KR102446983B1 - Composition for forming silica layer, and silica layer - 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 of 4,000 to 10,000 g/mol, and the α value of the silicon-containing polymer is greater than 0 and less than or equal to 1.5. is about The α value is defined by Equation 1 below.
[Equation 1]
α = B/A * 100
In Equation 1 above,
A is a peak area in a range of 4.5 ppm or more and less than 5.5 ppm in ¹ H-NMR spectrum, and B is a peak area in a range of 3.3 ppm or more and less than 3.5 ppm in ¹ H-NMR spectrum. However, the measurement conditions of the ¹ H-NMR spectrum are as described in the specification.

Description

A composition for forming a silica film and a silica film

The present disclosure relates to a composition for forming a silica film and a silica film prepared using the composition.

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 that transmits a scan signal for controlling the thin film transistor. ) and a data line transmitting a signal to be applied to the pixel electrode are provided in the flat panel display. In addition, an insulating film is formed between the semiconductor and the various electrodes to separate them.

The insulating film generally uses a silica film formed by converting a silicon-containing polymer into silica. At this time, depending on the structure of the silicon-containing polymer, etch resistance, gap-fill characteristics, planarization characteristics, etc. of the silica film vary, and the storage stability of the composition for forming a silica film is also affected. However, these properties tend to conflict with each other, and a silica film that simultaneously satisfies the above properties is required.

One embodiment provides a composition for forming a silica film having excellent etch resistance, gap-fill characteristics, and planarization characteristics.

Another embodiment provides a silica film including a silica component obtained by converting the silicon-containing polymer for forming a silica film.

Another embodiment 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 of 4,000 to 10,000 g/mol, and the α value of the silicon-containing polymer is greater than 0 and 1.5 It provides the following compositions for forming a silica film.

However, the α value is defined by the following formula:

[Equation 1]

α = B/A * 100

In Equation 1 above,

A is the peak area in the range of 4.5 ppm or more and less than 5.5 ppm in ¹ H-NMR spectrum,

B is a peak area in the range of 3.3 ppm or more and less than 3.5 ppm in ¹ H-NMR spectrum,

However, the ¹ H-NMR spectrum is measured according to the following condition 1:

[Condition 1]

A silicon-containing polymer was added to a dibutyl ether (DBE) solvent to prepare Sample 1 having a solid content of 18±0.1 wt%. Next, 3 cc of Sample 1 was taken, dispensed in the center of an 8-inch-diameter silicon wafer using a spin coater, and then spin-rotated at 1,500 rpm for 5 minutes to form a film on the silicon wafer. The membrane thus formed is collected with a cutter, and the collected membrane is mixed with a CDCl ₃ (Chloroform-d) solvent to prepare a solution. With respect to the total amount of the solution, the content of the sampled film was adjusted to 3.0% by weight, and this was referred to as sample 2. Then, the ¹ H-NMR spectrum of Sample 2 is measured at 300 MHz.

The α value may be 0.1 or more and 1.5 or less.

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

The solvent is benzene, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, triethylbenzene, cyclohexane, cyclohexene, decahydronaphthalene, dipentene, pentane, hexane, heptane, octane, nonane, decane, At least one selected from the group consisting of ethylcyclohexane, methylcyclohexane, cyclohexane, cyclohexene, p-mentane, dipropyl ether, dibutyl ether, anisole, butyl acetate, amyl acetate, methyl isobutyl ketone, and combinations thereof may include.

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

According to another embodiment, there is provided a silica film prepared from the above-described composition for forming a silica film.

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

The silicon-containing polymer for forming a silica film according to an exemplary embodiment has excellent etch resistance, gap-fill properties, and planarization properties. By providing a composition including the same, it is possible to implement a silica film having excellent etch resistance and planarization properties.

1 shows a ¹ H-NMR profile of a silicon-containing polymer according to Polymerization Example 1,
2 is a V-SEM image of a cross section of a film formed from the composition for forming a silica film according to Example 1;
3 is a V-SEM image of a cross section of a film formed from the composition for forming a silica film according to Comparative Example 1.

The embodiments of the present invention will be described in detail so that those of ordinary skill in the art to which the present invention pertains can easily implement them. However, the present invention may be embodied in many different forms and is not limited to the embodiments described herein.

In order to clearly express various layers and regions in the drawings, the thicknesses are enlarged. Throughout the specification, like reference numerals are assigned to similar parts. When a part of a layer, film, region, plate, etc. is said to be “on” another part, it includes not only cases where it is “directly on” another part, but also cases where there is another part in between. Conversely, when we say that a part is "just above" another part, we mean that there is no other part in the middle.

In this specification, unless otherwise defined, '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, amidino group, hydrazino group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, carboxyl group or its salt, sulfonic acid group or its salt, phosphoric acid or its salt, C1 to C20 alkyl group, 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 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 portion connected to the same or different atoms or chemical formulas.

Hereinafter, a silicon-containing polymer for forming a silica film according to an embodiment of the present invention will be described.

According to an embodiment of the present invention, 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 of 4,000 to 10,000 g/mol, and the α value of the silicon-containing polymer is It provides a composition for forming a silica film that is greater than 0 and less than or equal to 1.5.

Here, the α value is defined by the following formula:

[Equation 1]

α = B/A * 100

In Equation 1 above,

A is the peak area in the range of 4.5 ppm or more and less than 5.5 ppm in ¹ H-NMR spectrum,

B is a peak area in the range of 3.3 ppm or more and less than 3.5 ppm in ¹ H-NMR spectrum,

However, the ¹ H-NMR spectrum is measured according to the following condition 1:

[Condition 1]

A silicon-containing polymer was added to a dibutyl ether (DBE) solvent to prepare Sample 1 having a solid content of 18±0.1 wt%. Next, 3 cc of Sample 1 was taken, dispensed in the center of an 8-inch-diameter silicon wafer using a spin coater, and then spin-rotated at 1,500 rpm for 5 minutes to form a film on the silicon wafer. The membrane thus formed is collected with a cutter, and the collected membrane is mixed with a CDCl ₃ (Chloroform-d) solvent to prepare a solution. With respect to the total amount of the solution, the content of the sampled film was adjusted to 3.0% by weight, and this was referred to as Sample 2. Then, the ¹ H-NMR spectrum of Sample 2 is measured at 300 MHz.

In Equation 1, A means a peak area represented by SiH and SiH ₂ , and B means a peak area represented by dibutyl ether (DBE) used as a solvent in Condition 1 above. The ¹ H-NMR spectrum is an important indicator for defining the structural properties of the silicon-containing polymer.

The composition for forming a silica film according to an embodiment contains silicon having an α value in the range of greater than 0 and less than or equal to 1.5 under Condition 1, and at the same time satisfying a weight average molecular weight of 4,000 to 10,000 g/mol according to a polystyrene conversion value. contains a polymer. Accordingly, it is possible to form a film having less void generation and good gap filling in a subsequent gap-fill process. In addition, physicochemical properties may be enhanced by maintaining a low etch rate in a subsequent curing process.

The α value is ultimately due to the structural difference of the polymer. Due to the structural difference of the polymer, the penetration of moisture reaches a deep region inside the hole during subsequent high-temperature curing to increase the amount of SiO ₂ conversion, which occurs at this time The outgas that is produced should be well degassed. Accordingly, it is possible to reduce the etch rate of the deep hole and to make a silica film in which the generation of voids is minimized.

Etching resistance refers to the property that the etching gas is not etched by the etching solution, and the better the etching resistance, the harder the film can be realized.

The gap-fill characteristic refers to a characteristic in which a silica film formed from a silicon-containing polymer densely fills a gap formed in an integrated circuit (IC).

The film flatness refers to the degree to which the thickness of the silica film formed from the silicon-containing polymer is uniform. The better the film flatness, the easier the subsequent process after the formation of the silica film.

In general, these properties are in a conflicting relationship with each other. In the silicon-containing polymer for forming a silica film according to an embodiment, the polymer structure is designed such that the α value measured under the above condition 1 is in the range of greater than 0 and less than or equal to 1.5, and at the same time Since the weight average molecular weight according to the polystyrene conversion value satisfies 4,000 to 10,000 g/mol, etch resistance, gap-fill characteristics, and planarization characteristics can be simultaneously satisfied.

For example, the α value of the silicon-containing polymer contained in the composition for forming a silica film may be 0.1 or more and 1.5 or less, but is not limited thereto.

For example, the silicon-containing polymer may include polysilazane, polysiloxazane, or a combination thereof. For example, the silicon-containing polymer for forming a silica film may have a number average molecular weight of 500 to 10,000, but is not limited thereto.

Meanwhile, the silicon-containing polymer may include, for example, a moiety represented by the following Chemical Formula A.

[Formula A]

In Formula A, 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 , 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 hydroxyl 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 further include a moiety represented by the following Chemical Formula B in addition to the moiety represented by Chemical Formula A.

[Formula B]

R ₄ to R ₇ in Formula B 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, a carboxyl group, an aldehyde group, a hydroxyl group, or a combination thereof,

The "*" means a connection point.

In this case, the silicon-containing polymer comprises a silicon-oxygen-silicon (Si-O-Si) bonding moiety in addition to a silicon-nitrogen (Si-N) bonding moiety in its structure, so that such a silicon-oxygen-silicon (Si-O) -Si) When the bonding part is hardened by heat treatment, the stress can be relieved to reduce the shrinkage.

For example, the silicon-containing polymer may include a moiety represented by Formula A, a moiety represented by Formula B, and further include a moiety represented by Formula C below.

[Formula C]

The portion represented by Formula C has a structure in which the terminal portion is capped with hydrogen, and may be included in an amount of 15 to 35 wt% based on the total content of Si-H bonds in the polysilazane or polysiloxazane structure. When the portion of Formula 3 is included in the above range in the polysilazane or polysiloxazane structure, the oxidation reaction occurs sufficiently during heat treatment, while the SiH ₃ portion becomes SiH ₄ during heat treatment to prevent scattering to prevent shrinkage, and this It can prevent cracks from occurring.

The silicon-containing polymer may be included in an amount of 0.1 to 50 wt%, for example, 0.1 to 30 wt%, based on the total content of the composition for forming a silica film. When included in the above range, an appropriate viscosity may be maintained, and the film may be formed evenly and evenly without a void during film formation.

The solvent included 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, 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, dipropyl ether, 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.

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, and allows the organosilane-based condensation polymer included in the composition to 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 an acid (H ⁺ ) by heat, but may be activated at 90° C. or higher to generate sufficient acid and have low volatility.

The thermal acid generator may be selected from, for example, nitrobenzyltosylate, nitrobenzylbenzenesulfonate, phenol sulfonate, and combinations thereof.

The thermal acid generator may be included in an amount of 0.01 to 25% by weight based on the total content of the composition for forming a silica film, and when included in the above range, the condensation polymer may be developed at a relatively low temperature and at the same time improve coating properties. have.

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

The surfactant is not particularly limited, and for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene nonyl phenol ether Polyoxyethylene alkyl allyl ethers such as polyoxyethylene/polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, polyoxyethylene sorbi Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as tan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate, EFTOP EF301, EF303, EF352 (Tochem Co., Ltd.) Products), Megapack F171, F173 (Dainippon Ink Co., Ltd.), Prorad FC430, FC431 (Sumitomo 3M Co., Ltd.), Asahi Guard AG710, Saffron S-382, SC101, SC102, SC103, SC104, and fluorine-based surfactants such as SC105 and SC106 (manufactured by Asahi Glass Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) and other silicone-based surfactants.

The surfactant may be included in an amount of 0.001 to 10% by weight based on the total content of the composition for forming a silica film, and when included in the above range, it is possible to improve the dispersibility of the solution and increase the uniformity of the film thickness during film formation.

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 solvent.

According to another embodiment of the present invention, applying the above-described composition for forming a silica film on a substrate; drying the substrate coated with the composition for forming a silica film; And it provides a silica film manufacturing method comprising the step of curing in an inert gas atmosphere of about 150 ℃ or more.

The composition for forming a silica film may be applied by a solution process, for example, 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 a semiconductor or liquid crystal, but is not limited thereto.

According to another embodiment of the present invention, there is provided a silica film comprising a silica component obtained by converting the above-described silicon-containing polymer for forming a silica film.

The silica film may be, for example, an insulating film, a separator, a hard coating film, and the like, but is not limited thereto.

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 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 silicon-containing polymers

Comparative polymerization example 1

The inside of the reactor equipped with a stirring and temperature control device with a capacity of 1 L was replaced with dry nitrogen. Then, 800 g of dry pyridine was injected into the reactor and cooled to -1°C. Then, 60 g of dichlorosilane was injected over 65 minutes. And after aging for 1 hour while stirring, 37 g of ammonia was injected here over 4 hours. Next, it was aged for 2 hours while stirring. Dry nitrogen was injected for 12 hours to remove ammonia remaining in the reactor. The obtained white slurry-like product was filtered in a dry nitrogen atmosphere using a 0.1 µm Teflon filter to obtain 680 g of a filtrate. After adding 800 g of dry xylene, the operation of replacing the solvent from pyridine to xylene using a rotary evaporator was repeated three times in total, adjusting the solid content concentration to 20%, and using a 0.1 μm Teflon filter filtered. About 100 g of dry pyridine was added to the obtained inorganic polysilazane solution, and polymerization was carried out so that the weight average molecular weight was 4,100 at 100°C with a solid content of 10%. When polymerization is complete, the operation of replacing the solvent with dibutyl ether using a rotary evaporator is repeated 4 times at 70° C. to adjust the solid content concentration to 20%, filtration with a 0.1 μm Teflon filter, inorganic polysilazane got

The weight average molecular weight of the inorganic polysilazane in the present specification was measured using GPC (PLC Pump 1515) manufactured by Waters, and the α value was measured using NMR (300 MHz) manufactured by Bruker.

Comparative polymerization example 2

The inside of the reactor equipped with a stirring and temperature control device with a capacity of 1 L was replaced with dry nitrogen. Then, 800 g of dry pyridine was injected into the reactor and cooled to -1°C. Then, 60 g of dichlorosilane was injected over 65 minutes. Then, after aging for 1 hour while stirring, 37 g of ammonia was injected here over 4 hours. Next, it was aged for 2 hours while stirring. Dry nitrogen was injected for 12 hours to remove ammonia remaining in the reactor. The obtained white slurry-like product was filtered in a dry nitrogen atmosphere using a 0.1 µm Teflon filter to obtain 680 g of a filtrate. After adding 800 g of dry xylene, the operation of replacing the solvent from pyridine to xylene using a rotary evaporator was repeated three times in total, adjusting the solid content concentration to 20%, and using a 0.1 μm Teflon filter filtered. About 100 g of dry pyridine was added to the obtained inorganic polysilazane solution, and polymerization was carried out so that the weight average molecular weight was 5,500 at 100°C with a solid content of 10%. When polymerization is complete, the operation of replacing the solvent with dibutyl ether using a rotary evaporator is repeated 4 times at 70° C. to adjust the solid content concentration to 20%, filtration with a 0.1 μm Teflon filter, inorganic polysilazane got

Comparative polymerization example 3

The inside of the reactor equipped with a stirring and temperature control device with a capacity of 1 L was replaced with dry nitrogen. Then, 800 g of dry pyridine was injected into the reactor and cooled to -1°C. Then, 60 g of dichlorosilane was injected over 65 minutes. Then, after aging for 1 hour while stirring, 37 g of ammonia was injected here over 4 hours. Next, it was aged for 2 hours while stirring. Dry nitrogen was injected for 12 hours to remove ammonia remaining in the reactor. The obtained white slurry-like product was filtered in a dry nitrogen atmosphere using a 0.1 µm Teflon filter to obtain 680 g of a filtrate. After adding 800 g of dry xylene, the operation of replacing the solvent from pyridine to xylene using a rotary evaporator was repeated three times in total, adjusting the solid content concentration to 20%, and using a 0.1 μm Teflon filter filtered. About 100 g of dry pyridine was added to the obtained inorganic polysilazane solution, and polymerization was conducted at 100° C. with a solid content of 10% to a weight average molecular weight of 9,800. When polymerization is complete, the operation of replacing the solvent with dibutyl ether using a rotary evaporator is repeated 4 times at 70° C. to adjust the solid content concentration to 20%, filtration with a 0.1 μm Teflon filter, inorganic polysilazane got

Comparative polymerization example 4

The inside of the reactor equipped with a stirring and temperature control device with a capacity of 1 L was replaced with dry nitrogen. Then, 800 g of dry pyridine was injected into the reactor and cooled to -1°C. Then, 60 g of dichlorosilane was injected over 65 minutes. Then, after aging for 1 hour while stirring, 37 g of ammonia was injected here over 4 hours. Next, it was aged for 2 hours while stirring. Dry nitrogen was injected for 12 hours to remove ammonia remaining in the reactor. The obtained white slurry-like product was filtered in a dry nitrogen atmosphere using a 0.1 µm Teflon filter to obtain 680 g of a filtrate. After adding 800 g of dry xylene, the operation of replacing the solvent from pyridine to xylene using a rotary evaporator was repeated three times in total, adjusting the solid content concentration to 20%, and using a 0.1 μm Teflon filter filtered. About 100 g of dry pyridine was added to the obtained inorganic polysilazane solution, and polymerization was performed at 150° C. with a solid content of 10% to a weight average molecular weight of 120,000. When polymerization is complete, the operation of replacing the solvent with dibutyl ether using a rotary evaporator is repeated 4 times at 70° C. to adjust the solid content concentration to 20%, filtration with a 0.1 μm Teflon filter, inorganic polysilazane got

Comparative polymerization example 5

The inside of the reactor equipped with a stirring and temperature control device with a capacity of 1 L was replaced with dry nitrogen. Then, 800 g of dry pyridine was injected into the reactor and cooled to -1°C. Then, 60 g of dichlorosilane was injected over 65 minutes. Then, after aging for 1 hour while stirring, 37 g of ammonia was injected here over 4 hours. Next, it was aged for 2 hours while stirring. Dry nitrogen was injected for 12 hours to remove ammonia remaining in the reactor. The obtained white slurry-like product was filtered in a dry nitrogen atmosphere using a 0.1 µm Teflon filter to obtain 680 g of a filtrate. After adding 800 g of dry xylene, the operation of replacing the solvent from pyridine to xylene using a rotary evaporator was repeated three times in total, adjusting the solid content concentration to 20%, and using a 0.1 μm Teflon filter filtered. About 100 g of dry pyridine was added to the obtained inorganic polysilazane solution, and polymerization was carried out so that the weight average molecular weight was 3,000 at 150 DEG C with a solid content of 10%. When polymerization is complete, the operation of replacing the solvent with dibutyl ether using a rotary evaporator is repeated 4 times at 70° C. to adjust the solid content concentration to 20%, filtration with a 0.1 μm Teflon filter, inorganic polysilazane got

Polymerization Example 1

The inside of the reactor equipped with a stirring and temperature control device with a capacity of 1 L was replaced with dry nitrogen. Then, 800 g of dry pyridine was injected into the reactor and cooled to -1°C. Then, 60 g of dichlorosilane was injected over 65 minutes. Then, after aging for 1 hour while stirring, 37 g of ammonia was injected here over 4 hours. Next, it was aged for 24 hours while stirring. Dry nitrogen was injected for 12 hours to remove ammonia remaining in the reactor. The obtained white slurry-like product was filtered in a dry nitrogen atmosphere using a 0.1 µm Teflon filter to obtain 680 g of a filtrate. After adding 800 g of dry xylene, the operation of replacing the solvent from pyridine to xylene using a rotary evaporator was repeated three times in total, adjusting the solid content concentration to 20%, and using a 0.1 μm Teflon filter filtered. About 100 g of dry pyridine was added to the obtained solution, and polymerization was performed at 100° C. with a solid content of 10% to a weight average molecular weight of 4,100. When polymerization is complete, the operation of replacing the solvent with dibutyl ether using a rotary evaporator is repeated 4 times at 70° C. to adjust the solid content concentration to 20%, filtration with a 0.1 μm Teflon filter, inorganic polysilazane got

Polymerization Example 2

The inside of the reactor equipped with a stirring and temperature control device with a capacity of 1 L was replaced with dry nitrogen. Then, 800 g of dry pyridine was injected into the reactor and cooled to -1°C. Then, 60 g of dichlorosilane was injected over 65 minutes. Then, after aging for 1 hour while stirring, 37 g of ammonia was injected here over 4 hours. Next, it was aged for 24 hours while stirring. Dry nitrogen was injected for 12 hours to remove ammonia remaining in the reactor. The obtained white slurry-like product was filtered in a dry nitrogen atmosphere using a 0.1 µm Teflon filter to obtain 680 g of a filtrate. After adding 800 g of dry xylene, the operation of replacing the solvent from pyridine to xylene using a rotary evaporator was repeated three times in total, adjusting the solid content concentration to 20%, and using a 0.1 μm Teflon filter filtered. About 100 g of dry pyridine was added to the obtained solution, and polymerization was carried out at 100°C with a solid content of 10% so that the weight average molecular weight was 5,500. When polymerization is complete, the operation of replacing the solvent with dibutyl ether using a rotary evaporator is repeated 4 times at 70° C. to adjust the solid content concentration to 20%, filtration with a 0.1 μm Teflon filter, inorganic polysilazane got

Polymerization Example 3

The inside of the reactor equipped with a stirring and temperature control device with a capacity of 1 L was replaced with dry nitrogen. Then, 800 g of dry pyridine was injected into the reactor and cooled to -1°C. Then, 60 g of dichlorosilane was injected over 65 minutes. Then, after aging for 1 hour while stirring, 37 g of ammonia was injected here over 4 hours. Next, it was aged for 24 hours while stirring. Dry nitrogen was injected for 12 hours to remove ammonia remaining in the reactor. The obtained white slurry-like product was filtered in a dry nitrogen atmosphere using a 0.1 µm Teflon filter to obtain 680 g of a filtrate. After adding 800 g of dry xylene, the operation of replacing the solvent from pyridine to xylene using a rotary evaporator was repeated three times in total, adjusting the solid content concentration to 20%, and using a 0.1 μm Teflon filter filtered. About 100 g of dry pyridine was added to the obtained solution, and polymerization was carried out at 100°C with a solid content of 10% to a weight average molecular weight of 9,800. When polymerization is complete, the operation of replacing the solvent with dibutyl ether using a rotary evaporator is repeated 4 times at 70° C. to adjust the solid content concentration to 20%, filtration with a 0.1 μm Teflon filter, inorganic polysilazane got

Polymerization Example 4

The inside of the reactor equipped with a stirring and temperature control device with a capacity of 1 L was replaced with dry nitrogen. Then, 800 g of dry pyridine was injected into the reactor and cooled to -1°C. Then, 60 g of dichlorosilane was injected over 65 minutes. Then, after aging for 1 hour while stirring, 37 g of ammonia was injected here over 4 hours. Next, it was aged for 48 hours while stirring. Dry nitrogen was injected for 12 hours to remove ammonia remaining in the reactor. The obtained white slurry-like product was filtered in a dry nitrogen atmosphere using a 0.1 µm Teflon filter to obtain 680 g of a filtrate. After adding 800 g of dry xylene, the operation of replacing the solvent from pyridine to xylene using a rotary evaporator was repeated three times in total, adjusting the solid content concentration to 20%, and using a 0.1 μm Teflon filter filtered. About 100 g of dry pyridine was added to the obtained solution, and polymerization was performed at 100° C. with a solid content of 10% to a weight average molecular weight of 4,100. When polymerization is complete, the operation of replacing the solvent with dibutyl ether using a rotary evaporator is repeated 4 times at 70° C. to adjust the solid content concentration to 20%, filtration with a 0.1 μm Teflon filter, inorganic polysilazane got

Polymerization Example 5

The inside of the reactor equipped with a stirring and temperature control device with a capacity of 1 L was replaced with dry nitrogen. Then, 800 g of dry pyridine was injected into the reactor and cooled to -1°C. Then, 60 g of dichlorosilane was injected over 65 minutes. Then, after aging for 1 hour while stirring, 37 g of ammonia was injected here over 4 hours. Next, it was aged for 48 hours while stirring. Dry nitrogen was injected for 12 hours to remove ammonia remaining in the reactor. The obtained white slurry-like product was filtered in a dry nitrogen atmosphere using a 0.1 µm Teflon filter to obtain 680 g of a filtrate. After adding 800 g of dry xylene, the operation of replacing the solvent from pyridine to xylene using a rotary evaporator was repeated three times in total, adjusting the solid content concentration to 20%, and using a 0.1 μm Teflon filter filtered. About 100 g of dry pyridine was added to the obtained solution, and polymerization was performed at 100° C. with a solid content of 10% to a weight average molecular weight of 5,500. When polymerization is complete, the operation of replacing the solvent with dibutyl ether using a rotary evaporator is repeated 4 times at 70° C. to adjust the solid content concentration to 20%, filtration with a 0.1 μm Teflon filter, inorganic polysilazane got

Polymerization Example 6

The inside of the reactor equipped with a stirring and temperature control device with a capacity of 1 L was replaced with dry nitrogen. Then, 800 g of dry pyridine was injected into the reactor and cooled to -1°C. Then, 60 g of dichlorosilane was injected over 65 minutes. Then, after aging for 1 hour while stirring, 37 g of ammonia was injected here over 4 hours. Next, it was aged for 48 hours while stirring. Dry nitrogen was injected for 12 hours to remove ammonia remaining in the reactor. The obtained white slurry-like product was filtered in a dry nitrogen atmosphere using a 0.1 µm Teflon filter to obtain 680 g of a filtrate. After adding 800 g of dry xylene, the operation of replacing the solvent from pyridine to xylene using a rotary evaporator was repeated three times in total, adjusting the solid content concentration to 20%, and using a 0.1 μm Teflon filter filtered. About 100 g of dry pyridine was added to the obtained solution, and polymerization was carried out at 100°C with a solid content of 10% to a weight average molecular weight of 9,800. When polymerization is complete, the operation of replacing the solvent with dibutyl ether using a rotary evaporator is repeated 4 times at 70° C. to adjust the solid content concentration to 20%, filtration with a 0.1 μm Teflon filter, inorganic polysilazane got

of silicon-containing polymers ^One H-NMR analysis

Sample 1 having a solid content of 18±1 wt% was prepared by adding the silicon-containing polymers according to Comparative Polymerization Examples 1 to 5 and Polymerization Examples 1 to 6 to a dibutyl ether (DBE) solvent. Then, 3 cc of the sample 1 was taken and dispensed in the center of an 8-inch diameter silicon wafer (LG Siltron) using a spin coater (MIKASA, MS-A200), and then spin-rotated at 1,500 rpm for 5 minutes. to form a film on the silicon wafer. The membrane thus formed is collected with a cutter, and then the collected membrane is mixed with a CDCl ₃ (Chloroform-d) solvent to prepare a solution. With respect to the total amount of the solution, the content of the sampled film was adjusted to 3.0% by weight, and this was referred to as Sample 2. Then, the ¹ H-NMR spectrum of Sample 2 is measured at 300 MHz.

In ¹ H-NMR spectrum, the peak area in the range of 4.5 ppm or more and less than 5.5 ppm is the peak area (A) of SiH and SiH ₂ , and the peak area in the range of 3.3 ppm or more and less than 3.5 ppm is the peak area (B) of DBE. Thus, B/A*100 is calculated respectively.

The results are shown in Table 1 below.

B/A*100 Weight average molecular weight (g/mol) Comparative polymerization example 1 1.86 4,100 Comparative polymerization example 2 2.24 5,500 Comparative polymerization example 3 2.58 9,800 Comparative polymerization example 4 0.64 120,000 Comparative polymerization example 5 0.10 3,000 Polymerization Example 1 0.89 4,100 Polymerization Example 2 1.02 5,500 Polymerization Example 3 1.41 9,800 Polymerization Example 4 0.11 4,100 Polymerization Example 5 0.23 5,500 Polymerization Example 6 0.94 9,800

Referring to Table 1, the weight average molecular weight of the silicon-containing polymers according to Polymerization Examples 1 to 6 is 4,000 to 10,000 g/mol, and when measuring ¹ H-NMR spectrum, the α value defined as Formula 1 above is greater than 0 and 1.5 It can be seen that the following

Meanwhile, FIG. 1 shows a ¹ H-NMR profile of a silicon-containing polymer according to Polymerization Example 1. Referring to FIG. 1, the silicon-containing polymer according to Polymerization Examples 1 to 6 (peak area in the range of 3.3 ppm or more and less than 3.5 ppm, that is, DBE peak area (B))/(SiH and SH ₂ peak area (A) It can be seen that the value of ))*100 (ie, α value) exists within the range of greater than 0 and less than or equal to 1.5.

Preparation of a composition for forming a silica film

Examples 1 to 6 and Comparative Examples 1 to 5

The operation of replacing the solvent with dibutyl ether for the silicon-containing polymer obtained in Polymerization Examples 1 to 6 and Comparative Polymerization Examples 1 to 5 using a rotary evaporator was repeated 4 times at 70° C. to adjust the solid content concentration to 15%. and filtration with a 0.1 μm Teflon filter to obtain compositions for forming a silica film according to Examples 1 to 6 and Comparative Examples 1 to 5, respectively.

Corrosion resistance evaluation

3 cc of each of the compositions for forming a silica film according to Examples 1 to 6 and Comparative Examples 1 to 5 were dispensed with a spin coater (manufactured by MIKASA, MS-A200) in the center of an 8-inch diameter silicon wafer, followed by 1500 rpm was spin coated for 20 seconds. Thereafter, after heating and drying with a hot plate at 150° C. for 3 minutes, a WET curing process at 600° C. was performed for 30 minutes to form a silica film. Then, after immersion in 1wt% DHF (Dilute Hydrofluoric acid) for 120 seconds, the membrane cross-section was observed through a V-SEM photograph.

2 is a V-SEM image of a cross-section of a film formed from the composition for forming a silica film according to Example 1, and FIG. 3 is a V-SEM image of a cross-section of a film formed from the composition for forming a silica film according to Comparative Example 1.

2 and 3 , the film formed from the composition for forming a silica film according to Example 1 has an etch rate of the film cross-section after the wet etching process compared to the film formed from the composition for forming a silica film according to Comparative Example 1. It can be seen that relatively small

Although 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 by those skilled in the art using the basic concept of the present invention defined in the following claims are also It belongs to the scope of the present invention.

Claims (7)

A composition for forming a silica film comprising a silicon-containing polymer and a solvent, the composition comprising:
The silicon-containing polymer has a weight average molecular weight of 4,000 to 10,000 g/mol,
The α value of the silicon-containing polymer is 0.1 or more and 1.5 or less.
A composition for forming a silica film:
However, the α value is defined by the following formula (1).
[Equation 1]
α = B/A * 100
In Equation 1 above,
A is the peak area in the range of 4.5 ppm or more and less than 5.5 ppm in ¹ H-NMR spectrum,
B is the peak area in the range of 3.3 ppm or more and less than 3.5 ppm in ¹ H-NMR spectrum,
However, the ¹ H-NMR spectrum is measured according to the following condition 1:
[Condition 1]
A silicon-containing polymer was added to a dibutyl ether (DBE) solvent to prepare Sample 1 having a solid content of 18±0.1 wt%. Next, 3 cc of Sample 1 was taken, dispensed in the center of an 8-inch-diameter silicon wafer using a spin coater, and then spin-rotated at 1,500 rpm for 5 minutes to form a film on the silicon wafer. The membrane thus formed is collected with a cutter, and the collected membrane is mixed with a CDCl ₃ (Chloroform-d) solvent to prepare a solution. With respect to the total amount of the solution, the content of the collected film was adjusted to 3.0 wt%, and this was referred to as Sample 2. Then, the ¹ H-NMR spectrum of Sample 2 is measured at 300 MHz. delete In claim 1,
The silicon-containing polymer is a composition for forming a silica film comprising polysilazane, polysiloxazane, or a combination thereof. In claim 1,
The solvent is benzene, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, triethylbenzene, cyclohexane, cyclohexene, decahydronaphthalene, dipentene, pentane, hexane, heptane, octane, nonane, decane, At least selected from the group consisting of ethylcyclohexane, methylcyclohexane, cyclohexane, cyclohexene, p-mentane, dipropyl ether, dibutyl ether, anisole, butyl acetate, amyl acetate, methyl isobutyl ketone, and combinations thereof A composition for forming a silica film comprising one. In claim 1,
The silicon-containing polymer is included 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 prepared from the composition for forming a silica film of any one of claims 1 and 3 to 5. An electronic device comprising the silica film according to claim 6 .

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