 3,000 to 10,000 silica film forming composition. In paragraph 1,
A composition for forming a silica film comprising 50 particles/ml or less of particles having a particle size of 0.1 μm or more. In paragraph 1,
The silicon-containing polymer is polysilazane, polysiloxazane, or a composition for forming a silica film of a combination thereof. In paragraph 1,
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. A silica film comprising a silica component obtained by curing the composition for forming a silica film according to any one of claims 1 and 3 to 7. An electronic device comprising the silica film according to claim 8 .

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