KR102211158B1 - Semiconductor resist composition, and method of forming patterns using the composition - Google Patents

Abstract

상기 화학식 1에 대한 구체적인 내용은 명세서 상에서 정의된 것과 같다. The present description relates to a composition for a semiconductor resist comprising an organometallic compound represented by the following Chemical Formula 1 and a solvent, and a pattern forming method using the same.
[Formula 1]

Specific details for Formula 1 are as defined in the specification.

Description

A composition for semiconductor resist and a pattern formation method using the same {SEMICONDUCTOR RESIST COMPOSITION, AND METHOD OF FORMING PATTERNS USING THE COMPOSITION}

The present description relates to a composition for a semiconductor resist and a pattern forming method using the same.

As one of the element technologies for manufacturing next-generation semiconductor devices, EUV (extreme ultraviolet light) lithography is drawing attention. EUV lithography is a pattern formation technique using EUV light having a wavelength of 13.5 nm as an exposure light source. According to EUV lithography, it has been demonstrated that extremely fine patterns (for example, 20 nm or less) can be formed in the exposure process of the semiconductor device manufacturing process.

Implementation of extreme ultraviolet (EUV) lithography requires the development of compatible photoresists capable of performing at spatial resolutions of 16 nm or less. Currently, traditional chemically amplified (CA) photoresists are the resolution, photospeed, and feature roughness (also called line edge roughness or LER) for next generation devices. We are working to meet the specifications for

The inherent intrinsic image blur due to acid catalyzed reactions occurring in these polymeric photoresists limits the resolution at small feature sizes, which is the e-beam. It has been known for a long time in lithography. Chemically amplified (CA) photoresists are designed for high sensitivity, but because their typical elemental makeup lowers the absorbance of the photoresists at a wavelength of 13.5 nm, and consequently reduces the sensitivity, in part. It can be more difficult under EUV exposure.

CA photoresists can also suffer from roughness issues at small feature sizes and, in part due to the nature of acid catalytic processes, line edge roughness (LER) as the photospeed decreases. It has been shown by the experiment that is increasing. Due to the shortcomings and problems of CA photoresists, there is a need in the semiconductor industry for a new type of high performance photoresists.

One embodiment provides a composition for a semiconductor resist with high sensitivity and easy handling.

Another embodiment provides a pattern forming method using the semiconductor resist composition.

The composition for a semiconductor resist according to an embodiment includes an organometallic compound represented by Formula 1 below, and a solvent.

[Formula 1]

In Formula 1,

X ₁ to X ₂ are each independently a single bond, a substituted or unsubstituted C1 to C6 alkylene group, a substituted or unsubstituted phenylene group, -O-, -CO- ring, -NR _a - (R _a is hydrogen, substituted Or an unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group), and

Y ₁ to Y ₂ are each independently selected from hydrogen, a substituted or unsubstituted C1 to C6 alkyl group, and a substituted or unsubstituted phenyl group,

R ₁ to R ₄ are each independently hydrogen, a substituted or unsubstituted C1 to C6 alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted C1 to C6 alkenylene group, a substituted or unsubstituted C1 to C6 An alkynylene group, a substituted or unsubstituted C1 to C6 alkenyl alkyl group, a substituted or unsubstituted C1 to C6 alkynyl alkyl group, and

However, when R ₁ to R ₄ and Y ₁ to Y ₂ do not contain an unsaturated double bond, 2 or more of R ₁ , R ₂ , and Y ₁ and 2 or more of R ₃ , R ₄ and Y ₂ are each substituted Or it may be an unsubstituted C1 to C6 alkyl group,

2 ≤ n ≤ 100000.

The method of forming a pattern according to another embodiment includes forming an etching target layer on a substrate, forming a photoresist layer by applying the above-described semiconductor resist composition on the etching target layer, and patterning the photoresist layer to form a photoresist pattern. And etching the etching target layer by using the photoresist pattern as an etching mask.

The composition for a semiconductor resist according to an exemplary embodiment is relatively easy to handle and has excellent storage stability, and by using this, it is possible to provide a photoresist pattern in which the pattern does not collapse even if it has a high aspect ratio.

1 to 5 are cross-sectional views illustrating a method of forming a pattern using a composition for a semiconductor resist according to an embodiment.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, in describing the present description, descriptions of functions or configurations that are already known will be omitted in order to clarify the gist of the present description.

In order to clearly describe the present description, parts irrelevant to the description are omitted, and the same reference numerals are attached to the same or similar components throughout the specification. In addition, the size and thickness of each component shown in the drawings are arbitrarily shown for convenience of description, so the present description is not necessarily limited to the illustrated bar.

In the drawings, the thicknesses are enlarged to clearly express various layers and regions. In addition, the thicknesses of some layers and regions are exaggerated in the drawings for convenience of description. When a part of a layer, film, region, plate, etc. is said to be "on" or "on" another part, this includes not only the case where the other part is "directly above" but also the case where there is another part in the middle.

In the present description, "substituted" means a substituent selected from the group consisting of a halogen group, a C1 to C30 alkyl group, a C1 to C30 haloalkyl group, a C6 to C30 aryl group, a C1 to C20 alkoxy group, and combinations thereof. It means substituted with, and "unsubstituted" means that a hydrogen atom remains as a hydrogen atom without being substituted with another substituent.

The composition for a semiconductor resist according to an embodiment of the present invention includes an organometallic compound and a solvent.

The organometallic compound has various ligands bonded to a central metal atom located at the center, and is represented by the following formula (1).

[Formula 1]

In Formula 1,

X ₁ to X ₂ are each independently a single bond, a substituted or unsubstituted C1 to C6 alkylene group, a substituted or unsubstituted phenylene group, -O-, -CO- ring, -NR _a - (R _a is hydrogen, substituted Or an unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group), and

Y ₁ to Y ₂ are each independently selected from hydrogen, a substituted or unsubstituted C1 to C6 alkyl group, and a substituted or unsubstituted phenyl group,

R ₁ to R ₄ are each independently hydrogen, a substituted or unsubstituted C1 to C6 alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted C1 to C6 alkenylene group, a substituted or unsubstituted C1 to C6 An alkynylene group, a substituted or unsubstituted C1 to C6 alkenyl alkyl group, a substituted or unsubstituted C1 to C6 alkynyl alkyl group, and

However, when R ₁ to R ₄ and Y ₁ to Y ₂ do not contain an unsaturated double bond, 2 or more of R ₁ , R ₂ , and Y ₁ and 2 or more of R ₃ , R ₄ and Y ₂ are each substituted Or it may be an unsubstituted C1 to C6 alkyl group,

2 ≤ n ≤ 100000.

For example, X ₁ to X ₂ may each independently be selected from a single bond, a substituted or unsubstituted C1 to C6 alkylene group, a substituted or unsubstituted phenylene group, or a combination thereof.

For example, R ₁ to R ₄ are each independently hydrogen, a substituted or unsubstituted C1 to C6 alkyl group, a substituted or unsubstituted C1 to C6 alkenylene group, a substituted or unsubstituted C1 to C6 alkenyl alkyl group, It can be one selected.

The organometallic compound according to an embodiment has two organic groups bonded to one metal (tin) in one structural unit.

In one embodiment, R ₁ , R ₂ and Y ₁ (or R ₃ , R ₄ and Y ₂ ) may have a branched chain structure.

When the ends of the organic groups connected to the organometallic compound are connected to have a branched chain as described above, the ends of each organic group have a bulky three-dimensional structure. The degree of bulky at the end of the organic group may be varied by adjusting the type and number of carbon atoms of the aforementioned substituents of R ₁ to R ₄ and Y ₁ to Y ₂ .

For example, in Formula 1, R ₁ , R ₂ and Y ₁ (or R ₃ , R ₄ and Y ₂ ) are substituted or unsubstituted hydrocarbon groups (alkyl groups, phenyl groups, alkenylene groups, alkynylene groups, alkenyl alkyl groups) , Alkynyl alkyl group). In one embodiment, it is preferable to adjust the number of carbon atoms of R ₁ , R ₂ and Y ₁ (or R ₃ , R ₄ and Y ₂ ) to 1 to 6.

As described above, when the terminal of the organic group has a bulky three-dimensional structure, the sensitivity of the organometallic compound to extreme ultraviolet (EUV) can be improved.

Meanwhile, the organometallic compound according to another embodiment is represented by the above-described Chemical Formula 1, but each organic group may have an ethylenic double bond. The formation position of the ethylenic double bond is not particularly limited, but may be formed at any position inside each organic group. For example, the ethylenic double bond may be formed at the ends of each organic group, or may be formed inside each of the organic groups. For example, the carbon bonded to the X position, the R position, and the Y position may be carbon forming an ethylenic double bond.

The organometallic compound according to another embodiment may be represented by Formula 2 below.

[Formula 2]

In Formula 2,

X ₃ to X ₄ are each independently a single bond, a substituted or unsubstituted C1 to C6 alkylene group, a substituted or unsubstituted phenylene group, -O-, -CO-, -NR _b- (R _b is hydrogen, substituted Or an unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group), and

Y ₃ to Y ₄ are each independently selected from hydrogen, a substituted or unsubstituted C1 to C6 alkyl group, and a substituted or unsubstituted phenyl group,

R ₅ to R ₈ are each independently selected from hydrogen, a substituted or unsubstituted C1 to C6 alkyl group, and a substituted or unsubstituted phenyl group,

2 ≤ n ≤ 100000.

For example, X ₃ to X ₄ may each independently be one selected from a single bond, a substituted or unsubstituted C1 to C6 alkylene group.

For example, at least one of R ₅ and R ₆ and at least one of R ₇ and R ₈ may each be a substituted or unsubstituted C1 to C6 alkyl group.

In another embodiment, the organometallic compound has an ethylenic double bond in each organic group. The ethylenic double bond can improve the sensitivity of the organometallic compound to EUV, while generating radicals by EUV. Therefore, the generated radical acts to form an additional crosslinked structure at the ethylenic double bond position in the organometallic compound. As a result, if the organometallic compound according to another embodiment is used, a photoresist pattern having a more dense structure can be formed.

The organometallic compound represented by Formula 1 above has a bulky three-dimensional structure at the end of the organic group, as represented by any one of the following Formulas 3 to 8, or an organic tin containing an ethylenic double bond inside the organic group. Can be a compound:

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

In Chemical Formulas 3 to 8, 2≦n≦100000.

In the semiconductor resist composition according to an embodiment, the organometallic compound represented by Formula 1 may be included in an amount of 0.01% to 10% by weight based on the total weight of the composition. When included in such an amount, storage stability is excellent and thin film formation is easy.

Meanwhile, the solvent included in the semiconductor resist composition according to the embodiment may be an organic solvent, and as an example, an alcohol-based solvent may be used. The alcohol-based solvent may be, for example, 4-methyl-2-pentanol, but is not limited thereto.

In one embodiment, the semiconductor resist composition according to the embodiment may further include a resin in addition to the organometallic compound and the solvent.

The resin may be a phenolic resin including at least one aromatic moiety listed in Group 1 below.

[Group 1]

The resin may have a weight average molecular weight of 500 to 20,000.

The resin may be included in an amount of 0.1% to 50% by weight based on the total content of the composition for semiconductor resist.

When the resin is contained in the above content range, it may have excellent etch resistance and heat resistance.

On the other hand, the composition for a semiconductor resist according to an embodiment is preferably made of the above-described organometallic compound, a solvent, and a resin. However, the composition for a semiconductor resist according to the above-described embodiment may further include an additive in some cases. Examples of the additives include surfactants, crosslinking agents, and leveling agents.

Surfactants may be, for example, alkylbenzenesulfonic acid salts, alkylpyridinium salts, polyethylene glycols, quaternary ammonium salts, and the like, but are not limited thereto.

The crosslinking agent may be, for example, melamine-based, substituted urea-based, or these polymer-based, but is not limited thereto. A crosslinking agent having at least two crosslinking substituents, for example, methoxymethylated glycoruryl, butoxymethylated glycoruryl, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine , Methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or methoxymethylated thiourea may be used.

The leveling agent is for improving coating flatness during printing, and a known leveling agent available in a commercial way may be used.

The amount of these additives used may be easily adjusted according to desired physical properties, or may be omitted.

In addition, the semiconductor resist composition may further use a silane coupling agent as an additive as an adhesion promoter to improve adhesion to the substrate. The silane coupling agent is, for example, vinyl trimethoxysilane, vinyl triethoxysilane, vinyl trichlorosilane, vinyl tris (β-methoxyethoxy) silane; Or 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryl trimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldi Ethoxysilane; A silane compound containing a carbon-carbon unsaturated bond, such as trimethoxy[3-(phenylamino)propyl]silane, may be used, but is not limited thereto.

In the semiconductor resist composition, pattern collapse may not occur even when a pattern having a high aspect ratio is formed. Thus, for example, a fine pattern having a width of 5 nm to 100 nm, for example, a fine pattern having a width of 5 nm to 80 nm, for example, a fine pattern having a width of 5 nm to 70 nm, for example, Fine pattern having a width of 5 nm to 60 nm, for example, a fine pattern having a width of 5 nm to 50 nm, for example, a fine pattern having a width of 5 nm to 40 nm, for example, having a width of 5 nm to 30 nm A photoresist process using light of a wavelength of 5 nm to 150 nm, for example, a photoresist process using light of a wavelength of 5 nm to 100 nm to form a fine pattern, for example, a fine pattern having a width of 5 nm to 20 nm , For example, a photoresist process using light of a wavelength of 5nm to 80nm, for example, a photoresist process using light of a wavelength of 5nm to 50nm, for example, a photoresist using light of a wavelength of 5nm to 30nm It can be used in a process, for example, a photoresist process using light having a wavelength of 5 nm to 20 nm. Therefore, if the composition for a semiconductor resist according to an embodiment is used, extreme ultraviolet lithography using an EUV light source having a wavelength of about 13.5 nm can be implemented.

Meanwhile, according to another embodiment, a method of forming a pattern using the above-described composition for a semiconductor resist may be provided. For example, the manufactured pattern may be a photoresist pattern.

In one embodiment, another pattern formation method includes forming an etching target layer on a substrate, forming a photoresist layer by applying the above-described semiconductor resist composition on the etching target layer, and patterning the photoresist layer to form a photoresist pattern. And etching the etching target layer by using the photoresist pattern as an etching mask.

Hereinafter, a method of forming a pattern using the above-described semiconductor resist composition will be described with reference to FIGS. 1 to 5. 1 to 5 are cross-sectional views illustrating a method of forming a pattern using a composition for a semiconductor resist according to the present invention.

Referring to FIG. 1, first, an object to be etched is prepared. An example of the object to be etched may be the thin film 102 formed on the semiconductor substrate 100. Hereinafter, only the case where the object to be etched is the thin film 102 will be described. The surface of the thin film 102 is pre-cleaned to remove contaminants and the like remaining on the thin film 102. The thin film 102 may be, for example, a silicon nitride film, a polysilicon film, or a silicon oxide film.

Subsequently, a composition for forming a resist underlayer film for forming the resist underlayer film 104 on the cleaned surface of the thin film 102 is coated by applying a spin coating method.

The resist underlayer coating process may be omitted. Hereinafter, a case of coating the resist underlayer layer will be described.

Thereafter, drying and baking processes are performed to form a resist underlayer 104 on the thin film 102. The baking treatment may be performed at about 100 to about 500°C, and for example, at about 100 to about 300°C.

The resist underlayer film 104 is formed between the substrate 100 and the photoresist film 106, so that irradiation rays reflected from the interface between the substrate 100 and the photoresist film 106 or an interlayer hardmask are not intended. In the case of scattering into the uneven photoresist region, it is possible to prevent unevenness of the photoresist linewidth and disturbance of pattern formation.

Referring to FIG. 2, a photoresist film 106 is formed by coating the above-described semiconductor resist composition on the resist underlayer film 104. The photoresist layer 106 may be formed by coating the above-described composition for semiconductor resist on the thin film 102 formed on the substrate 100 and then curing through a heat treatment process.

More specifically, the step of forming a pattern using the composition for semiconductor resist is a process of applying the above-described composition for semiconductor resist on the substrate 100 on which the thin film 102 is formed by spin coating, slit coating, inkjet printing, etc. And drying the applied semiconductor resist composition to form a photoresist film 106.

Since the semiconductor resist composition has already been described in detail, redundant descriptions will be omitted.

Subsequently, a first baking process of heating the substrate 100 on which the photoresist film 106 is formed is performed. The first baking process may be performed at a temperature of about 80°C to about 120°C.

3, the photoresist film 106 is selectively exposed.

As an example, examples of light that can be used in the exposure process include light having a long wavelength such as i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), as well as EUV (Extreme UltraViolet; Wavelength 13.5 nm), E-Beam (electron beam), and other high-energy light having a short wavelength.

More specifically, the exposure light according to an embodiment may be a short wavelength light having a wavelength range of 5 nm to 150 nm, and the number of light having a high energy short wavelength such as EUV (Extreme UltraViolet; wavelength 13.5 nm), E-Beam (electron beam), etc. have.

As described above, the exposed region 106a of the photoresist film 106 forms a polymer by the dehydration and condensation reaction of the carboxyl group and the hydroxy group contained in the organometallic compound, so that the photoresist film 106 is unexposed. It has a different solubility than the region 106b.

Subsequently, a second baking process is performed on the substrate 100. The second baking process may be performed at a temperature of about 90°C to about 200°C. By performing the second baking process, the exposed region 106a of the photoresist film 106 becomes difficult to dissolve in the developer.

4 shows a photoresist pattern 108 formed by dissolving and removing the photoresist film 106b corresponding to the unexposed area using a developer. Specifically, the photoresist pattern 108 is completed by dissolving and removing the photoresist film 106b corresponding to the unexposed region using an organic solvent such as 2-heptanone.

As described above, the developer used in the pattern formation method according to the exemplary embodiment may be an organic solvent. An example of an organic solvent used in the pattern formation method according to an embodiment, ketones such as 2-heptanone and cyclohexanone, isopropanol, 4-methyl-2 pentanol Alcohols such as (4-methyl-2-pentanol), esters such as ethyl lactate, or combinations thereof.

As described above, not only light having wavelengths such as i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), but also EUV (Extreme UltraViolet; wavelength 13.5 nm), E-Beam The photoresist pattern 108 formed by exposure to light having high energy such as (electron beam) or the like may have a width of 5 nm to 100 nm. For example, the photoresist pattern 108 may be formed in a width of a thickness of 5nm to 90nm, 5nm to 80nm, 5nm to 70nm, 5nm to 60nm, 10nm to 50nm, 10nm to 40nm, 10nm to 30nm, 10nm to 20nm. have.

Subsequently, the resist underlayer 104 is etched using the photoresist pattern 108 as an etching mask. The organic layer pattern 112 is formed by the above etching process. The formed organic layer pattern 112 may also have a width corresponding to the photoresist pattern 108.

Referring to FIG. 5, the exposed thin film 102 is etched by applying the photoresist pattern 108 as an etching mask. As a result, the thin film is formed as a thin film pattern 114.

The etching of the thin film 102 may be performed by dry etching using, for example, an etching gas, and the etching gas may be CHF ₃ , CF ₄ , Cl ₂ , BCl _3, and a mixed gas thereof.

In the exposure process performed above, the thin film pattern 114 formed using the photoresist pattern 108 formed by the exposure process performed using an EUV light source may have a width corresponding to the photoresist pattern 108. . For example, the photoresist pattern 108 may have a width of 5 nm to 100 nm, the same as the photoresist pattern 108. For example, the thin film pattern 114 formed by the exposure process performed using an EUV light source is 5nm to 90nm, 5nm to 80nm, 5nm to 70nm, 5nm to 60nm, 10nm to 50nm, like the photoresist pattern 108 , 10nm to 40nm, 10nm to 30nm, may have a width of 10nm to 20nm, and more specifically, may be formed with a width of 20nm or less.

Hereinafter, the present invention will be described in more detail through examples of the synthesis of the above-described polymer and the preparation of a composition for a semiconductor resist including the same. However, the technical limitations of the present invention are not limited by the following examples.

Synthesis Example 1

After dissolving tin (IV) chloride (10g, 38 mmol) in 100 mL of anhydrous toluene, put it in an ice bath and stirred while slowly adding 20 mL of a 2M solution of isopropyl Magnesium Bromide (i-PrMgBr). I did. After raising the reaction temperature to room temperature, stirring was performed for 24 hours. Thereafter, water was slowly added to the stirred mixture to decompose unreacted i-PrMgBr, and the resulting organic layer was extracted with toluene and distilled under reduced pressure to obtain 9.9 g of tetra-isopropylstannane.

Tin (IV) chloride (4.5 g, 17 mmol) was slowly added dropwise to the obtained tetra-isopropylstanene (5 g, 17 mmol). After the dropwise addition is complete and the colorless liquid turns into a yellow liquid, the temperature is raised to a temperature of 190° C. to 200° C. and reacted for 2 hours to form a gray-colored high-viscosity substance. The formed material was solidified at room temperature and recrystallized using hexane to obtain di-isopropyltin dichloride.

After dissolving the obtained di-isopropyltindichloride (3 g, 10.9 mmol) in 30 mL of ether, 25 mL of 1M sodium hydroxide (NaOH) aqueous solution was added, followed by stirring for 1 hour. After stirring, the resulting solid was filtered and washed three times with 25 mL of deionized water, and then dried under reduced pressure at 100° C. to obtain an organometallic compound having a weight average molecular weight of 1,500, represented by the following formula (3).

[Formula 3]

Synthesis Example 2

After dissolving tin (IV) chloride (10g, 38 mmol) in 100 mL of anhydrous toluene, 20 mL of a 2M solution of t-butyl magnesium bromide was slowly added while stirring in an ice bath. . After raising the reaction temperature to room temperature, stirring was performed for 24 hours. Thereafter, water was slowly added to the stirred mixture to decompose unreacted i-PrMgBr, and the resulting organic layer was extracted with toluene and distilled under reduced pressure to obtain tetra-t-butylstannane. Then, instead of tetra-isopropylstanene, di-t-butyltin dichloride was obtained through the same procedure as in Synthesis Example 1 for the obtained tetra-t-butylstanene.

Thereafter, instead of di-isopropyltin dichloride, the obtained di-t-butyltin dichloride was subjected to the same procedure as in Synthesis Example 1 to obtain an organometallic compound having a weight average molecular weight of 1,500 represented by the following Chemical Formula 4.

[Formula 4]

Synthesis Example 3

After dissolving tin (IV) chloride (10 g, 38 mmol) in 100 mL of anhydrous toluene, 20 mL of a 2M solution of neopentyl magnesium bromide was slowly added while stirring in an ice bath and stirring. After raising the reaction temperature to room temperature, stirring was performed for 24 hours. Thereafter, water was slowly added to the stirred mixture to decompose unreacted i-PrMgBr, and the resulting organic layer was extracted with toluene and distilled under reduced pressure to obtain tetra-neopentylstannane.

Thereafter, instead of tetra-isopropylstannene, di-neopentyltin dichloride was obtained through the same procedure as in Synthesis Example 1 for the obtained tetra-neopentyltinstanene. Thereafter, instead of di-isopropyltin dichloride, the obtained di-neopentyltin dichloride was subjected to the same procedure as in Synthesis Example 1 to obtain an organometallic compound having a weight average molecular weight of 1,500, represented by the following Chemical Formula 5.

[Formula 5]

Synthesis Example 4

After dissolving tin (IV) chloride (10 g, 38 mmol) in 100 mL anhydrous toluene, put it in an ice bath and stirred while stirring, 20 mL of a 2M solution of but-2-enylmagnesium bromide Was slowly added. After raising the reaction temperature to room temperature, stirring was performed for 24 hours. Thereafter, water was slowly added to the stirred mixture to decompose unreacted i-PrMgBr, and the resulting organic layer was extracted with toluene, and distilled under reduced pressure to obtain tetra-but-2-enylstannane. ).

Then, instead of tetra-isopropylstanene, di-but-2-enyltin dichloride (di-but-2-enyltin) was carried out in the same manner as in Synthesis Example 1 for the obtained tetra-but-2-enylstanene. dichloride) was obtained.

Thereafter, instead of di-isopropyltin dichloride, the obtained di-but-2-enyltin dichloride was subjected to the same procedure as in Synthesis Example 1 to obtain an organometallic compound having a weight average molecular weight of 1,800 represented by Formula 6 below.

[Formula 6]

Synthesis Example 5

After dissolving tin (IV) chloride (10 g, 38 mmol) in 100 mL anhydrous toluene, put it in an ice bath and stirred while stirring (3-methylbut-2-enyl) magnesium bromide [(3-methylbut-2 -enyl)magnesium bromide] 2M solution 20 mL was slowly added. After raising the reaction temperature to room temperature, stirring was performed for 24 hours. Thereafter, water was slowly added to the stirred mixture to decompose the unreacted i-PrMgBr, and the organic layer produced was extracted with toluene, and distilled under reduced pressure, followed by tetrakis(3-methylbut-2-enyl)stannen [tetrakis( 3-methylbut-2-enyl)stannane] was obtained.

Thereafter, instead of tetra-isopropylstannene, the obtained tetrakis(3-methylbut-2-enyl)stannene was subjected to the same procedure as in Synthesis Example 1, and di-(3-methylbut-2-enyl)tin Dichloride [di-(3-methylbut-2-enyl)tin dichloride] was obtained. Thereafter, instead of di-isopropyltindichloride, the obtained di-(3-methylbut-2-enyl)tin dichloride was subjected to the same process as in Synthesis Example 1, and the weight average molecular weight of 1,500 A metal compound was obtained.

[Formula 7]

Synthesis Example 6

After dissolving tin (IV) chloride (10 g, 38 mmol) in 100 mL of anhydrous toluene, put it in an ice bath and stirred while stirring (2-methylallyl) magnesium bromide [(2-methylallyl)magnesium bromide] 2M solution 20 mL was slowly added. After raising the reaction temperature to room temperature, stirring was performed for 24 hours. Thereafter, water was slowly added to the stirred mixture to decompose the unreacted i-PrMgBr, and the resulting organic layer was extracted with toluene, and distilled under reduced pressure to tetrakis (2-methylallyl). stannane]. Thereafter, instead of tetra-isopropylstanene, the obtained tetrakis(2-methylallyl)stannene was subjected to the same procedure as in Synthesis Example 1 described above, and di-(2-methylallyl)tin dichloride [di-(2- methylallyl)tin dichloride] was obtained.

Thereafter, instead of di-isopropyltindichloride, the obtained di-(2-methylallyl)tin dichloride was subjected to the same procedure as in Synthesis Example 1 to obtain an organometallic compound having a weight average molecular weight of 1,500, represented by Formula 8 below. .

[Formula 8]

Comparative Synthesis Example

After dissolving dibutyltin dichloride (10 g, 33 mmol) in 30 mL of ether, 70 mL of 1M sodium hydroxide (NaOH) aqueous solution was added, followed by stirring for 1 hour. After stirring, the resulting solid was filtered, washed three times with 25 mL of deionized water, and then dried under reduced pressure at 100° C. to obtain an organometallic compound having a weight average molecular weight of 1,500, represented by the following formula (9).

Examples 1 to 6

The organometallic compounds synthesized in Synthesis Examples 1 to 6 were each dissolved in 4-methyl-2-pentanol at a concentration of 1 wt%, and then filtered through a 0.1 µm PTFE syringe filter to form a semiconductor resist. A composition for use was prepared.

A 4 inch circular silicon wafer with a native-oxide surface was used as a substrate for thin film deposition, and the substrate was pretreated for 10 minutes under a UV ozone cleaning system. Thereafter, the resist compositions for semiconductors according to Examples 1 to 6 were spin-coated on the pretreated substrate at 1500 rpm for 30 seconds, and fired on a hot plate at 100° C. for 120 seconds to form a thin film.

The thickness of the film after coating and baking was measured by ellipsometry, and the measured thickness was 20 nm.

Comparative example

After dissolving the organometallic compound synthesized in Comparative Synthesis Example at a concentration of 1 wt% in 4-methyl-2-pentanol, it was filtered through a 0.1 µm PTFE syringe filter to obtain a composition for semiconductor resist. Was prepared.

Thereafter, a thin film was formed on the substrate through the same process as in the above-described Example for the prepared composition for a semiconductor resist according to the comparative example.

The thickness of the film after coating and baking was measured by ellipsometry, and the measured thickness was 22 nm.

Electron beam exposure evaluation

In order to form a pattern on the coated substrates of Examples 1 to 6 and Comparative Examples at a dose of 1000 μC/cm ² , it was exposed to an electron beam scanning line of 50 KeV of HV voltage using a JEOL-9300 facility. The scanning line exposure was performed in a vacuum chamber. The patterned resist and the substrate were fired at 150° C. for 2 minutes (fired after exposure, PEB). Thereafter, the exposed film was developed by immersing in 2-heptanone for 30 seconds, washed in the same solvent, and a portion not exposed to the scanning line was removed to form a negative tone image. After development, it was finally baked at 180° C. for 5 minutes at high temperature.

The obtained resist pattern was evaluated as follows.

[Sensitivity]

An exposure amount for forming a line and space pattern composed of a line portion with a line width of 50 nm and a space portion of 50 nm formed between adjacent line portions is set as the optimum exposure amount, and the optimum exposure amount is the sensitivity (μC/ Cm2).

The sensitivity means that the smaller the numerical value is, the higher the sensitivity is, and it can be evaluated that 800 µC/cm 2 or less is good, and more than 1000 µC/cm 2 is not good.

[Limited Resolution]

Among the line and space patterns, the half-pitch of the pattern in which the sum of the line width and the space width is the minimum was defined as the limiting resolution (nm). The limiting resolution means that the smaller the numerical value is, the better the resolution is, and it can be evaluated that 40 nm or less is good and more than 40 nm is not good.

Table 1 shows the resolution results of the resist film.

compound After coating
Film quality uniformity PEB temperature ( ^o C) Sensitivity (μC/cm ² ) Limit resolution (nm) Example 1 Synthesis Example 1 OK 150 700 32 Example 2 Synthesis Example 2 OK 150 600 30 Example 3 Synthesis Example 3 OK 150 700 35 Example 4 Synthesis Example 4 OK 150 700 36 Example 5 Synthesis Example 5 OK 150 700 34 Example 6 Synthesis Example 6 OK 150 600 36 Comparative example Comparative Synthesis Example OK 150 1200 50

From the results of Table 1, it can be seen that when a resist pattern is formed using the resist compositions according to Examples 1 to 6, higher sensitivity and superior limit resolution are exhibited compared to the comparative examples. [0038] In the foregoing, specific embodiments of the present invention will be described. Although shown, the present invention is not limited to the disclosed embodiments, and it is apparent to those of ordinary skill in the art that various modifications and variations can be made without departing from the spirit and scope of the present invention. Therefore, such modifications or variations should not be individually understood from the technical spirit or point of view of the present invention, and the modified embodiments should be said to belong to the claims of the present invention.

100: substrate 102: thin film
104: resist underlayer film 106: photoresist film
106a: exposed area 106b: unexposed area
108: photoresist pattern 112: organic film pattern
114: thin film pattern

Claims (10)

A composition for a semiconductor resist comprising an organometallic compound represented by the following Formula 1, and a solvent:
[Formula 1]

In Formula 1,
X ₁ to X ₂ are each independently a single bond, a substituted or unsubstituted C1 to C6 alkylene group, a substituted or unsubstituted phenylene group, -O-, -CO- ring, -NR _a - (R _a is hydrogen, substituted Or an unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group), and
Y ₁ to Y ₂ are each independently selected from hydrogen, a substituted or unsubstituted C1 to C6 alkyl group, and a substituted or unsubstituted phenyl group,
R ₁ to R ₄ are each independently hydrogen, a substituted or unsubstituted C1 to C6 alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted C1 to C6 alkenylene group, a substituted or unsubstituted C1 to C6 An alkynylene group, a substituted or unsubstituted C1 to C6 alkenyl alkyl group, a substituted or unsubstituted C1 to C6 alkynyl alkyl group, and
However, when R ₁ to R ₄ and Y ₁ to Y ₂ do not contain an unsaturated double bond, 2 or more of R ₁ , R ₂ , and Y ₁ and 2 or more of R ₃ , R ₄ and Y ₂ are each substituted Or it may be an unsubstituted C1 to C6 alkyl group,
2 ≤ n ≤ 100000. In claim 1,
In Formula 1,
Each of X ₁ to X ₂ is independently a single bond, a substituted or unsubstituted C1 to C6 alkylene group, a substituted or unsubstituted phenylene group, or a combination thereof. In claim 1,
In Formula 1,
R ₁ to R ₄ are each independently selected from hydrogen, a substituted or unsubstituted C1 to C6 alkyl group, a substituted or unsubstituted C1 to C6 alkenylene group, and a substituted or unsubstituted C1 to C6 alkenyl alkyl group, Composition for semiconductor resist. In claim 1,
The organometallic compound is represented by the following Formula 2, a composition for a semiconductor resist:
[Formula 2]

In Formula 2,
X ₃ to X ₄ are each independently a single bond, a substituted or unsubstituted C1 to C6 alkylene group, a substituted or unsubstituted phenylene group, -O-, -CO-, -NR _b- (R _b is hydrogen, substituted Or an unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group), and
Y ₃ to Y ₄ are each independently selected from hydrogen, a substituted or unsubstituted C1 to C6 alkyl group, and a substituted or unsubstituted phenyl group,
R ₅ to R ₈ are each independently selected from hydrogen, a substituted or unsubstituted C1 to C6 alkyl group, and a substituted or unsubstituted phenyl group,
2 ≤ n ≤ 100000. In claim 4,
In Chemical Formula 2,
X ₃ to X ₄ are each independently a single bond, one selected from a substituted or unsubstituted C1 to C6 alkylene group, a composition for a semiconductor resist. In claim 4,
In Chemical Formula 2,
At least one of R ₅ and R ₆ and at least one of R ₇ and R ₈ are each a substituted or unsubstituted C1 to C6 alkyl group. In claim 1,
The organometallic compound comprises at least one selected from compounds represented by the following Chemical Formulas 3 to 8, wherein the composition for a semiconductor resist.
[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

In Chemical Formulas 3 to 8,
2 ≤ n ≤ 100000. Forming a layer to be etched on the substrate;
Forming a photoresist film by applying the composition for a semiconductor resist according to any one of claims 1 to 7 on the etching target film;
Forming a photoresist pattern by patterning the photoresist film; And
And etching the target layer to be etched using the photoresist pattern as an etching mask. In clause 8,
The step of forming the photoresist pattern is a pattern forming method using light having a wavelength of 5 nm to 150 nm. In clause 8,
The step of forming the photoresist pattern includes removing a part of the photoresist film using 2-heptanone.

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