KR101806328B1

KR101806328B1 - Composition for forming silica based layer, silica based layer, and electronic device

Info

Publication number: KR101806328B1
Application number: KR1020140188905A
Authority: KR
Inventors: 윤희찬; 김우한; 고상란; 곽택수; 김보선; 김진교; 나융희; 노건배; 박새미; 배진희; 사공준; 이은선; 임완희; 장준영; 정일; 황병규
Original assignee: 삼성에스디아이 주식회사
Priority date: 2014-10-07
Filing date: 2014-12-24
Publication date: 2017-12-07
Also published as: JP2016074875A; CN106189267A; TWI575024B; TW201614007A; KR20160041728A; JP6599640B2

Abstract

A silicon-containing polymer having a weight average molecular weight of 20,000 to 70,000 and a polydispersity of 5.0 to 17.0; and a solvent; A silica-based film obtained by using the same; And an electronic device including the silica-based film.

Description

TECHNICAL FIELD [0001] The present invention relates to a composition for forming a silica-based film, a silica-based film, and an electronic device,

The present invention relates to an electronic device comprising a composition for forming a silica-based film, a silica-based film, and the silica-based film.

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

Accordingly, a silica-based film formed of a silicon-containing material is widely used as an interlayer insulating film, a planarizing film, a passivation film, an interdevice separating insulating film, and the like of semiconductor devices for proper separation between devices. The silica-based film is used not only for a semiconductor device but also as a protective film or an insulating film for a display device or the like. For example, Korean Patent Laid-Open Publication No. 2002-0025680 discloses a semiconductor device to which a silicon nitride film is applied, and Korean Patent Publication No. 2005-0104610 discloses a display device to which an insulating film which is a silicon layer is applied.

The silica-based film is generally formed by applying a silicon-containing material to a predetermined region of the device and then curing the film. The silica-based film is formed by forming a film satisfying both a gap-fill characteristic and a gap etch characteristic Is required.

One embodiment provides a composition for forming a silica-based film capable of simultaneously securing a gap-fill property and a gap-etch property.

Another embodiment provides a silica-based film using the composition for forming a silica-based film.

Another embodiment provides an electronic device comprising the silica-based film.

According to one embodiment, there is provided a composition for forming a silica-based film comprising a silicon-containing polymer having a weight average molecular weight of 20,000 to 70,000 and a polydispersity of 5.0 to 17.0, and a solvent.

Wherein the silicon-containing polymer is a silicon-containing polymer having a weight average molecular weight of 20,000 to 50,000 and a polydispersity of 5.0 to 14.0, a silicon-containing polymer having a weight-average molecular weight of 50,000 or more and 70,000 or less and a polydispersity of 11.5 to 17.0, . &Lt; / RTI >

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

The silicon-containing polymer may have a polydispersity of 5.3 to 15.5.

The silicon-containing polymer may have a weight average molecular weight of 22,000 to 65,000

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, . &Lt; / 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-based film.

Containing polymer is 0.01 to 3% by weight based on 100% by weight of the silicon-containing polymer, and the -SiH ₃ group content of the silicon-containing polymer is a sum of Si-H bonds present in the silicon-containing polymer And may be from 15% to 40% with respect to the content.

According to another embodiment, there is provided a silica-based film produced by using the above-mentioned composition for forming a silica-based film.

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

A silica-based film capable of simultaneously ensuring the flatness of the film and the compactness of the gap can be realized.

FIG. 1 is a photograph of a silica film prepared from the composition of Example 1 having a gap-fill property of 'good', taken by an electron microscope.
FIG. 2 is a photograph of a silica film prepared from the composition of Comparative Example 2 in which the gap-fill characteristic is 'poor', by an electron microscope.
FIG. 3 is a photograph of a silica film prepared from the composition of Example 3 having a gap etch characteristic of 'very good', taken by an electron microscope.
FIG. 4 is a photograph of a silica film prepared from the composition of Example 1 having a 'good' gap etch characteristic, taken by an electron microscope.
5 is a photograph of a silica film prepared from the composition of Comparative Example 1 in which the gap etch characteristic is 'poor', by an electron microscope.

Hereinafter, exemplary 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.

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

Hereinafter, the composition for forming a silica-based film according to one embodiment will be described.

The composition for forming a silica-based film according to an embodiment includes a silicon-containing polymer and a solvent.

The silicon-containing polymer is not particularly limited as long as it is a polymer containing silicon (Si) atoms, and may include, for example, polysilazane, polysiloxazane, or a combination thereof.

The silicon-containing polymer has a weight average molecular weight of 20,000 to 70,000 and a polydispersity index (PDI) of 5.0 to 17.0.

The composition for forming a silica-based film according to an embodiment contains a silicon-containing polymer having a weight-average molecular weight and a polydispersity value in a predetermined range, so that the uniformity of the film to be produced can be ensured, it is possible to minimize the occurrence of defects inside the film by increasing the density of the gap.

Wherein the silicon-containing polymer is a silicon-containing polymer having a weight average molecular weight of 20,000 to 50,000 and a polydispersity of 5.0 to 14.0, a silicon-containing polymer having a weight-average molecular weight of 50,000 or more and 70,000 or less and a polydispersity of 11.5 to 17.0, . &Lt; / RTI > The composition containing the silicon-containing polymer satisfying the weight average molecular weight and the polydispersity in the above range is excellent in the applicability and is capable of forming a uniform film quality as well as excellent etch characteristics. In addition, the curing time of the composition is relatively long, and the film can be stably produced.

The polydispersity of the silicon-containing polymer may be, for example, 5.3 to 15.5 in the above range, and the weight average molecular weight of the silicon-containing polymer may be, for example, 22,000 to 65,000 in the above range.

For example, the silicon-containing polymer may be 0.01 wt% to 3 wt%, specifically 0.2 wt% to 3 wt% based on 100 wt% of the silicon-containing polymer.

When it is contained in the above-mentioned range, shrinkage can be prevented during heat treatment, and cracks can be prevented from being generated in the filling pattern formed. More specifically 0.4 to 2% by weight.

In addition, the silicon-containing polymer may have -SiH ₃ And may be contained in an amount of 15 to 40% by weight based on the total amount of Si-H bonds in the silicon-containing polymer. In this specification, the oxygen content is measured using FlashEA 1112 (manufactured by Thermo Fisher Scientific Inc.), and SiH ₃ / SiH is measured using Proton NMR: AC-200 (manufactured by Bruker) at 200 MHz.

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-based film. When it is included in the above-mentioned range, it is possible to maintain an appropriate viscosity and to be formed evenly and without gap at gap-fill.

The solvent may be an aromatic compound, an aliphatic compound, a saturated hydrocarbon compound, an ether, an ester, or a ketone. Specific examples of the solvent include benzene, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, triethylbenzene, cyclohexane , Cyclohexene, decahydronaphthalene, dipentene, pentane, hexane, heptane, octane, nonane, decane, ethylcyclohexane, methylcyclohexane, cyclohexane, cyclohexene, p- menthane, dipropyl ether, dibutyl ether, Anisole, butyl acetate, amyl acetate, methyl isobutyl ketone, and combinations thereof.

In particular, at least one of the solvents preferably comprises a solvent having a high boiling point of 130 ° C or higher. As a result, the flatness of the film can be increased.

The solvent may be included in the remainder of the total amount of the composition for forming a silica-based film except for the above-mentioned components.

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

The thermal acid generator is not particularly limited as long as it is a compound capable of generating an acid (H ^& lt ^{; +} & gt ^; ) by heat, but it can be activated at 90 DEG C or higher to generate sufficient acid and have low volatility. Such thermal acid generators can 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-based film.

The composition for forming a silica-based 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 monolaurate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan fatty acid ester, (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 Fluorine surfactants such as Asahi Guard AG710, SHAPLON S-382, SC101, SC102, SC103, SC104, SC105 and SC106 (manufactured by Asahi Kasei Corporation), organosiloxane polymer KP341 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-based film. When the surfactant is included in the above range, the dispersibility of the solution is improved, .

The method for producing a silica-based film includes the steps of: applying a composition for forming a silica-based insulating layer on a substrate on a substrate; Drying the substrate coated with the composition for forming a silica-based insulating layer; And curing the substrate.

The silica-based film-forming composition may be in the form of a solution in which the silicon-containing polymer and the solvent are mixed and may be subjected to a solution process such as spin coating, slit coating, screen printing, inkjet, one drop filling, . &Lt; / RTI > The step of curing the substrate may include, for example, a heat treatment at a temperature of about 150 캜 or higher.

The silica-based film can be used for, for example, a protective film such as an insulating film, a filled film, a hard coating, or a semiconductor capacitor. The insulating film may be used, for example, between a transistor element and a bit line, between a transistor element and a capacitor, but is not limited thereto.

According to another embodiment, there is provided an electronic device including the silica-based film described above. The electronic device may include a display device, a semiconductor, an image sensor, and the like.

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

Preparation of composition for silica-based film formation

[ Comparative Example One]

A stirrer having a capacity of 2 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 30 minutes to remove ammonia remaining in the reactor. The resulting white slurry-like product was filtered through a 1-μm 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 > filtered through a Teflon filter.

300 g of dry pyridine was added to the filtered solution and heated to 100 캜 until the weight average molecular weight reached 23,000.

1000 g of dry dibutyl ether was added, and then the solvent was replaced with dibutyl ether using a rotary evaporator, and the solid content was adjusted to 20% by weight while repeating this operation three times.

Through the above procedure, a polysilazane having a weight average molecular weight of 23,000 and a polydispersity of 4.8 was obtained. The weight average molecular weight and polydispersity of the polysilazane in the present specification were measured using GPC (PLC Pump 1515, RI Detector 2414, manufactured by Waters).

Then, the obtained polysilazane solution was filtered to prepare a composition for forming a silica-based film.

[ Comparative Example 2]

The same procedure as in Comparative Example 1 was followed until the weight average molecular weight reached 100,000. Then, a polysilazane dibutyl ether solution having a weight average molecular weight of 100,000 and a polydispersity of 13.5 obtained through the same solvent substitution as in Comparative Example 1 was filtered to prepare a composition for forming a silica-based film.

[ Comparative Example 3]

The same procedure as in Comparative Example 1 was followed until the weight average molecular weight reached 140,000. Then, a polysilazane dibutyl ether solution having a weight average molecular weight of 140,000 and a polydispersity of 17.5 was filtered through the same solvent substitution as in Comparative Example 1 to prepare a composition for forming a silica-based film.

[ Example One]

The same procedure as in Comparative Example 1 was followed until the weight average molecular weight reached 8,000. Thereafter, the same solvent substitution as in Comparative Example 1 was carried out to obtain a polysilazan dibutyl ether solution having a weight average molecular weight of 8,000 and a polydispersity of 2.9.

The solution was mixed with the polysilazan dibutyl ether solution obtained in Comparative Example 2 at a ratio (weight ratio) of 8: 2 to obtain a polysilazan dibutyl ether solution having a weight average molecular weight of 23,000 and a polydispersity of 6.4. The obtained polysilazane solution was filtered to prepare a composition for forming a silica-based film.

[ Example 2]

The solution was mixed with the polysilazan dibutyl ether solution obtained in Comparative Example 3 at a ratio (weight ratio) of 9: 1 to obtain a polysilazan dibutyl ether solution having a weight average molecular weight of 23,000 and a polydispersity of 7.3. The obtained polysilazane solution was filtered to prepare a composition for forming a silica-based film.

[ Example 3]

The solution was mixed with the polysilazan dibutyl ether solution obtained in Comparative Example 2 at a ratio (weight ratio) of 6: 4 to obtain a polysilazan dibutyl ether solution having a weight average molecular weight of 46,000 and a polydispersity of 11.7. The obtained polysilazane solution was filtered to prepare a composition for forming a silica-based film.

[ Example 4]

The solution was mixed with the polysilazan dibutyl ether solution obtained in Comparative Example 3 at a ratio of 3: 1 (weight ratio) to obtain a polysilazan dibutyl ether solution having a weight average molecular weight of 46,000 and a polydispersity of 12.6. The obtained polysilazane solution was filtered to prepare a composition for forming a silica-based film.

[ Example 5]

The solution was mixed with the polysilazan dibutyl ether solution obtained in Comparative Example 2 at a ratio (weight ratio) of 4: 6 to obtain a polysilazan dibutyl ether solution having a weight average molecular weight of 61,000 and a polydispersity of 14.9. The obtained polysilazane solution was filtered to prepare a composition for forming a silica-based film.

[ Example 6]

The solution was mixed with the polysilazan dibutyl ether solution obtained in Comparative Example 3 at a ratio (weight ratio) of 6: 4 to obtain a polysilazan dibutyl ether solution having a weight average molecular weight of 61,000 and a polydispersity of 15.4. The obtained polysilazane solution was filtered to prepare a composition for forming a silica-based film.

[ Example 7]

And the mixture was heated until the weight average molecular weight reached 10,000 by the same procedure as in Comparative Example 1. Thereafter, the same solvent substitution as in Comparative Example 1 was carried out to obtain a polysilazan dibutyl ether solution (1) having a weight average molecular weight of 10,000 and a polydispersity of 3.2, and a weight average molecular weight of 30,000 Lt; / RTI > Thereafter, the same solvent substitution as in Comparative Example 1 was carried out to obtain a polysilazan dibutyl ether solution (2) having a weight average molecular weight of 30,000 and a polydispersity of 5.8.

The solutions of the above (1) and (2) were mixed at a ratio of 4: 6 (weight ratio) to obtain a polysilazan dibutyl ether solution having a weight average molecular weight of 22,000 and a polydispersity of 5.3. The obtained polysilazane solution was filtered to prepare a composition for forming a silica-based film.

The GPC molecular weight measurement conditions are as follows.

1. Model of GPC

- Waters GPC (PLC Pump 1515, RI Detector 2414)

- Column Type: Shodex LF-804

2. Measurement conditions

- Eluent: THF

- Measurement concentration: 1% (Xylene)

- Injection volume: 50 μl

- Flow rate: 1 ml / min

3. Calibration curve

- STD Type: Poly Styrene STD (Shodex)

- Number: 12

(580 / 1,200 / 2,340 / 3,950 / 6,180 / 13,000 / 16,500 / 20,000 / 55,100 / 133,000 / 288,000 / 1,280,000)

- Precision: 5th order polynomial, R ² > 0.99

Evaluation 1: Gap-fill characteristic

The silica-based film forming composition according to Comparative Examples 1 to 3 and Examples 1 to 7 was coated on 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. 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 1 below.

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

Referring to Table 1, 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 those of Comparative Examples 2 and 3, The characteristic result is "defective ". This shows that the gap-fill property of the film formed using the polysilazane composition satisfying the predetermined range of weight average molecular weight and polydispersity is excellent.

Evaluation 2: Gap Etch ( Gap etch ) Characteristics

The silica-based film forming composition according to Comparative Examples 1 to 3 and Examples 1 to 7 was coated on a silicon wafer having a pattern formed thereon, and baked to form a thin film. Subsequently, dipping was carried out for 30 seconds while maintaining the etching solution (aqueous solution of HF 0.5% by weight) at 18 占 폚, and then rinsed for 30 seconds using ultrapure water. The remaining water was then removed with nitrogen. Thereafter, the cross section was attached to a mount, and then Pt sputtering was performed for 8 seconds at 6 mA using an HR coater. The pretreated sample was observed with an electron microscope (S5500, Hitachi) at a magnification of 100,000 times.

The results are shown in Table 2 below.

Gap etch Gap etch Example 1 Good Comparative Example 1 Bad Example 2 Good Comparative Example 2 - Example 3 Very good Comparative Example 3 - Example 4 Very good Example 5 Very good Example 6 Very good Example 7 Very good

Based on Table 2, the results of the gap-fill characteristics of the silica-based film-forming compositions according to Examples 1 to 7 are "good" or "very good" The gap-fill characteristic result is "defective ". Further, in the case of Comparative Examples 2 and 3, the gap fill characteristic was poor and the Gap etch characteristics could not be evaluated.

Referring to Table 2, it can be seen that the gap etch characteristics of the film formed using the polysilazane composition satisfying the weight average molecular weight and polydispersity in a predetermined range are excellent.

Rating 3: Gelling time

The composition for forming a silica-based film according to Comparative Examples 1 to 3 and Examples 1 to 7 was filled in a 40 ml glass vial in half and then left in a clean room at 22 ° C / 50 RH%. The glass vials were observed by visual observation at intervals of one hour to confirm the gelation.

It was evaluated as being good when the gelation time was not more than 7 hours, good when it was not less than 7 hours but not more than 12 hours, and very good when it was more than 12 hours.

The results are shown in Table 3 below.

Gelation time (Hr) Gelation time (Hr) Example 1 Very good Comparative Example 1 Good Example 2 Very good Comparative Example 2 Bad Example 3 Very good Comparative Example 3 Bad Example 4 Good Example 5 Good Example 6 Good Example 7 Good

Table 3 shows that the gelation time evaluation results of the compositions for forming a silica-based film according to Examples 1 to 7 are "good" or "very good" Is evaluated as "defective ". This shows that the gelation time of the film formed using the polysilazane composition satisfying the predetermined range of weight average molecular weight and polydispersity is relatively long and the stability of the composition is excellent.

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, And falls within the scope of the invention.

Claims

A silicon-containing polymer having a weight average molecular weight of 20,000 to 50,000 and a polydispersity of 5.0 to 14.0, a silicon-containing polymer having a weight-average molecular weight of 50,000 to 70,000 and a polydispersity of 11.5 to 17.0, or a combination thereof; And
menstruum
Containing
Based film-forming composition.

delete

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 polydispersity of 5.3 to 15.5.

delete

The method of claim 1,
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, Based film-forming composition.

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-based film.

4. The method of claim 3,
The oxygen content of the silicon-containing polymer is 0.01 wt% to 3 wt% with respect to 100 wt% of the silicon-containing polymer,
Wherein the -SiH ₃ group content of the silicon-containing polymer is 15% to 40% based on the total content of Si-H bonds present in the silicon-containing polymer.

A silica-based film produced by using the composition for forming a silica-based film according to any one of claims 1, 3, 4, and 6 to 8.

An electronic device comprising the silica-based film according to claim 9.