TW201811671A - Composition for forming silica layer, silica layer, and electronic device - Google Patents

Abstract

The present invention provide a composition for forming a silica layer, a silica layer, and an electronic device. The composition for forming a silica layer includes a silicon-containing polymer satisfying Equations 1 and 2 in a1H-NMR spectrum and a solvent. [Equation 1] B/A = 0.2 to 0.4 [Equation 2] (A+B)/C = 4.8 to 12.0 Definitions of Equations 1 and 2 are the same as in the detailed description. The silicon-containing polymer for forming a silica layer according to one embodiment has excellent etch resistance, gap-fill characteristics, and planarization characteristics. By providing a composition including the same, the obtained silica layer may accomplish excellent etch resistance and planarization characteristics.

Description

Composition for forming a ruthenium dioxide layer, a ruthenium dioxide layer, and an electronic device

This application claims the priority of Korean Patent Application No. 10-2016-0112026, which was filed with the Korea Intellectual Property Office on August 31, 2016, and No. 10-2016-0121750, which was filed at the Korea Intellectual Property Office on September 22, 2016. And rights, the entire contents of which are incorporated herein by reference.

The present invention relates to a composition for forming a ruthenium dioxide layer and a ruthenium dioxide layer produced using the composition.

The flat panel display uses a thin film transistor (TFT) including a gate electrode, a source electrode, a drain electrode, and a semiconductor as a switching device, and is equipped with a gate line that transmits a scanning signal for controlling the thin film transistor and A data line that transmits a signal applied to the pixel electrode. In addition, an insulating layer is formed between the semiconductor and the electrodes to separate them.

The insulating layer is generally a cerium oxide layer formed by converting a cerium-containing polymer into cerium oxide. Herein, depending on the structure of the ruthenium-containing polymer, the etch resistance, gap fill characteristics, planarization characteristics, and the like of the ruthenium dioxide layer may be different, and may affect the storage stability of the composition for forming the ruthenium dioxide layer. Sex. These features have a trade-off relationship with each other and therefore require a layer of erbium oxide that simultaneously satisfies the characteristics.

One embodiment provides a composition for forming a hafnium oxide layer having improved etch resistance, gap fill features, and planarization characteristics.

Another embodiment provides a cerium oxide layer comprising a cerium oxide component obtained by converting a cerium-containing polymer used to form a cerium oxide layer.

Yet another embodiment provides an electronic device comprising a ruthenium dioxide layer.

According to one embodiment, the composition for forming the ruthenium dioxide layer comprises a ruthenium containing polymer and a solvent, wherein the ¹ H-NMR spectrum of the ruthenium containing polymer satisfies Equations 1 and 2. [Equation 1] B/A = 0.2 to 0.4 [Equation 2] (A+B)/C = 4.8 to 12.0 In Equations 1 and 2, A is a peak area of 4.5 ppm or more and less than 5.5 ppm. , B is a peak area greater than or equal to 3.8 ppm and less than 4.5 ppm, and C is a peak area greater than or equal to 0.2 ppm and less than 2.5 ppm: ¹ H-NMR spectrum is measured according to Condition 1: [Condition 1] Polymerization containing ruthenium Adding to dibutyl ether (DBE) solvent to prepare sample 1 with a solid content of 15 ± 0.1% by weight, obtaining sample 1 of 3 cubic centimeters, and dispensing sample 1 at the center of a 8 inch diameter tantalum wafer using a spin coater. And rotating it at 1,500 rpm (1500 rpm) for 5 minutes to form a film on the ruthenium wafer, taking the film with a cutter and mixing the obtained film with CDCl ₃ (chloroform-d) solvent A solution was prepared, and Sample 2 was prepared in which the film content obtained was 3.0% by weight based on the total amount of the solution, and the ¹ H-NMR spectrum of Sample 2 was measured at 300 MHz (MHz). In Equation 2, (A+B)/C may be in the range of 5.0 to 10.5. In Equation 2, (A+B)/C may be in the range of 5.2 to 9.0.

The cerium-containing polymer may comprise polysilazane, polysiloxazane, or a combination thereof.

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

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

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

The cerium-containing polymer may be included in an amount of from 0.1% by weight to 30% by weight based on the total amount of the composition for forming the cerium oxide layer.

According to another embodiment, a ruthenium dioxide layer made of a composition for forming a ruthenium dioxide layer is provided.

According to still another embodiment, an electronic device including a ruthenium dioxide layer is provided.

The ruthenium containing polymer used to form the ruthenium dioxide layer according to one embodiment has excellent etch resistance, gap fill characteristics, and planarization characteristics. By providing a composition comprising the same, the obtained ruthenium dioxide layer can achieve excellent etch resistance and planarization characteristics.

Exemplary embodiments of the present invention will be described in detail below, and can be easily performed by persons having common knowledge in the related art. However, the invention may be embodied in many different forms and should not be construed as being limited to the exemplary embodiments set forth herein.

In the drawings, the thickness of layers, films, panels, regions, etc., are exaggerated for clarity. Like reference numerals indicate like elements throughout the specification. It will be understood that when an element, such as a layer, film, region or substrate, is referred to as being "on" another element, it may be directly on the other element or the intervening element may also be present. In contrast, when an element is referred to as being "directly on" another element, there is no intervening element.

As used herein, when a definition is not otherwise provided, 'substitution' means that the hydrogen of the compound is replaced by a substituent selected from the group consisting of a halogen atom (F, Br, Cl or I), a hydroxyl group, an alkoxy group, a nitro group, Cyano group, amino group, azido group, formyl group, fluorenyl group, fluorenylene group, carbonyl group, carbamoyl group, thiol group, ester group, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphate group or Salt, C1 to C20 alkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, C6 to C30 aryl, C7 to C30 aralkyl, C1 to C30 alkoxy, C1 to C20 heteroalkyl, C2 to C20 Heteroaryl, C3 to C20 heteroarylalkyl, C3 to C30 cycloalkyl, C3 to C15 cycloalkenyl, C6 to C15 cycloalkynyl, C2 to C30 heterocycloalkyl, and combinations thereof. As used herein, when a definition is not otherwise provided, the term 'hetero' refers to one of 1 to 3 heteroatoms selected from N, O, S, and P.

In addition, in the specification, "*" means a point of attachment to the same or different atom or chemical formula.

Hereinafter, a ruthenium-containing polymer for a ruthenium dioxide layer according to an embodiment of the present invention will be described.

According to an embodiment of the present invention, the composition for forming a ceria layer comprises a ruthenium-containing polymer satisfying the equations 1 and 2 and a solvent in a ¹ H-NMR spectrum. [Equation 1] B/A = 0.2 to 0.4 [Equation 2] (A+B)/C = 4.8 to 12.0 In Equations 1 and 2, A is a peak area of 4.5 ppm or more and less than 5.5 ppm. , B is a peak area greater than or equal to 3.8 ppm and less than 4.5 ppm, and C is a peak area greater than or equal to 0.2 ppm and less than 2.5 ppm: The constraint is ¹ H-NMR spectrum measured according to Condition 1: [Condition 1] The cerium-containing polymer was added to a dibutyl ether (DBE) solvent to prepare a sample 1 having a solid content of 15 ± 0.1% by weight, obtaining 3 cubic centimeters (cc) of sample 1, and using a spin coater at a diameter of 8 inches of twins. Sample 1 was dispensed at the center of the circle, and it was rotated at 1,500 rpm for 5 minutes to form a film on the ruthenium wafer, the film was taken with a cutter and the obtained film was combined with CDCl ₃ (chloroform-d) solvent. The mixture was prepared to prepare a solution, and Sample 2 was prepared in which the film content obtained was 3.0% by weight based on the total amount of the solution, and the ¹ H-NMR spectrum of Sample 2 was measured at 300 MHz.

In Equations 1 and 2, A refers to an area in which SiH and SiH ₂ are exhibited; B means an area in which SiH ₃ is exhibited; and C means that NH _{1, 2} is exhibited therein. The area within the range. ^{The 1} H-NMR spectrum became an important index defining the structural characteristics of the ruthenium containing polymer.

1 is a graph of understanding the peak area of SiH, SiH ₂ , SiH _{3 ,} and NH _1,2 in the ¹ H-NMR spectrum of a ruthenium-containing polymer to help understand the degree of crosslinking of the ruthenium-containing polymer. Reference diagram of the structure.

Referring to Fig. 1, a polyazide polymer has a repeating unit of hydrazine and nitrogen, and a portion other than a bonded portion having a hydrazine and a nitrogen for a repeating unit forms a bond with hydrogen. In view of this, the ratio of SiH _1,2,3 /NH _1,2 can be a measure for confirming the degree of crosslinking of the polymer. Since polyazide has a higher degree of crosslinking _{, the} ratio of SiH _{1, 2, 3} / NH _{1, 2} analyzed by ¹ H-NMR spectroscopy becomes large. The results show that when the polyazide polymer is changed to the ceria layer, the layer compactness and etching resistance in the gap can be improved.

Since the ruthenium-containing polymer satisfies Equations 1 and 2 simultaneously under the ¹ H-NMR spectrum and has structural features, when the ruthenium dioxide layer is formed, it can simultaneously provide excellent etching resistance, gap filling characteristics, and planarization characteristics.

Etching resistance means having a lower etching rate for an etching gas or an etching liquid, and thus a higher etching resistance can realize a rigid layer.

The excellent gap fill feature enhances the compactness of the inner oxide layer by tightly filling the ceria layer formed of the germanium containing polymer into the interstitial of the integrated circuit (IC).

The film flatness refers to the thickness uniformity of the cerium oxide layer formed of the cerium-containing polymer, and thus can be more conducive to the subsequent process after the formation of the cerium oxide layer because the film has a higher flatness.

In general, features are trade-offs with each other. However, by satisfying both of Equations 1 and 2 by the control structure, the ruthenium-containing polymer for the ruthenium dioxide layer according to one embodiment can simultaneously satisfy the etch resistance, the gap fill feature, and the planarization characteristics.

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

For example, the ruthenium-containing polymer may comprise polyazide, polyoxazane or a combination thereof, and may have a weight average molecular weight of, for example, 1,000 to 100,000, but is not limited thereto. For example, the cerium-containing polymer used to form the cerium oxide layer may have a number average molecular weight of 500 to 10,000, but is not limited thereto.

On the other hand, the ruthenium-containing polymer may contain, for example, a moiety represented by Chemical Formula A. [Chemical Formula A]

In Chemical Formula A, R ₁ to R _{3 are} independently hydrogen, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C3 to C30 cycloalkyl, substituted or unsubstituted C6 To a C30 aryl, substituted or unsubstituted C7 to C30 arylalkyl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C2 to C30 heterocycloalkyl, Substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted alkoxy, carboxy, aldehyde, hydroxy or a combination thereof, and "*" indicate a point of attachment.

For example, the ruthenium containing polymer can be a polyazane produced by the reaction of a halogenated decane with ammonia.

For example, the cerium-containing polymer used in the composition for forming the cerium oxide layer may further contain a portion represented by Chemical Formula B, in addition to the portion represented by Chemical Formula A. [Chemical Formula B]

R ₄ to R _{7 of} formula B are independently hydrogen, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C3 to C30 cycloalkyl, substituted or unsubstituted C6 to C30 Aryl, substituted or unsubstituted C7 to C30 arylalkyl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C2 to C30 heterocycloalkyl, substituted or Unsubstituted C2 to C30 alkenyl, substituted or unsubstituted alkoxy, carboxy, aldehyde, hydroxy or a combination thereof, and "*" indicate a point of attachment.

In this case, in addition to the cerium-nitrogen (Si-N) bonding moiety, the cerium-containing polymer contains a cerium-oxygen-strontium (Si-O-Si) bonding moiety in its structure, and thus 矽-oxygen-矽 ( The Si-O-Si) bonding portion can reduce the stress during curing by heat treatment and shrinkage shrinkage.

For example, the ruthenium-containing polymer contains a moiety represented by Chemical Formula A and a moiety represented by Chemical Formula B, and may further include a moiety represented by Chemical Formula C. [Chemical Formula C]

The portion represented by the chemical formula C has a structure in which the terminal is terminated with hydrogen, and may be contained in an amount of 15 to 35 % by weight based on the total amount of the Si-H bond of the polyazane or the polyoxazide structure. When a portion of the chemical formula C is contained in the polyazide or polyoxazide structure within the range, the SiH ₃ portion is prevented from being partially dispersed to the SiH ₄ while the oxidation reaction is sufficiently performed during the heat treatment, and the filler pattern is prevented. Cracks appear in the middle.

The rhodium-containing polymer may be included in an amount of from 0.1% by weight to 50% by weight, such as from 0.1% by weight to 30% by weight, based on the total amount of the composition for forming the cerium oxide layer. When it is included within the range, it maintains an appropriate viscosity and produces a flat and uniform layer without gaps (voids).

The solvent for forming the composition of the ceria layer may be, but not limited to, any solvent that can dissolve the ruthenium-containing polymer, and particularly may include at least one selected from the group consisting of benzene, toluene, xylene, Ethylbenzene, diethylbenzene, trimethylbenzene, triethylbenzene, cyclohexane, cyclohexene, decahydronaphthalene, dipentene, pentane, hexane, heptane, octane, decane, decane, ethyl Cyclohexane, methylcyclohexane, p-menthane, dipropyl ether, dibutyl ether, anisole, butyl acetate, amyl acetate, methyl isobutyl ketone, and combinations thereof.

The composition for forming the ceria layer may further comprise a thermal acid generator (TAG).

The thermal acid generator may be an additive for improving the developing characteristics of the composition for forming the ceria layer, and thus the polymer of the composition is developed at a relatively low temperature.

If the thermal acid generator generates an acid (H ⁺ ) due to heat, it may contain any compound without particular limitation. Specifically, it may comprise a compound that is activated at 90 ° C or higher and produces sufficient acid and low volatility.

The thermal acid generator can be selected, for example, from nitrobenzyl toluenesulfonate, nitrobenzyl benzenesulfonate, phenolsulfonate, and combinations thereof.

The thermal acid generator may be included in an amount of 0.01 to 25% by weight based on the total amount of the composition for forming the ceria layer. Within the stated range, the polymer can be developed at low temperatures while having improved coating characteristics.

The composition for forming the ceria layer may further comprise a surfactant.

The surfactant is not particularly limited, and may be, for example, a nonionic surfactant such as a polyoxyethylene alkyl ether such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene 16 Alkyl ether, polyoxyethylene oleyl ether and the like; polyoxyethylene alkyl allyl ether, such as polyoxyethylene nonylphenol ether and the like; polyoxyethylene polyoxypropylene block copolymer; polyoxygen Ethylene sorbitol fatty acid esters such as sorbitan monolaurate, sorbitol monopalmitate, sorbitan monostearate, sorbitan monooleate, polyoxyethylene sorbitan monostearate, polyoxygen Ethylene sorbitol trioleate, polyoxyethylene sorbitan tristearate and the like; fluorosurfactant of EFTOP EF301, EFTOP EF303, EFTOP EF352 (Tochem Products Co., Ltd.) )), Magna FIS F171 (MEGAFACE F171), Magnus F173 (Dainippon Ink & Chem., Inc.), Flora FC430 (FLUORAD FC430), Fluorola FC431 ( Sumitomo 3M (Sumitomo 3M)), Asahi Protection AG710 (As Ahi guard AG710), Sorong S-382 (Surflon S-382), SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.) and the like; other anthrones A surfactant such as an organic siloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.) and the like.

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 the cerium oxide layer. Within the range, the dispersion of the solution can be improved, and at the same time, the uniform thickness of the layer can be improved.

The composition for forming the cerium oxide layer may be a solution obtained by dissolving the cerium-containing polymer and components in a mixed solvent.

In accordance with another embodiment of the present invention, a method for fabricating a ruthenium dioxide layer includes: coating a composition for forming a ruthenium dioxide layer on a substrate; and drying coating the layer for forming a ruthenium dioxide layer The substrate of the composition; and the resultant is cured under an inert gas atmosphere of 150 ° C or higher.

For example, the composition for forming the ceria layer can be applied by a solution method such as a spin coating method, a slit coating, or an inkjet printing.

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

According to another embodiment of the invention, the cerium oxide layer comprises a cerium oxide component obtained by converting a cerium-containing polymer for use in a cerium oxide layer.

The ruthenium dioxide layer may be, for example, an insulating layer, a separator layer or a hard coat layer, but is not limited thereto.

The present invention provides an electronic device comprising a ruthenium dioxide layer. The electronic device can be, for example, a display device such as an LCD or LED; or a semiconductor device.

The following examples illustrate embodiments of the invention in more detail. However, these examples are exemplary, and the invention is not limited thereto.

Preparation of a composition for forming a ruthenium dioxide layer

Polymerization Comparative Example 1 used dry nitrogen instead of the inside of a 3 liter reactor equipped with a stirrer and a temperature controller. 2,000 grams of dry pyridine was placed in the reactor and the mixture was kept warm at 0 °C. Subsequently, 100 g of dichloromethane was slowly added thereto over one hour. 85 g of ammonia was slowly injected into it over 12 hours while stirring the obtained mixture. Next, dry nitrogen gas was injected into the reactor for 120 minutes, and ammonia gas remaining in the reactor was removed.

The obtained white slurry phase product was filtered through a 1 micron Teflon filter under a dry nitrogen atmosphere to obtain 1,000 g of a filtered solution. Next, 1,000 g of dry xylene was added thereto, and the mixture was adjusted to have a solid concentration of 30% by weight by solvent exchange of a total of three times pyridine to xylene with a rotary evaporator, and then Teflon having a pore diameter of 0.03 μm was used. Filter filtered.

By way of procedure, a polyazaxane having a weight average molecular weight of 3,200 and (A+B)/C=4.29 was obtained.

In the present specification, the weight average molecular weight of polyazane is measured by using GPC (PLC pump 1515, RI detector 2414) produced by Waters and measured by NMR (300 MHz) generated by Bruker. (A+B)/C.

Polymerization Comparative Example 2 used dry nitrogen instead of the inside of a 3 liter reactor equipped with a stirrer and a temperature controller. 2,000 grams of dry pyridine was placed in the reactor and the mixture was kept warm at 0 °C. Subsequently, 100 g of dichloromethane was slowly added thereto over one hour. 85 g of ammonia gas was slowly injected thereto over 3 hours while stirring the obtained mixture. Next, dry nitrogen gas was injected into the reactor for 120 minutes, and ammonia gas remaining in the reactor was removed.

The obtained white slurry phase product was filtered through a 1 micron Teflon filter under a dry nitrogen atmosphere to obtain 1,000 g of a filtered solution. Next, 1,000 g of dry xylene was added thereto, and the mixture was adjusted to have a solid concentration of 30% by weight by solvent exchange of a total of three times pyridine to xylene with a rotary evaporator, and then Teflon having a pore diameter of 0.03 μm was used. Filter filtered.

By way of procedure, a polyazaxane having a weight average molecular weight of 1,800 and (A+B)/C=3.86 was obtained.

Polymerization Example 1 used dry nitrogen instead of the inside of a 3 liter reactor equipped with a stirrer and a temperature controller. 1,500 grams of dry pyridine was placed in the reactor and the mixture was kept warm at 0 °C. Subsequently, 100 g of dichloromethane was slowly added thereto over one hour. Next, 70 g of ammonia gas was slowly added thereto over 3 hours. Next, dry nitrogen gas was injected into the reactor for 120 minutes, and ammonia gas remaining in the reactor was removed.

The obtained white slurry phase product was filtered through a 1 micron Teflon filter under a dry nitrogen atmosphere to obtain 1,000 g of a filtered solution. Next, 1,000 g of dry xylene was added thereto, and the mixture was adjusted to have a solid concentration of 30% by weight by solvent exchange of a total of three times pyridine to xylene with a rotary evaporator, and then Teflon having a pore diameter of 0.03 μm was used. Filter filtered.

By the procedure, a polyazazane having a weight average molecular weight of 3,200 and (A+B)/C=4.84 was obtained.

Aggregation instance 2

The inside of a 3 liter reactor equipped with a stirrer and a temperature controller was replaced with dry nitrogen. 1,500 grams of dry pyridine was placed in the reactor and the mixture was kept warm at 0 °C. Subsequently, 100 g of dichloromethane was slowly added thereto over one hour. Subsequently, 70 g of ammonia gas was slowly added thereto over 3 hours. Next, dry nitrogen gas was injected into the reactor for 120 minutes, and ammonia gas remaining in the reactor was removed.

The obtained white slurry phase product was filtered through a 1 micron Teflon filter under a dry nitrogen atmosphere to obtain 1,000 g of a filtered solution. Next, 1,000 g of dry xylene was added thereto, and the mixture was adjusted to have a solid concentration of 30% by weight by solvent exchange of a total of three times pyridine to xylene with a rotary evaporator, and then Teflon having a pore diameter of 0.03 μm was used. Filter filtered.

300 g of dry pyridine was placed in the filtration solution and the resultant was heated to 100 ° C until its weight average molecular weight was 5,400.

By the procedure, a polyazaxane having a weight average molecular weight of 5,400 and (A+B)/C=5.46 was obtained.

Polymerization Example 3 A polyxazane polymer having a weight average molecular weight of 11,200 and (A+B)/C=6.10 was obtained by the same procedure as in Polymerization Example 2.

Polymerization Example 4 A polyazazane polymer having a weight average molecular weight of 22,400 and (A+B)/C=6.70 was obtained by the same procedure as in Polymerization Example 2.

Polymerization Example 5 A polyazazane polymer having a weight average molecular weight of 64,200 and (A+B)/C=7.22 was obtained by the same procedure as in Polymerization Example 2.

Polymerization Example 6 A polymer having a weight average molecular weight of 98,000 and (A+B)/C=8.52 was obtained via the same procedure as in Polymerization Example 2.

Polymerization Example 7 used dry nitrogen instead of the inside of a 3 liter reactor equipped with a stirrer and a temperature controller. 1,500 grams of dry pyridine was placed in the reactor and the mixture was kept warm at 10 °C. Subsequently, 100 g of dichloromethane was slowly added thereto over one hour. 50 g of ammonia gas was slowly injected thereto over 6 hours while stirring the obtained mixture. Next, dry nitrogen gas was injected into the reactor for 120 minutes, and ammonia gas remaining in the reactor was removed.

The obtained white slurry phase product was filtered through a 1 micron Teflon filter under a dry nitrogen atmosphere to obtain 1,000 g of a filtered solution. Next, 1,000 g of dry xylene was added thereto, and the mixture was adjusted to have a solid concentration of 30% by weight by solvent exchange of a total of three times pyridine to xylene with a rotary evaporator, and then Teflon having a pore diameter of 0.03 μm was used. Filter filtered.

300 g of dry pyridine was placed in the filtration solution and the resultant was heated to 100 ° C until its weight average molecular weight was 3,400.

By way of procedure, a polyazaxane having a weight average molecular weight of 3,400 and (A+B)/C=8.12 was obtained.

Measurement of the peak areas of SiH , SiH ₂ , SiH ₃ and NH in the ¹ H-NMR spectrum. Each of the ruthenium-containing polymers obtained from the polymerizations Comparative Examples 1 to 2 and Polymerization Examples 1 to 7 was added to a dibutyl ether (DBE) solvent. To prepare Sample 1 having a solid content of 15 ± 0.1% by weight. Subsequently, 3 cubic centimeters of sample 1 was taken and dispensed in a 8 inch diameter tantalum wafer (LG Siltron) center using a spin coater (MS-A200, MIKASA Co., Ltd.). And spinning at 1,500 rpm for 5 minutes to provide a film on the ruthenium wafer. The obtained film was taken with a cutter and the film was mixed with a CDCl ₃ (chloroform-d) solvent to provide a solution. The amount of the film was adjusted to 3.0% by weight based on the total amount of the solution to provide Sample 2. Subsequently, Sample 2 was measured for ¹ H-NMR spectroscopy at 300 MHz.

The peak area in the range of greater than or equal to 4.5 ppm to less than 5.5 ppm in the ¹ H-NMR spectrum is defined as the peak area (A) of SiH and SiH _{2 ;} the peak area in the range of 3.8 ppm or more to less than 4.5 ppm The peak area (B) defined as SiH _{3 ;} the peak area greater than or equal to 0.2 ppm to less than 2.5 ppm is defined as the peak area (C) of NH; thus, B/A and (A+B)/C are each calculated.

The results are shown in Table 1. (Table 1)

Referring to Table 1, it is understood that when the ¹ H-NMR spectrum was measured, the ruthenium-containing polymers of Comparative Examples 1, 2 and Polymerization Examples 1 to 7 satisfied the ranges set by the following Equations 1 and 2. [Equation 1] B/A = 0.2 to 0.4 [Equation 2] (A+B)/C = 4.8 to 12.0

Preparation of a composition for forming a ruthenium dioxide layer

Comparative Examples 1 and 2 used a rotary evaporator, and each solvent obtained by polymerizing the polyazoxanes of Comparative Comparative Examples 1 and 2 was replaced with dibutyl ether to provide a cerium oxide layer having a solid content of 15% by weight. Each composition.

Examples 1 to 7 used a rotary evaporator, and each solvent of the polyazane obtained from the polymerization examples 1 to 7 was replaced with dibutyl ether to provide each of the layers for forming a cerium oxide having a solid content of 15% by weight. Composition.

Evaluation 1 : Film flatness According to Comparative Examples 1 and 2 and Examples 1 to 7, the composition for the ceria layer was respectively obtained by 3 cm 3 , and then with a spin coater, the center of the 8-inch diameter crucible wafer was omitted. And spin coating at 1500 rpm for 20 seconds (MS-A200, Sanken Company). Subsequently, the coated wafer was heated on a hot plate at 150 ° C for 3 minutes and dried to form a cerium oxide layer.

Next, the thickness of the cerium oxide layer was measured by using a reflection spectroscopy film thickness meter (ST-5000, K-MAC) as shown in FIG. 2 at nine positions on the cross-shaped (+) wafer. The average thickness, the thickness range (minimum thickness - maximum thickness), and thickness uniformity of the cerium oxide layer were obtained, and the film flatness of the cerium oxide layer was obtained by the following equation.

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

The results are shown in Table 2. (Table 2)

Referring to Table 2, it should be understood that Examples 1 through 7 have relatively low film flatness compared to Comparative Examples 1 and 2. This shows that the cerium oxide layer obtained from the composition containing the polyazide polymer (B/A and (A+B)/C satisfies the predetermined range) has a relatively uniform thickness, as in Examples 1 to 7.

Evaluation 2 : Gap fill feature

Each of the compositions for forming a ceria-based layer according to Comparative Examples 1 and 2 and Examples 1 to 7 was coated on a patterned tantalum wafer and baked to provide a film. Subsequently, its cross section was attached to the holder and platinum sputtering (Pt sputtering) was performed at 6 mA for 8 seconds using an HR applicator. The pretreated sample was observed using an electron microscope (S5500, Hitachi) at a value of 100,000.

The results are shown in Table 3 and Figures 3 and 4. (table 3)

As shown in Table 3, it should be understood that the compositions for forming a ceria-based layer according to Examples 1 to 7 showed "good" gap-filling feature results, and on the other hand, according to Comparative Examples 1 and 2 The composition forming the cerium oxide layer shows a "poor" gap filling feature result.

This shows that the layer formed of the composition containing the polyazide polymer (B/A and (A+B)/C satisfies the predetermined range) has excellent gap filling characteristics.

In addition, as shown in FIGS. 3 and 4, it was confirmed that the gap filling of the ceria layer obtained from Example 2 was better formed than the ceria layer obtained in Comparative Example 2.

Evaluation 3 : Etching resistance of cerium oxide layer ( Compactness ) evaluation of

Each of the compositions for forming a ceria-based layer according to Comparative Examples 1 and 2 and Examples 1 to 7 was spin-coated on a pattern wafer (manufactured by Sanken, MS-A200) having a size of 3 cm × 3 cm. It was then soft baked at 150 ° C for 3 minutes. Subsequently, it was carried out together with a high-temperature oxidation reaction to convert the composition into an oxide layer at 800 ° C and then immersed in an aqueous solution (DHF 100:1) in which hydrofluoric acid and ammonium fluoride were mixed for 5 minutes. The pattern was then etched into dimensions of 40 nm, 100 nm, and 200 nm, respectively, and the amount of etching inside the gap (ie, inside the pattern) formed was calculated according to trigonometry (manufactured by Hitachi: S-5500).

According to the same method, a polyazane solution was spin-coated on a bare wafer and soft baked at 150 ° C for 3 minutes. Subsequently, it was carried out together with a high-temperature oxidation reaction to convert the composition into an oxide layer at 800 ° C, and the thickness thereof was measured. It was then immersed in an aqueous solution (DHF 100:1) in which hydrofluoric acid and ammonium fluoride were mixed for 5 minutes, and then the etched surface was measured by a reflection spectral film thickness meter (ST-5000) manufactured by K-MAC. The thickness and the amount of etching of the outer surface were calculated to find the compactness of the inner oxide layer.

The density of the internal oxide layer is obtained as follows:

Density of the inner oxide layer = amount of etching of the outer surface / amount of etching inside the pattern

The results are shown in Table 4. (Table 4)

As shown in Table 4, it was confirmed that the composition according to Examples 1 to 7 had a pole inside the gap in all the patterns each having a size of less than or equal to 200 nm, as compared with the case of using the compositions according to Comparative Examples 1 and 2. The situation of good compactness.

Although the present invention has been described in connection with what is presently considered as a practical example embodiment, it is understood that the invention is not limited to the disclosed embodiments, but rather, the invention is intended to cover the spirit and scope of the appended claims Various modifications and equivalent configurations are included.

1 is a reference diagram illustrating the degree of crosslinking of a ruthenium-containing polymer by quantifying the peak areas of SiH, SiH ₂ , SiH _{3 ,} and NH _1,2 under a ¹ H-NMR spectrum of a ruthenium-containing polymer. 2 is a reference diagram illustrating a method of evaluating thickness uniformity of each layer obtained by using the compositions according to Examples 1 to 7 and Comparative Examples 1 and 2. 3 is an electron micrograph of the ceria layer obtained from Example 2. 4 is an electron microscopic image of the ceria layer obtained in Comparative Example 2.

Claims (10)

A composition for forming a ruthenium dioxide layer, comprising: a ruthenium-containing polymer and a solvent, wherein a ¹ H-NMR spectrum of the ruthenium-containing polymer satisfies Equations 1 and 2: [Equation 1] B/A = 0.2 to 0.4 [Equation 2] (A+B)/C = 4.8 to 12.0 where, in Equation 1 and Equation 2, A is a peak area greater than or equal to 4.5 ppm and less than 5.5 ppm, and B is greater than or A peak area equal to 3.8 ppm and less than 4.5 ppm, and C is a peak area greater than or equal to 0.2 ppm and less than 2.5 ppm: The constraint is that the ¹ H-NMR spectrum is measured according to Condition 1: [Condition 1] Polymerization containing ruthenium Adding to dibutyl ether solvent to prepare sample 1 having a solid content of 15 ± 0.1% by weight, obtaining 3 cubic centimeters of sample 1, and dispensing the sample 1 at a center of a diameter of 8 inches using a spin coater, and It was rotated at 1,500 rpm for 5 minutes to form a film on the ruthenium wafer, the film was taken with a cutter, and the obtained film was mixed with a CDCl ₃ solvent to prepare a solution, and Sample 2 was prepared, wherein The content of the film obtained was 3.0% by weight based on the total amount of the solution, and at 300 MHz. The ¹ H-NMR spectrum of the sample 2 was measured. The composition for forming a cerium oxide layer according to claim 1, wherein in the formula 2, (A+B)/C is in the range of 5.0 to 10.5. The composition for forming a ceria layer as described in claim 2, wherein in the formula 2, (A+B)/C is in the range of 5.2 to 9.0. The composition for forming a cerium oxide layer according to claim 1, wherein the cerium-containing polymer comprises polyazane, polyoxazane or a combination thereof. The composition for forming a cerium oxide layer according to claim 1, wherein the cerium-containing polymer has a weight average molecular weight of 1,000 to 100,000. The composition for forming a cerium oxide layer according to claim 1, wherein the cerium-containing polymer has a number average molecular weight of 500 to 10,000. The composition for forming a cerium oxide layer according to claim 1, wherein the solvent comprises benzene, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, triethylbenzene, and cyclohexane. Alkane, cyclohexene, decahydronaphthalene, dipentene, pentane, hexane, heptane, octane, decane, decane, ethylcyclohexane, methylcyclohexane, p-menthane, dipropyl At least one selected from the group consisting of ether, dibutyl ether, anisole, butyl acetate, amyl acetate, methyl isobutyl ketone, and combinations thereof. The composition for forming a cerium oxide layer according to claim 1, wherein the cerium-containing polymer is 0.1% by weight based on the total amount of the composition for forming the cerium oxide layer. An amount of up to 30% by weight is included. A cerium oxide layer made of a composition for forming a cerium oxide layer as described in claim 1 of the patent application. An electronic device comprising the ceria layer as described in claim 9 of the patent application.