TWI643902B - Composition having high heat-and chemical-resistance and method for preparing protective thin film using same - Google Patents

Abstract

The invention relates to a composition comprising an aromatic compound with high heat resistance and chemical resistance, and a method for preparing a protective film using the composition. The protective film prepared from the composition of the present invention can maintain its physical shape without thermal deformation even when exposed to a high temperature of 300°C or higher, it exhibits excellent chemical resistance to acids, alkalis or organic solvents, and The shape of an exposed surface is maintained during the plasma treatment process, thereby effectively serving as a protective film for protecting a basic material.

Description

Composition with high heat resistance and chemical resistance and method for preparing protective film using the composition Field of invention

The invention relates to a composition comprising an aromatic compound with high heat resistance and chemical resistance, and a method for preparing a protective film using the composition. Specifically, the present invention relates to a composition for forming a protective film for preventing high heat, chemical exposure, etc. More specifically, it relates to a protective and selective chemistry for forming a basic material The composition of the protective film to be treated.

Background of the invention

Conventionally, most of the organic synthetic materials used to form a protective film, a dielectric material, or a protective film in a display device or semiconductor device are acrylic or amide-based compositions (see US 2010/0147564 A1 ). When applied to a device, the acrylic composition can be easily synthesized and exhibit excellent overall processability and coating performance. However, its properties have limitations such as heat resistance and chemical resistance. Although the imide-based composition exhibits excellent properties such as heat resistance and chemical resistance, its synthesis method And the manufacturing method is difficult, and because of its low solubility, it is limited in the choice of solvent.

Therefore, the present inventors have worked hard to find an excellent Aromatic compounds of heat, solubility and chemical resistance can be easily synthesized, and by using the aromatic compounds, a curable resin material suitable for forming a protective film, a dielectric material or a protective film can be obtained. Complete the present invention.

Summary of the invention

Therefore, an object of the present invention is to provide a composition having excellent heat resistance, solubility and chemical resistance. The composition can be used in semiconductor manufacturing methods. In particular, the composition may be a composition for forming a protective film.

Another object of the present invention is to provide a method of forming a protective film by using the composition.

Yet another object of the present invention is to provide a protective film obtained from the composition.

Yet another object of the present invention is to provide a semiconductor device including the composition.

Yet another object of the present invention is to provide a method for manufacturing the semiconductor device.

According to an aspect of the present invention, there is provided a composition comprising an aromatic compound, wherein the aromatic compound has at least one of the repeating unit of Formula 1 and the repeating unit of Formula 2:

Wherein, A is any one selected from the group consisting of formulas (a-1) to (a-4) represented by the following structural formulas: B is any one selected from the group consisting of formulas (b-1) to (b-8) represented by the following structural formulas: X is any one selected from the group consisting of formulas (c-1) to (c-3) represented by the following structural formulas: R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently hydrogen, hydroxyl, -OR (where R is C _1-10 alkyl or C _6-10 aryl), C _1-5 alkyl, C _6-10 aryl, nitrogen, -NR'R" (wherein R'and R" are each independently hydrogen or C _1-5 alkyl) or halogen.

According to another aspect of the present invention, it provides a method for preparing a protective film, which comprises coating the composition of the present invention on a substrate, followed by a heat treatment.

According to yet another aspect of the present invention, it provides a protective film obtained from the composition of the present invention.

According to yet another aspect of the present invention, it provides a semiconductor device including the composition of the present invention.

According to yet another aspect of the present invention, it provides a method for manufacturing a semiconductor device, which includes the following steps: (1) forming an etching target layer on a semiconductor substrate; (2) forming on the etching target layer A mask pattern; and (3) etching the target layer by using the mask pattern, wherein the mask pattern is obtained by the composition of the present invention.

A protective film obtained according to the composition of the present invention maintains its physical shape without thermal deformation even when exposed to a high temperature of 300°C or higher, and exhibits excellent chemical resistance to acids, alkalis or organic solvents , And maintain the shape of the exposed surface during the plasma treatment. Therefore, the protective film can be effectively used as a protective film for protecting a basic material.

100‧‧‧Semiconductor substrate

200‧‧‧Equipment

310‧‧‧The first interlayer dielectric film

320‧‧‧Second interlayer dielectric film

330‧‧‧Interlayer dielectric film

410‧‧‧First wiring layer

420‧‧‧Second wiring

500‧‧‧Target device pattern

501‧‧‧Etching target layer

600‧‧‧mask pattern

601‧‧‧ Mask layer

700‧‧‧Photoresist pattern

The above and other objects and features of the present invention will be apparent from the following description and accompanying drawings, which are shown: FIG. 1: a cross-sectional view illustrating that a semiconductor device includes an embodiment according to the present invention The obtained dielectric layer; and FIG. 2: a cross-sectional view illustrating a semiconductor device in each manufacturing method according to an embodiment of the present invention.

<Explanation of reference number>

100: semiconductor substrate,

200: device components,

310: The first interlayer dielectric film,

320: the second interlayer dielectric film,

330: The third interlayer dielectric film,

410: first wiring layer,

420: second wiring layer,

500: target device pattern,

501: Etching the target layer,

600: mask pattern,

601: Mask layer,

700: photoresist pattern

Detailed description of the preferred embodiment

The present invention provides a composition comprising an aromatic compound, wherein the aromatic compound has at least one of the repeating unit of Formula 1 and the repeating unit of Formula 2 as shown above. According to an embodiment of the present invention, the aromatic compound may include a repeating unit of Formula 1. According to another embodiment of the present invention, the aromatic compound may include a repeating unit of formula 1 and a formula 2 Of repeating units.

According to another embodiment of the present invention, the aromatic compound may include a repeating unit of formula 3:

Among them, A, B and X are the same as defined in the above formulas 1 and 2.

The aromatic compound may comprise an oligomer or a polymer of the above repeating units.

A substituent or a linker shown in formulas (a-1) to (a-4), formulas (b-1) to (b-8) and formulas (c-1) to (c-3) may be It is substituted or connected on any carbon that can replace or form a joint.

For example, formula (a-1) may include the following formulas (i) to (iv):

In formulas 1 and 3, A is selected from any one of the groups consisting of the above formulas (a-1) to (a-4). According to an embodiment, A is formula (a-1) or (a-2). According to another embodiment, A is formula (a-1).

In formulae (a-1) to (a-4), R ₁ and R ₂ are each independently hydrogen, hydroxyl, -OR (where R is C _1-10 alkyl or C _6-10 aryl), C _1-5 alkyl, C _6-10 aryl, nitrogen, -NR'R" (wherein R'and R" are each independently hydrogen or C _1-5 alkyl) or halogen. According to an embodiment, R ₁ and R ₂ are each independently hydrogen, hydroxyl, or -OR (wherein R is C _1-10 alkyl or C _6-10 aryl). According to another embodiment, R ₁ is hydrogen, hydroxyl or -OCH ₃ ; R ₂ is hydrogen, hydroxyl, -NH ₂ or -OCH ₃ . According to yet another embodiment, R ₁ and R ₂ are each independently hydrogen or hydroxyl. According to yet another embodiment, R ₁ and R ₂ are each independently hydroxyl.

In Formulas 2 and 3, B is selected from any one of the groups consisting of the above formulas (b-1) to (b-8). According to an embodiment, B is any one selected from the group consisting of formulas (b-1), (b-5), (b-6), (b-7) and (b-8) By. According to another embodiment, B is selected from any one of the group consisting of formulas (b-1), (b-2), (b-3) and (b-4).

In formulas (b-1) to (b-8), R ₃ and R ₄ are each independently hydrogen, hydroxyl, -OR (wherein R is C _1-10 alkyl or C _6-10 aryl), C _1-5 alkyl, C _6-10 aryl, nitrogen, -NR'R" (wherein R'and R" are each independently hydrogen or C _1-5 alkyl) or halogen. According to an embodiment, R ₃ and R ₄ are each independently hydrogen or hydroxyl.

In formulae 1 to 3, X is selected from any one of the group consisting of the above formulae (c-1) to (c-3). According to an embodiment, X is formula (c-1).

In formulas (c-1) to (c-3), R ₅ is hydrogen, hydroxyl, -OR (where R is C _1-10 alkyl or C _6-10 aryl), C _1-5 alkyl, C _6-10 aryl, nitrogen, -NR'R" (wherein R'and R" are each independently hydrogen or C _1-5 alkyl) or halogen. According to an embodiment, R ₅ is hydrogen or hydroxyl. According to another embodiment, R ₅ is hydrogen.

The aromatic compound may include a repeating unit (Ra) of Formula 1 and a repeating unit (Rb) of Formula 2, wherein the molar ratio (Ra:Rb) is 0.01:0.99 to 0.99:0.01. According to an embodiment, the molar ratio of the repeating units (Ra: Rb) may be 0.1:0.9 to 0.9:0.1. According to another embodiment, the molar ratio (Ra:Rb) of the repeating units may be 0.4:0.6 to 0.6:0.4. According to yet another embodiment, the molar ratio (Ra:Rb) of the repeating units may be 0.5:0.5.

Under conventional reaction conditions, the aromatic compound can be obtained by combining a compound containing a part A and/or a compound containing a part B with 1,3,5- , 1,4-bismethoxymethylbenzene or benzaldehyde is obtained by a coupling reaction in an organic solvent, and preferably an acid (for example, toluenesulfonic acid) can be added. During the above-mentioned coupling reaction, due to the characteristics of the aromatic moiety, a bond (linkage) can be formed at multiple carbon positions in the A part and/or the B part.

The aromatic compound may have a weight average of 1,000 to 50,000 The average molecular weight is, for example, 1,000 to 20,000, more specifically, 1,000 to 10,000.

The aromatic compound is not only due to high heat of 350℃ or higher The conditions show a residue amount (wt%) of at least 93% while exhibiting excellent heat resistance, also exhibiting excellent solubility and being completely dissolved in various organic solvents (see Experimental Examples 1 and 2).

In addition to the aromatic compound, the composition of the present invention can be One step contains one selected from cyclohexanone, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), ethyl lactate, γ-butyrolactone (GBL), N-methyl-1, 2-Pyrrolidone (NMP), chloroform, toluene and mixtures of solvents.

Based on the total weight of the composition, the composition of the present invention may contain The aromatic composition with a content of 0.1 to 30 wt% and a solvent with a content of 70 to 99.9 wt%.

Further, the present invention provides a method for preparing a protective film The method includes coating the composition on a substrate, followed by a heat treatment.

Any conventional coating method known in this art, for example, Spin coating, slot coating, bar coating or spray coating can be used in the method for preparing a protective film.

The thickness of the coating or the conditions for heat treatment of the composition are not Specific restrictions. However, the composition can be coated on a substrate with a thickness of 10 nm to 5 μm, and then subjected to heat treatment at a temperature of 200°C to 600°C, preferably at 240°C to 400°C for 1 to 5 minutes to obtain A protective film.

The protective film prepared by this may have a thickness of 5nm to 5,000nm Degree, preferably 10 nm to 3,000 nm, more preferably 50 nm to 500 nm.

According to an embodiment of the present invention, the composition of the present invention can be borrowed It is coated by a spin method and can be heat-treated at 350°C for 2 minutes, thereby forming a protective film having a thickness of about 350 nm.

Further, the present invention provides a warranty obtained from the composition Protect film.

According to an embodiment of the present invention, by the composition of the present invention The obtained protective film can sufficiently maintain its overall physical shape. In addition, the film exhibits excellent chemical resistance, so the film and its thickness will not change even after exposure to acids, alkalis, organic solvents, etc.; and even during a plasma etching process (when exposed to plasma ) Presents a slow degradation and undesirable phenomena such as cracking and peeling of the film after the etching process can be avoided (see Experimental Examples 3 to 5).

Therefore, the protective film of the present invention can be used in the metal assembly of the machine Surface treatment, filling materials for electronic products, and a protective film used in a display device or semiconductor manufacturing process. More specifically, the protective film can be used in a method for preparing a flat screen display device or a semiconductor device as a protective film for planarization, a protective material, a dielectric material, a dielectric film or A mask for selective treatment of a basic layer.

Further, the present invention provides a warranty obtained from the composition A protective film, specifically, a semiconductor device including the protective film.

Specifically, the present invention provides a semiconductor device including a package A dielectric film containing an aromatic compound, wherein the aromatic compound has at least one repeating unit of Formula 1 and a repeating unit of Formula 2 (wherein A, B, and X in Formulas 1 and 2 are the same as defined above).

More specifically, referring to FIG. 1, a semiconductor according to an embodiment The device may include a semiconductor substrate (100), a device element (200), an interlayer dielectric layer (310, 320, and 330) and a wiring layer (410 and 420).

The semiconductor substrate (100) may be a silicon substrate. The semiconductor base The board (100) may include a dielectric layer such as a silicon monoxide layer.

The device element (200) is formed on the semiconductor substrate (100) of. The device element may be a transistor, an image sensor or a capacitor.

Interlayer dielectric films (310, 320 and 330) are attached to the semiconductor substrate (100). For example, the first interlayer dielectric film (310) is formed on the semiconductor substrate (100). The first interlayer dielectric film (310) is placed on the device element (200).

In addition, the second interlayer dielectric film (320) is attached to the first interlayer dielectric Formed on the electrical film (310). The second interlayer dielectric film (320) is placed on the first wiring layer (410).

The third interlayer dielectric film (330) is attached to the second interlayer dielectric film (320). The third interlayer dielectric film (330) is placed on the second wiring layer (420).

The first wiring layer (410) is placed on the first interlayer dielectric film (310) above. The first wiring layer (410) is connected to the device element (200).

The second wiring layer (420) is placed on the second interlayer dielectric film (320) above. The second wiring layer (420) is connected to the device element (200) and/or the first wiring layer (410).

The first interlayer dielectric film (310) and the second interlayer dielectric film (320) And the third interlayer dielectric film (330) may include a composition according to the above embodiments or the embodiments to be described below.

More specifically, in order to form the first interlayer dielectric film (310), The device element (200) is formed on the semiconductor substrate (100), and then the composition according to the embodiments of the present invention is coated thereon. The composition can be applied by using conventional coating methods such as spin coating, slit coating, bar coating, and spray coating.

Then, the composition coated thereby is cured by a heat treatment method or the like to form the first interlayer dielectric film (310). ’

In a similar manner, the second interlayer dielectric film (320) and the third interlayer dielectric film (330) can be formed.

Further, the present invention provides a method for preparing a semiconductor device The method includes the following steps: forming an etching target layer on a semiconductor substrate; forming a mask pattern layer on the etching target layer; and etching the etching target layer by using the mask pattern layer, wherein the The mask pattern layer includes a composition according to the present invention, that is, a composition including an aromatic compound, wherein the aromatic compound has at least one repeating unit of Formula 1 and a repeating unit of Formula 2 (wherein Formulas 1 and 2 A, B and X are the same as defined above).

As illustrated in FIG. 2, a semiconductor device can be used by using a Prepared according to the embodiments of the present invention.

Referring to FIG. 2(a), an etching target layer (501) is attached to a semiconductor Formed on the substrate (100). The etching target layer (501) may be a metal layer or a silicon layer.

Referring to FIG. 2(b), a photomask layer (601) is attached to the etch target layer (501). The photomask layer (601) may include a composition according to the embodiments of the present invention. More specifically, the composition is coated on the etch target layer (501). Then, the composition coated thereby is cured, and the mask layer is formed.

Referring to (c) of FIG. 2, a photoresist layer is formed on the photomask layer (601) The photoresist layer is subjected to an exposure process and a development process. Therefore, the photoresist pattern (700) is formed on the photomask layer (601).

Referring to (d) of FIG. 2, through the photoresist pattern (700), a pattern is Formed on the mask layer (601). Therefore, a mask pattern (600) is formed.

Referring to (e) of FIG. 2, through the mask pattern (600), the etching target The layer (501) is etched, and the target device pattern (500) is formed on the semiconductor substrate (100).

2 (f), the mask pattern (600) and the photoresist pattern (700) was removed. Then, an additional layer may be formed on the target device pattern (500) to form a semiconductor device.

Therefore, the mask pattern is obtained by using the The composition of the embodiment is formed, and the semiconductor device is formed through the mask pattern.

In the following, the present invention will be described more specifically by the following examples Bright. However, these embodiments are for illustrative purposes only, and the present invention is not limited thereto.

Example I-1: Synthesis of aromatic compounds for protecting films

A 500mL round bottom three-necked flask is equipped with a thermometer, condenser, The dropping funnel was placed in a constant temperature oil bath at 120°C. The oil bath was placed on a hot plate and a magnetic stirrer for stirring was introduced. The temperature of the cooling water of the condenser is maintained at 10°C.

In the three-necked flask, 63.0 g of 1,1'-bi-2-naphthol (0.22 mol) and 25.8 g of 1,3,5- (0.286 mol) was dissolved in 212 g of cyclohexanone as a solvent. Next, 2.1 g of p-toluenesulfonic acid monohydrate (11 mmol) was added thereto, and the mixture was stirred for 12 hours to perform a reaction. The reaction temperature is maintained at 120°C.

During the reaction, sample the reaction mixture and measure the The weight average molecular weight of the sample. When the weight average molecular weight reaches a desired level, the reaction is terminated by slowly cooling the reactant at room temperature.

Prepare a 600 g of n-hexane and B at a weight ratio of 80:20 A mixed solution of alcohol, and the reactant obtained above was added dropwise to the solution with stirring. A supernatant formed from the reaction was discarded, and a polymer polymer formed at the bottom of the flask was separated. Next, the polymer was dried in a vacuum oven at 80°C for 24 hours to exclude remaining solvents and impurities, and thus a powdery aromatic compound was obtained.

Permeate the layer through the gel under the condition of tetrahydrofuran (THF) solvent GPC analysis of the aromatic compound thus obtained, and the results showed that the aromatic compound had a weight average molecular weight of 3,500 and a polydispersity index (weight distribution) of 1.9.

Example I-2: Synthesis of aromatic compounds for protecting films

An aromatic compound was prepared by using the same method as in Example I-1, except that 63.0 g of 2,2′-dimethoxy-1,1′-binaphthalene (0.2 mol) was used instead of 63.0 g of 1 , 1'-bi-2-naphthol (0.22mol).

The aromatic compound thus obtained was analyzed by GPC under the condition of THF, and the result showed that the aromatic compound had a weight average molecular weight of 2,200 and a polydispersity index (weight distribution) of 2.1.

Example I-3: Synthesis of aromatic compounds for protecting films

An aromatic compound was prepared by using the same method as Example I-1, except that 62.8 g of 2-amino-2′-hydroxy-1,1′-binaphthalene (0.22 mol) was used instead of 63.0 g of 1, 1'-Bi-2-naphthol (0.22mol).

The aromatic compound thus obtained was analyzed by GPC under the condition of THF, and the results showed that the aromatic compound had a weight average molecular weight of 1,900 and a polydispersity index (weight distribution) of 2.2.

Example I-4: Synthesis of aromatic compounds for protecting films

A 500mL round bottom three-necked flask is equipped with a thermometer, condenser, The dropping funnel was placed in a constant temperature oil bath at 140°C. The oil bath was placed on a hot plate and a magnetic stirrer for stirring was introduced. The temperature of the cooling water of the condenser is maintained at 10°C.

In the three-necked flask, 65.7 grams of 2,2'-dihydroxy-1,1'-bianthracene (0.17mol) and 19.9 grams of 1,3,5- (0.22 mol) was dissolved in 207 g of cyclohexanone as a solvent. Next, 3.23 g of p-toluenesulfonic acid monohydrate (17 mmol) was added thereto, and the mixture was stirred for 24 hours to perform a reaction. The reaction temperature was maintained at 140°C.

During the reaction, sample the reaction mixture and measure the The weight average molecular weight of the sample. When the weight average molecular weight reaches a desired level, the reaction is terminated by slowly cooling the reactant at room temperature.

Prepare a 600 g of n-hexane and B at a weight ratio of 80:20 A mixed solution of alcohol, and the reactant obtained above was added dropwise to the solution with stirring. A supernatant formed from the reaction was discarded, and a polymer polymer formed at the bottom of the flask was separated. Next, the polymer was dried in a vacuum oven at 80°C for 24 hours to exclude remaining solvents and impurities, and thus a powdery aromatic compound was obtained.

The aromatics obtained by GPC analysis under THF Aromatic compounds, and the results show that the aromatic compounds have a weight average molecular weight of 1,700 and a polydispersity index (weight distribution) of 2.4.

Example II-1: Synthesis of aromatic compounds for protecting films

A 500mL round bottom three-necked flask is equipped with a thermometer, condenser, The dropping funnel was placed in a constant temperature oil bath at 120°C. The oil bath was placed on a hot plate and a magnetic stirrer for stirring was introduced. The temperature of the cooling water of the condenser is maintained at 10°C.

In the three-necked flask, 43.0 g of 1,1′-bi-2-naphthol (0.15 mol), 14.1 g of phenol (0.15 mol) and 35.1 g of 1,3,5- (0.39 mol) was dissolved in 222 g of cyclohexanone as a solvent. Next, 2.85 g of p-toluenesulfonic acid monohydrate (15 mmol) was added thereto, and the mixture was stirred for 12 hours to perform a reaction. The reaction temperature is maintained at 120°C.

During the reaction, sample the reaction mixture and measure the The weight average molecular weight of the sample. When the weight average molecular weight reaches a desired level, the reaction is terminated by slowly cooling the reactant at room temperature.

Prepare a 600 g of n-hexane and B at a weight ratio of 80:20 A mixed solution of alcohol, and the reactant obtained above was added dropwise to the solution with stirring. A supernatant formed from the reaction was discarded, and a polymer polymer formed at the bottom of the flask was separated. Next, the polymer was dried in a vacuum oven at 80°C for 24 hours to exclude remaining solvents and impurities, and thus a powdery aromatic compound was obtained.

The aromatics obtained by GPC analysis under THF Aromatic compound, and the results show that the aromatic compound has a weight average molecular weight of 5,500 and a polydispersity index (weight distribution) of 1.8.

Example II-2: Synthesis of aromatic compounds for protecting films

A 500mL round bottom three-necked flask is equipped with a thermometer, condenser, The dropping funnel was placed in a 150°C constant temperature oil bath. The oil bath was placed on a hot plate and a magnetic stirrer for stirring was introduced. The temperature of the cooling water of the condenser is maintained at 10°C.

In this three-necked flask, 43.0 g of 1,1'-bi-2-naphthol (0.15 mol), 29.1 g of 2-hydroxyanthracene (0.15 mol) and 35.1 g of 1,3,5- (0.39 mol) was dissolved in 263 g of cyclohexanone as a solvent. Next, 5.7 g of p-toluenesulfonic acid monohydrate (30 mmol) was added thereto, and the mixture was stirred for 20 hours to perform a reaction. The reaction temperature is maintained at 150°C.

During the reaction, sample the reaction mixture and measure the The weight average molecular weight of the sample. When the weight average molecular weight reaches a desired level, the reaction is terminated by slowly cooling the reactant at room temperature.

Prepare a 600 g of n-hexane and B at a weight ratio of 80:20 A mixed solution of alcohol, and the reactant obtained above was added dropwise to the solution with stirring. A supernatant formed from the reaction was discarded, and a polymer polymer formed at the bottom of the flask was separated. Next, the polymer was dried in a vacuum oven at 80°C for 24 hours to exclude remaining solvents and impurities, and thus a powdery aromatic compound was obtained.

The aromatics obtained by GPC analysis under THF Aromatic compounds, and the results show that the aromatic compounds have a weight average molecular weight of 2,300 and a polydispersity index (weight distribution) of 2.1.

Example II-3: Synthesis of aromatic compounds for protecting films

An aromatic compound is obtained by using the same method of Example II-2 Prepared by the method, except for the use of 25.2 g of 4-hydroxyvinylnaphthalene (0.15 mole) Instead of 29.1 g of 2-hydroxyanthracene (0.15 mol).

The aromatics obtained by GPC analysis under THF Aromatic compound, and the results show that the aromatic compound has a weight average molecular weight of 2,800 and a polydispersity index (weight distribution) of 2.0.

Example II-4: Synthesis of aromatic compounds for protecting films

An aromatic compound is obtained by using the same method of Example II-2 Prepared by the method, except that 27.3 g of 3-hydroxystilbene (0.15 mol) was used instead of 29.1 g of 2-hydroxyanthracene (0.15 mol).

The aromatics obtained by GPC analysis under THF Aromatic compounds, and the results show that the aromatic compounds have a weight average molecular weight of 2,100 and a polydispersity index (weight distribution) of 2.3.

Example II-5: Synthesis of aromatic compounds for protecting films

An aromatic compound is obtained by using the same method of Example II-1 Prepared by the method, except that 30.3 g of pyrene (0.15 mol) was used instead of 14.1 g of phenol (0.15 mol).

The aromatics obtained by GPC analysis under THF Aromatic compounds, and the results show that the aromatic compound has a weight average molecular weight of 3,200 and a polydispersity index (weight distribution) of 1.9.

Example III-1: Synthesis of aromatic compounds for protecting films

A 500mL round bottom three-necked flask is equipped with a thermometer, condenser, The dropping funnel was placed in a constant temperature oil bath at 100°C. The oil bath was placed on a hot plate and a magnetic stirrer for stirring was introduced. The temperature of the cooling water of the condenser is maintained at 10°C.

In the three-necked flask, 71.6 g of 1,1′-bi-2-naphthol (0.25 mol), 8.3 g of hydroquinone (0.075 mol) and 40.5 g of 1,3,5- (0.45 mol) was dissolved in 128 g of cyclohexanone as a solvent. Next, 7.1 g of p-toluenesulfonic acid monohydrate (38 mmol) was added thereto, and the mixture was stirred to perform a reaction. The reaction temperature is maintained at 100°C.

During the reaction, sample the reaction mixture and measure the The weight average molecular weight of the sample. When the weight average molecular weight reaches a desired level, the reaction is terminated by slowly cooling the reactant at room temperature.

Prepare an 800 g of n-hexane and B at a weight ratio of 80:20 A mixed solution of alcohol, and the reactant obtained above was added dropwise to the solution with stirring. A supernatant formed from the reaction was discarded, and a polymer polymer formed at the bottom of the flask was separated. Next, the polymer It was dried in a vacuum oven at 80° C. for 24 hours to exclude remaining solvents and impurities, and thus a powdery aromatic compound was obtained.

The aromatics obtained by GPC analysis under THF Aromatic compounds, and the results show that the aromatic compounds have a weight average molecular weight of 4,300 and a polydispersity index (weight distribution) of 1.9.

Example III-2: Synthesis of aromatic compounds for protecting films

A 500mL round bottom three-necked flask is equipped with a thermometer, condenser, The dropping funnel was placed in a constant temperature oil bath at 130°C. The oil bath was placed on a hot plate and a magnetic stirrer for stirring was introduced. The temperature of the cooling water of the condenser is maintained at 10°C.

In the three-necked flask, 71.6 g of 1,1′-bi-2-naphthol (0.25 mol), 18.0 g of 1-naphthol (0.125 mol) and 40.5 g of 1,3,5- (0.45 mol) was dissolved in 137 g of cyclohexanone as a solvent. Next, 7.1 g of p-toluenesulfonic acid monohydrate (38 mmol) was added thereto, and the mixture was stirred to perform a reaction. The reaction temperature is maintained at 130°C.

During the reaction, sample the reaction mixture and measure the The weight average molecular weight of the sample. When the weight average molecular weight reaches a desired level, the reaction is terminated by slowly cooling the reactant at room temperature.

Prepare an 800 g of n-hexane and B at a weight ratio of 80:20 A mixed solution of alcohol, and the reactant obtained above was added dropwise to the solution with stirring. A supernatant formed from the reaction was discarded, and a polymer polymer formed at the bottom of the flask was separated. Next, the polymer was dried in a vacuum oven at 80°C for 24 hours to exclude remaining solvents and impurities, and thus a powdery aromatic compound was obtained.

The aromatic compound thus obtained was analyzed by GPC under the condition of THF, and the result showed that the aromatic compound had a weight average molecular weight of 7,400 and a polydispersity index (weight distribution) of 2.1.

Example III-3: Synthesis of aromatic compounds for protecting films

An aromatic compound was prepared by using the same method as Example III-2, except that 43.8 g of 9,9-bis(4-hydroxybenzene) stilbene (0.125 mol) was used instead of 18.0 g of 1-naphthol (0.125 mol).

The aromatic compound thus obtained was analyzed by GPC under the condition of THF, and the result showed that the aromatic compound had a weight average molecular weight of 5,800 and a polydispersity index (weight distribution) of 2.1.

Example III-4: Synthesis of aromatic compounds for protecting films

An aromatic compound is the same as in Example III-2 Prepared by the method, except that 56.3 grams of 6,6'-(9hydro-fusel-9,9-diyl)bis(2-naphthol) (0.125mol) is used instead of 18.0 grams of 1-naphthol (0.125mol) .

The aromatics obtained by GPC analysis under THF Aromatic compound, and the results show that the aromatic compound has a weight average molecular weight of 5,100 and a polydispersity index (weight distribution) of 2.3.

Example III-5: Synthesis of aromatic compounds for protecting films

An aromatic compound was prepared by using the same method of Example III-2, except that 83.1 g of 1,4-bis(methoxymethyl)benzene (0.50 mol) was used instead of 40.5 g of 1,3,5 - (0.45mol).

The aromatics obtained by GPC analysis under THF Aromatic compounds, and the results show that the aromatic compounds have a weight average molecular weight of 3,800 and a polydispersity index (weight distribution) of 1.9.

Example III-6: Synthesis of aromatic compounds for protecting films

An aromatic compound was prepared by using the same method as Example III-2, except that 53.1 g of benzaldehyde (0.50 mol) was used instead of 40.5 g of 1,3,5- (0.45mol).

The aromatics obtained by GPC analysis under THF Aromatic compound, and the results show that the aromatic compound has a weight average molecular weight of 3,200 and a polydispersity index (weight distribution) of 2.0.

Comparative Example I: Synthesis of aromatic compounds used to protect films

An aromatic compound for protecting the film is prepared according to the method disclosed in US Patent Application Publication No. 2010/0147564 A1. Specifically, 3,4'-oxodiphenylamine (3 mmol) and a stirrer were placed in a sufficiently dry and sealed reactor, and dissolved in 7.3 mL of dehydrated N-methyl-1,2-pyrrolidone ( NMP). Next, 1,2,3,5-pyromellitic dianhydride powder (3 mmol) was added to the solution. The mixture thus obtained was stirred at room temperature for 3 hours to obtain a transparent, uniform and viscous linear polyimide precursor solution. The linear polyimide precursor solution was appropriately diluted to a concentration of 10 to 20 wt%, and 10 mL of cyclodehydration reagent (acetic anhydride/pyridine=7/3 volume) was added dropwise, and stirred at room temperature 12 hours for amide imidization. The polyimide solution thus obtained was added dropwise to a large amount of methanol, and then the polyimide precipitate was collected and dried to obtain a powdery polyimide.

Comparative Example II: Synthesis of aromatic compounds used to protect films film

Polyimide powder was prepared by using the same method of Comparative Example I, except that a diamine component 2,2-bis(4-(4-aminophenoxy)phenyl)propane (BAPP) And 4,4'-oxodiphenylamine (4,4'-ODA) instead of 3,4'-oxodiphenylamine, where the molar ratio is 70:30 (BAPP: 4,4'-ODA).

Experimental Example 1: Evaluation of heat resistance

Weigh 20 mg of each aromatic compound prepared in the examples and the comparative examples, and evaluate the resistance of the compound by using a thermogravimetric analyzer instrument (TF-DTA2000, Bruker AXS Inc.) Hot. The compounds were heated at a rate of 10°C/min and in the presence of nitrogen, and the weight change of each compound was measured. These results are presented in Table 1.

As shown in Table 1, the aromatic compounds of these examples have a residual weight of at least 93% at a temperature of 350° C. or higher, thereby exhibiting excellent heat resistance.

Experimental Example 2: Solubility evaluation

Place 0.5g in these examples and these comparative examples Each of the prepared aromatic compounds was in a variety of solvents of 5 g each, and the solubility of each aromatic compound was analyzed at room temperature. In this test, γ-butyrolactone (GBL), tetrahydrofuran, cyclohexanone (CH), CP mixture (monocyclohexanone: PGMEA=50:50 mixture, w/w), and propylene glycol monomethyl ether acetic acid Ester (PGMEA) is used as these solvents. These results are presented in Table 2.

As shown in Table 2, the aromatic compounds prepared in the examples of the present invention exhibit good solubility in most solvents, The aromatic compounds of Comparative Examples I and II exhibit poor solubility.

Experimental Example 3: Film formation

0.5 g of each aromatic compound prepared in these examples was dissolved in 4.5 g of cyclohexanone to prepare a sample solution (a composition for protecting the film). Each prepared sample solution was applied to an 8-inch silicon wafer by spin coating, and the silicon wafer was dried at 350°C for 2 minutes to form a thin film with a thickness of 300 nm.

In addition, by using the same method as described above to prepare a thin film, except that the aromatic compound powder prepared in the comparative examples was dissolved in NMP instead of cyclohexanone. These results are presented in Table 3.

As shown in Table 3, including the aromatic compounds of the present invention The compositions exhibit a good film shape, however, the compositions including the aromatic compounds of Comparative Examples I and II have defects such as edge shrinkage.

Experimental Example 4: Evaluation of chemical resistance of thin films

The film samples prepared by using the aromatic compounds of the examples and the comparative examples in Experimental Example 3 were immersed in an aqueous HCl solution (HCl: water=15:85wt%) at room temperature ), a NaOH aqueous solution (NaOH: water=15:85wt%), cyclohexanone and propylene glycol monomethyl ether acetate for 2 minutes, and then evaluate the resistance of these samples by checking the changes in the shape and thickness of the films Chemical. These results are presented in Table 4.

As shown in Table 4, the thin film samples prepared from the aromatic compounds of the present invention did not show changes in the shape or thickness of the film, thereby exhibiting good chemical resistance.

Experimental Example 5: Evaluation of film shape after etching

The thin film samples prepared by using the aromatic compounds of the examples and the comparative examples in Experimental Example 3 were subjected to plasma by using a CH ₂ F ₂ /CF ₄ mixture Etching, and measuring the degradation rate (film loss rate) of these thin films. In addition, evaluate any changes in the shape of the films (for example, cracking or peeling of the film, etc.). These results are presented in Table 5.

As shown in Table 5, compared with those of these comparative examples, by The thin film samples prepared by using the aromatic compounds according to the embodiments exhibited a slower etching rate and maintained a good shape after the etching process without any defects such as cracking and peeling of the thin film. Based on the above results, a composition prepared from the aromatic compound of the present invention can be effectively used as a protective film or a photomask for a basic material in a plasma-application process.

Claims (18)

A composition comprising an aromatic compound, wherein the aromatic compound has at least one of the repeating unit of Formula 1 and the repeating unit of Formula 2:

Wherein, A is any one selected from the group consisting of formulas (a-1) to (a-4) represented by the following structural formulas:

B is any one selected from the group consisting of formulas (b-1) to (b-8) represented by the following structural formulas:

X is any one selected from the group consisting of formulas (c-2) and (c-3) represented by the following structural formulas:

R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently hydrogen, hydroxyl, -OR (where R is C _1-10 alkyl or C _6-10 aryl), C _1-5 alkyl, C _6-10 aryl, nitrogen, -NR'R" (wherein R'and R" are each independently hydrogen or C _1-5 alkyl) or halogen, wherein the aromatic compound contains a repeating unit of Formula 1. The composition of claim 1, wherein A is formula (a-1) or (a-2). As in the composition of claim 2, wherein A is formula (a-1). The composition of claim 1, wherein the aromatic compound comprises a repeating unit (Ra) of Formula 1 and a repeating unit (Rb) of Formula 2, wherein the molar ratio (Ra:Rb) is 0.01:0.99 to 0.99:0.01 . The composition of claim 4, wherein the molar ratio (Ra:Rb) of the repeating unit (Ra) of the formula 1 and the repeating unit (Rb) of the formula 2 is in the range of 0.4:0.6 to 0.6:0.4. The composition of claim 1, wherein B is selected from the group consisting of formulas (b-1), (b-5), (b-6), (b-7) and (b-8) . The composition of claim 1, wherein B is selected from the group consisting of formulas (b-1), (b-2), (b-3) and (b-4). The composition of claim 4, wherein the aromatic compound comprises a repeating unit of formula 3:

Among them, A, B and X are the same as defined in claim 1. The composition of claim 1, wherein R ₁ and R ₂ are each independently hydrogen, hydroxyl, or -OR (wherein R is C _1-10 alkyl or C _6-10 aryl). The composition of claim 1, wherein R ₁ is hydrogen, hydroxyl or -OCH ₃ ; R ₂ is hydrogen, hydroxyl, -NH ₂ or -OCH ₃ ; and R ₃ , R ₄ and R ₅ are each independently hydrogen or Hydroxyl. The composition of claim 10, wherein R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently hydrogen or hydroxyl. The composition of claim 1, wherein the aromatic compound has a weight average molecular weight of 1,000 to 50,000. The composition of claim 1, wherein the composition may further comprise a member selected from cyclohexanone, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), ethyl lactate, γ- A solvent consisting of butyrolactone (GBL), N-methyl-1,2-pyrrolidone (NMP), chloroform, toluene and mixtures thereof. The composition of claim 13, wherein the composition contains the aromatic compound in a content of 0.1 to 30% by weight and a solvent in a content of 70 to 99.9% by weight based on the total weight of the composition. A method for preparing a protective film, which comprises applying the composition of any one of claims 1 to 14 on a substrate, followed by a heat treatment. A protective film obtained from the composition of any one of claims 1 to 14. A semiconductor device including a dielectric layer obtained from the composition of any one of claims 1 to 14. A method for preparing a semiconductor device, comprising the steps of: forming an etching target layer on a semiconductor substrate; forming a mask pattern on the etching target layer; and etching the etching target by using the mask pattern Layer, wherein the mask pattern is obtained from the composition of any one of claims 1 to 14.