KR101998730B1 - Composition for forming silica layer, and silica layer - Google Patents

Abstract

Containing polymer and a solvent that satisfy the following formulas 1 and 2 under ¹ H-NMR spectrum.
[Formula 1]
B / A = 0.2 to 0.4
[Formula 2]
(A + B) / C = 4.8 to 12.0
The definitions of the above formulas 1 and 2 are as described in the specification.

Description

COMPOSITION FOR FORMING SILICA LAYER, AND SILICA LAYER < RTI ID = 0.0 >

The present disclosure relates to a composition for forming a silica film, a silica film produced using the composition.

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 is generally made of a silica film formed by converting a silicon-containing polymer into silica. At this time, depending on the structure of the silicon-containing polymer, corrosion resistance, gap-fill characteristics, and planarization characteristics of the silica film are changed and the storage stability of the composition for forming a silica film is also affected. However, these characteristics tend to be in conflict with each other, and a silica film satisfying the above properties simultaneously is required.

One embodiment provides a composition for forming a silica film that is excellent in corrosion resistance, gap-fill property, and planarization property.

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

Another embodiment provides an electronic device comprising the silica film.

According to one embodiment, there is provided a composition for forming a silica film comprising a silicon-containing polymer and a solvent, wherein the ¹ H-NMR spectrum of the silicon-containing polymer satisfies the following formulas 1 and 2: do.

[Formula 1]

B / A = 0.2 to 0.4

[Formula 2]

(A + B) / C = 4.8 to 12.0

In the above formulas 1 and 2,

A is a peak area ranging from 4.5 ppm to less than 5.5 ppm,

B is a peak area ranging from 3.8 ppm to less than 4.5 ppm,

C is a peak area ranging from 0.2 ppm to less than 2.5 ppm:

However, the ¹ H-NMR spectrum was measured according to the following condition 1.

[Condition 1]

A silicon-containing polymer is added to a solvent of dibutylether (DBE) to prepare a sample 1 having a solids content of 15 +/- 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 spin-rotated at 1,500 rpm for 5 minutes to form a film on the silicon wafer. The membrane thus formed is taken with a cutter, and the collected membrane is mixed with a solvent of CDCl ₃ (Chloroform-d) to prepare a solution. The content of the collected membrane was adjusted to 3.0% by weight with respect to the total amount of the solution to obtain Sample 2. The ¹ H-NMR spectrum of Sample 2 is then measured at 300 MHz.

The value of (A + B) / C in the above formula 2 may be 5.0 to 10.5.

The value of (A + B) / C in the above formula 2 may be 5.2 to 9.0.

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

The silicon-containing polymer may have a weight average molecular weight of 1,000 to 100,000.

The silicon-containing polymer may have a number average molecular weight of 500 to 10,000.

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

According to another embodiment, there is provided a silica film produced from the composition for forming a silica film.

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

The silicon-containing polymer for forming a silica film according to one embodiment is excellent in corrosion resistance, gap-fill property and planarization property. By providing a composition containing the same, a silica film having excellent corrosion resistance and planarization characteristics can be realized.

1 is a graph showing the results of ¹ H-NMR spectroscopy of SiH, SiH ₂ , SiH ₂ And the degree of crosslinking of the silicon-containing polymer through quantification of the peak area of NH < RTI ID = 0.0 > _1,2 . ≪ / RTI >
Fig. 2 is a reference diagram for explaining a method for evaluating the thickness uniformity of a film obtained by using the compositions according to Examples 1 to 7 and Comparative Examples 1 and 2. Fig.
3 is an electron micrograph of a silica film prepared according to Example 2. Fig.
4 is an electron micrograph of a silica film prepared according to Comparative Example 2. Fig.

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 thio group, an ester group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkenyl group, a C2 to C20 alkenyl group, A C3 to C30 heteroaryl group, a C3 to C30 heteroaryl group, a C3 to C30 cycloalkyl group, a C3 to C30 aryl group, a C7 to C30 arylalkyl group, a C1 to C30 alkoxy group, a C1 to C20 heteroalkyl group, a C2 to C20 hetero aryl group, Substituted with a substituent selected from the group consisting of a cycloalkenyl group, a C 6 to C 15 cycloalkynyl group, a C 2 to C 30 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 silicon-containing polymer for forming a silica film according to an embodiment of the present invention will be described.

According to one embodiment of the present invention, there is provided a silicon-containing polymer satisfying the following formulas 1 and 2 under ¹ H-NMR spectrum, and a composition for forming a silica film containing a solvent.

[Formula 1]

B / A = 0.2 to 0.4

* [Equation 2]

(A + B) / C = 4.8 to 12.0

In the above formulas 1 and 2,

A is a peak area ranging from 4.5 ppm to less than 5.5 ppm,

B is a peak area ranging from 3.8 ppm to less than 4.5 ppm,

C is a peak area ranging from 0.2 ppm to less than 2.5 ppm:

However, the ¹ H-NMR spectrum was measured according to the following condition 1.

[Condition 1]

A silicon-containing polymer is added to a solvent of dibutylether (DBE) to prepare a sample 1 having a solids content of 15 +/- 0.1 wt%. Next, 3 cc of the sample 1 was taken, dispensed in the center of an 8-inch diameter silicon wafer using a spin coater (MIKASA, MS-A200), and spin-rotated at 1,500 rpm for 5 minutes to form a Thereby forming a film quality. The membrane thus formed is taken with a cutter, and the collected membrane is mixed with a solvent of CDCl ₃ (Chloroform-d) to prepare a solution. The content of the collected membrane was adjusted to 3.0% by weight with respect to the total amount of the solution to obtain Sample 2. The ¹ H-NMR spectrum of Sample 2 is then measured at 300 MHz.

In the above formulas 1 and 2, A represents an area in which SiH and SiH ₂ appear, B represents an area in which SiH ₃ appears, and C represents an area in which NH ₂ and ₁ appear it means. The < ¹ > H-NMR spectrum is an important index that defines the structural characteristics of the silicon-containing polymer.

1 is a graph showing the results of ¹ H-NMR spectra of SiH, SiH ₂ , SiH ₃ And quantifying the peak area of NH < RTI ID = 0.0 > _1,2 . ≪ / RTI >

Referring to FIG. 1, the polysilazane polymer has repeating units of silicon and nitrogen. The remainder of the repeating unit except for the bonding portion of silicon and nitrogen forms a bond with hydrogen. From this point of view, the ratio of SiH _{1 , 2, 3} / NH _2, can be a measure for confirming the degree of crosslinking of the polymer. As the degree of cross-linking of the polysilazane increases, the ratio of SiH _{1 , 2, 3} / NH _1,2 through ¹ H-NMR spectrum is increased. These results show that when the polysilazane polymer is converted into a silica film, the denseness of the gap and the corrosion resistance are improved.

The silicon-containing polymer satisfies the above equations (1) and (2) simultaneously in ¹ H-NMR spectrum. By having such structural characteristics, excellent corrosion resistance, gap-fill property and planarization property can be secured at the time of manufacturing a silica film.

The etch rate of etch gas is also lower than that of etchant, and the better the corrosion resistance, the harder the film can be realized.

The gap-fill property is such that a silica film formed from a silicon-containing polymer densely fills a gap formed in an integrated circuit (IC), and an excellent gap-fill property improves the internal oxide film density.

The film flatness is a uniform thickness of the silica film formed from the silicon-containing polymer, and the better the flatness of the film, the easier the subsequent process after the formation of the silica film.

Generally, these characteristics are generally in conflict with each other. The silicon-containing polymer for forming a silica film according to one embodiment controls its structure so as to simultaneously satisfy the above-mentioned formulas 1 and 2, thereby improving corrosion resistance, gap- Characteristics can be satisfied at the same time.

For example, the value of (A + B) / C in Formula 2 may be 5.0 to 10.5, and more specifically, the value of (A + B) / C in Formula 2 may be 5.2 to 9.0, But is not limited thereto.

For example, the silicon-containing polymer may comprise polysilazane, polysiloxazane, or a combination thereof, and may have, for example, a weight average molecular weight ranging from 1,000 to 100,000, but is not limited thereto. 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.

On the other hand, the silicon-containing polymer may include, for example, a moiety represented by the following formula (A).

(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 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 reacting a halosilane with 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 (B) in addition to the moiety represented by the formula (A).

[Chemical 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, 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 the formula (A), a moiety represented by the formula (B), and further represented by the following formula (C).

≪ RTI ID = 0.0 &

The moiety represented by the above formula (C) is a structure in which the terminal portion is capped with hydrogen, which may be contained 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 organosilane-based condensate contained in the composition can be developed at a relatively low temperature.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Preparation of silicon-containing polymer

Comparative Polymerization Example  One

A stirrer having a capacity of 3 L and a reactor equipped with a temperature control device were replaced with dry nitrogen. Then, it was put into a 2,000 g dry pyridine reactor and then kept at 0 캜. Subsequently, 100 g of dichlorosilane was slowly added over 1 hour. Then, while stirring, 85 g of ammonia was slowly added thereto over 1.2 hours. Next, dry nitrogen was injected for 120 minutes to remove ammonia remaining in the reactor.

The resulting white slurry-like 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 concentration to 30% by weight, and pore size 0.03 Lt; RTI ID = 0.0 > g / m < / RTI >

The polysilazane having a weight average molecular weight of 3,200 and (A + B) / C = 4.29 was obtained through the above process.

The weight average molecular weight of the polysilazane in the present specification was measured using a GPC (PLC Pump 1515, RI Detector 2414) manufactured by Waters, and (A + B) / C was measured using a NMR (300 MHz) Respectively.

Comparative Polymerization Example  2

A stirrer having a capacity of 3 L and a reactor equipped with a temperature control device were replaced with dry nitrogen. Then, it was put into a 2,000 g dry pyridine reactor and then kept at 0 캜. Subsequently, 100 g of dichlorosilane was slowly added over 1 hour. Then, while stirring, 85 g of ammonia was slowly added thereto over 3 hours. Next, dry nitrogen was injected for 120 minutes to remove ammonia remaining in the reactor.

The resulting white slurry-like 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 concentration to 30% by weight, and pore size 0.03 Lt; RTI ID = 0.0 > g / m < / RTI >

The polysilazane having a weight average molecular weight of 1,800 and (A + B) / C = 3.86 was obtained through the above process.

Polymerization Example  One

A stirrer having a capacity of 3 L and a reactor equipped with a temperature control device were replaced with dry nitrogen. And put into a 1,500 g dry pyridine reactor, which was then maintained at 0 ° 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 120 minutes to remove ammonia remaining in the reactor.

The resulting white slurry-like 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 concentration to 30% by weight, and pore size 0.03 Lt; RTI ID = 0.0 > g / m < / RTI >

The polysilazane having a weight average molecular weight of 3,200 and (A + B) / C = 4.84 was obtained through the above-mentioned procedure.

Polymerization Example  2

A stirrer having a capacity of 3 L and a reactor equipped with a temperature control device were replaced with dry nitrogen. And put into a 1,500 g dry pyridine reactor, which was then maintained at 0 ° 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 120 minutes to remove ammonia remaining in the reactor.

The resulting white slurry-like 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 concentration to 30% by weight, and pore size 0.03 Lt; RTI ID = 0.0 > g / m < / RTI >

To the filtered solution was added 300 g of dry pyridine and heated to 100 캜 until the weight average molecular weight reached 5,400.

The polysilazane having a weight average molecular weight of 5,400 and (A + B) / C = 5.46 was obtained through the above process.

Polymerization Example  3

Polysilazane polymer having a weight average molecular weight of 11,200, (A + B) / C = 6.10 was prepared in the same manner as in Polymerization Example 2.

Polymerization Example  4

Polysilazane polymer having a weight average molecular weight of 22,400, (A + B) / C = 6.70 was prepared in the same manner as in Polymerization Example 2.

Polymerization Example  5

(A + B) / C = 7.22 was prepared in the same manner as in Polymerization Example 2, and a polysilazane polymer having a weight average molecular weight of 64,200 and (A + B) / C = 7.22 was prepared.

Polymerization Example  6

(A + B) / C = 8.52 polymer having a weight average molecular weight of 98,000 was prepared in the same manner as in Polymerization Example 2.

Polymerization Example  7

A stirrer having a capacity of 3 L and a reactor equipped with a temperature control device were replaced with dry nitrogen. Then, the mixture was placed in a 1,500 g dry pyridine reactor and maintained at 10 ° C. Subsequently, 100 g of dichlorosilane was slowly added over 1 hour. Then, while stirring, 50 g of ammonia was slowly added thereto over 6 hours. Next, dry nitrogen was injected for 120 minutes to remove ammonia remaining in the reactor.

The resulting white slurry-like 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 concentration to 30% by weight, and pore size 0.03 Lt; RTI ID = 0.0 > g / m < / RTI >

To the filtered solution was added 300 g of dry pyridine and heated to 100 캜 until the weight average molecular weight reached 3,400.

Through the above procedure, a polysilazane having a weight average molecular weight of 3,400, (A + B) / C = 8.12 was obtained.

^One ≪ 1 > H-NMR spectrum SiH , SiH ₂ , SiH ₃  And peak areas of NH

The silicon-containing polymer according to Comparative Polymerization Examples 1 to 2 and Polymerization Examples 1 to 7 was added to a solvent of dibutylether (DBE) to prepare Sample 1 having a solids content of 15 ± 0.1 wt%. 3 cc of Sample 1 was sampled and dispensed into the center of an 8-inch diameter silicon wafer (LG Siltron) using a spin coater (MIKASA, MS-A200), and spin-spinning was performed at 1,500 rpm for 5 minutes To form a film on the silicon wafer. The membrane thus formed is taken with a cutter, and the collected membrane is mixed with a solvent of CDCl ₃ (Chloroform-d) to prepare a solution. The content of the collected membrane was adjusted to 3.0% by weight with respect to the total amount of the solution to obtain Sample 2. The ¹ H-NMR spectrum of Sample 2 is then measured at 300 MHz.

¹ in the H-NMR spectrum, of less than 5.5ppm 4.5ppm or more ranges of peak area for SiH and SiH ₂ peak area (A) with and, 3.8ppm peak area of the peak area of the above range of less than 4.5ppm of SiH ₃ (B) (A + B) / C, respectively, with a peak area of NH in the range of 0.2 ppm or more and less than 2.5 ppm as the peak area (C) of NH 3.

The results are shown in Table 1 below.

B / A (A + B) / C Weight average molecular weight Comparative Polymerization Example 1 0.245 4.29 3,200 Comparative Polymerization Example 2 0.223 3.86 1,800 Polymerization Example 1 0.271 4.84 3,200 Polymerization Example 2 0.273 5.46 5,400 Polymerization Example 3 0.279 6.10 11,200 Polymerization Example 4 0.288 6.70 22,400 Polymerization Example 5 0.296 7.23 64,200 Polymerization Example 6 0.310 8.52 98,000 Polymerization Example 7 0.252 8.12 3,400

Referring to Table 1, it can be seen that the ranges of the following formulas 1 and 2 are satisfied at the same time in the ¹ H-NMR spectroscopic measurement of the silicon-containing polymer according to Comparative Polymerization Examples 1 and 2 and Polymerization Examples 1 to 7.

[Formula 1]

B / A = 0.2 to 0.4

[Formula 2]

(A + B) / C = 4.8 to 12.0

Preparation of composition for silica film formation

Comparative Example  1 and 2

The polysilazane obtained in Comparative Polymerization Examples 1 and 2 was replaced with a dibutyl ether using a rotary evaporator to prepare a composition for forming a silica film having a solid content of 15% by weight.

Example  1 to 7

The polysilazane obtained in Polymerization Examples 1 to 7 was replaced with a dibutyl ether using a rotary evaporator to prepare a composition for forming a silica film having a solid content of 15% by weight.

Evaluation 1: membrane Flatness

3cc of each of the compositions for forming a silica film according to Comparative Examples 1 and 2 and Examples 1 to 7 was dispensed to a center portion of a silicon wafer having a diameter of 8 inches by a spin coater (MIKASA, MS-A200) (MIKASA, MS-A200) for 20 seconds. Thereafter, the resultant was heated at 150 DEG C for 3 minutes with a hot plate and dried to form a silica-based film.

Subsequently, nine points on the wafer having a silica-based film as shown in FIG. 2 were measured in cross (+) using a reflection spectrophotometer (K-MAC, ST-5000) Thickness - minimum thickness) and thickness uniformity were confirmed, and the silica-based film flatness was obtained according to the following formula.

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

The results are shown in Table 2 below.

Average thickness (Å) Thickness Range (Å)  Film planarity Comparative Example 1 4554 167 1.8 Comparative Example 2 3961 177 2.2 Example 1 4949 101 1.0 Example 2 5952 104 0.9 Example 3 5964 87 0.7 Example 4 5951 75 0.6 Example 5 5932 77 0.6 Example 6 5988 62 0.5 Example 7 5912 75 0.6

       Referring to Table 1, it can be seen that Comparative Examples 1 and 2 have comparatively small film flatness in Examples 1 to 7. This shows that the silica-based film formed from the composition containing the polysilazane polymer having the B / A and (A + B) / C values satisfies a predetermined range as in Examples 1 to 7 has a relatively uniform thickness .

Evaluation 2: Gap-fill characteristic

The silica-based film forming compositions according to Comparative Examples 1 and 2 and Examples 1 to 7 were applied to a silicon wafer having a pattern formed thereon, and baked to form a thin film. Subsequently, the cross section was attached to a mount, and then platinum sputtering was performed for 8 seconds at 6 mA using an HR coater (HR coater). The pre-processed samples were observed with an electron microscope (S5500, Hitachi) at a magnification of 100,000 times.

The results are shown in Table 3 below, and in Figures 3 and 4.

Gap-fill characteristic Comparative Example 1 Bad Comparative Example 2 Bad Example 1 Good Example 2 Good Example 3 Good Example 4 Good Example 5 Good Example 6 Good Example 7 Good

Referring to Table 3, the results of the gap-fill characteristics of the compositions for forming a silica-based film according to Examples 1 to 7 are "good ", whereas the results of the gap- The characteristic result is "defective ".

This shows that the gap-fill property of a film formed from a composition containing a polysilazane polymer having a B / A and (A + B) / C value satisfies a predetermined range.

3 and 4, it can be seen that the silica film produced according to Example 2 has a better gap-fill than the silica film produced according to Comparative Example 2. [

Evaluation 3: Awareness of corrosion  Evaluation (film density)

The silica-based film-forming compositions according to Comparative Examples 1 and 2 and Examples 1 to 7 were spin-coated on a patterned wafer of 3 cm x 3 cm in size (MIKASA, MS-A200). Thereafter, soft baking was performed at 150 캜 for 3 minutes. Subsequently, a high-temperature oxidation reaction was carried out, and after conversion to an oxide film at 800 ° C., the substrate was immersed in an aqueous solution (DHF 100: 1) mixed with hydrofluoric acid and ammonium fluoride for 5 minutes. Thereafter, the pattern was etched with a size of 40 nm, 100 nm, and 200 nm, respectively, and the etching amount inside the formed gap (that is, inside the pattern) was calculated by trigonometry (S-5500 ).

The polysilazane solution was spin-coated on a bare wafer in the same manner as above and soft-baked at 150 ° C for 3 minutes. Subsequently, a high-temperature oxidation reaction was carried out to convert the oxide film to an oxide film at 800 ° C. Then, the thickness of the oxide film was measured, and the film was immersed in an aqueous solution (DHF 100: 1) mixed with hydrofluoric acid and ammonium fluoride for 5 minutes. (ST-5000) manufactured by MAC Co., Ltd. to calculate the outer surface etching amount, and the inner oxide film density was checked therefrom.

The value of the internal oxide film density is obtained according to the following formula.

Internal oxide film density = external surface etching amount / pattern internal etching amount

The results are shown in Table 4 below.

Internal oxide film density Pattern size 40 nm Pattern size 100 nm Pattern size 200 nm Comparative Example 1 0.35 0.35 0.33 Comparative Example 2 0.32 0.31 0.32 Example 1 0.49 0.47 0.48 Example 2 0.49 0.47 0.48 Example 3 0.51 0.51 0.50 Example 4 0.52 0.52 0.51 Example 5 0.54 0.53 0.52 Example 6 0.54 0.54 0.53 Example 7 0.53 0.54 0.52

Referring to Table 4, when the composition according to Examples 1 to 7 was used, the film compactness in the gap was excellent in all the patterns of sizes of 200 nm or less as compared with the case of using the composition according to Comparative Examples 1 and 2 can confirm.

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 (10)

A composition for forming a silica film comprising a silicon-containing polymer and a solvent,
The ¹ H-NMR spectrum of the silicon-containing polymer satisfies the following formulas 1 and 2,
The silicon-containing polymer is contained in an amount of 0.1 to 50% by weight based on the total amount of the composition for forming a silica film
Composition for forming a silica film:
[Formula 1]
B / A = 0.2 to 0.4
[Formula 2]
(A + B) / C = 5.0 to 10.5
In the above formulas 1 and 2,
A is a peak area ranging from 4.5 ppm to less than 5.5 ppm,
B is a peak area ranging from 3.8 ppm to less than 4.5 ppm,
C is a peak area ranging from 0.2 ppm to less than 2.5 ppm:
However, the ¹ H-NMR spectrum was measured according to the following condition 1.
[Condition 1]
A silicon-containing polymer is added to a solvent of dibutylether (DBE) to prepare a sample 1 having a solids content of 15 +/- 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 spin-rotated at 1,500 rpm for 5 minutes to form a film on the silicon wafer. The membrane thus formed is taken with a cutter, and the collected membrane is mixed with a solvent of CDCl ₃ (Chloroform-d) to prepare a solution. The content of the collected membrane was adjusted to 3.0% by weight with respect to the total amount of the solution to obtain Sample 2. The ¹ H-NMR spectrum of Sample 2 is then measured at 300 MHz. delete The method of claim 1,
Wherein the value of (A + B) / C in the above formula 2 is 5.2 to 9.0. The method of claim 1,
Wherein the silicon-containing polymer comprises polysilazane, polysiloxazane, or a combination thereof. The method of claim 1,
Wherein the silicon-containing polymer has a weight average molecular weight of 1,000 to 100,000. The method of claim 1,
Wherein the silicon-containing polymer has a number average molecular weight of 500 to 10,000. The method of claim 1,
The solvent is selected from the group consisting of benzene, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, triethylbenzene, decahydronaphthalene, dipentene, pentane, hexane, heptane, octane, nonane, decane, ethylcyclohexane, Silica film formation comprising at least one selected from the group consisting of hexane, cyclohexane, cyclohexene, p-menthane, dipropyl ether, dibutyl ether, anisole, butyl acetate, amyl acetate, methyl isobutyl ketone and combinations thereof / RTI > The method of claim 1,
Wherein the silicon-containing polymer is contained in an amount of 0.1 to 30% by weight based on the total amount of the composition for forming a silica film. 9. A silica film produced from the composition for forming a silica film according to any one of claims 1 to 8. An electronic device comprising the silica film according to claim 9.

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